WO2020111022A1 - エチレン性不飽和樹脂組成物、及び感光性樹脂組成物 - Google Patents
エチレン性不飽和樹脂組成物、及び感光性樹脂組成物 Download PDFInfo
- Publication number
- WO2020111022A1 WO2020111022A1 PCT/JP2019/046060 JP2019046060W WO2020111022A1 WO 2020111022 A1 WO2020111022 A1 WO 2020111022A1 JP 2019046060 W JP2019046060 W JP 2019046060W WO 2020111022 A1 WO2020111022 A1 WO 2020111022A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethylenically unsaturated
- group
- resin
- resin composition
- unsaturated resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 123
- 229920005989 resin Polymers 0.000 claims abstract description 239
- 239000011347 resin Substances 0.000 claims abstract description 239
- 239000002904 solvent Substances 0.000 claims abstract description 90
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 48
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 43
- 239000003112 inhibitor Substances 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 28
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 119
- 150000001875 compounds Chemical class 0.000 claims description 116
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- 239000003822 epoxy resin Substances 0.000 claims description 57
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- 150000007519 polyprotic acids Polymers 0.000 claims description 55
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 238000007142 ring opening reaction Methods 0.000 claims description 26
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 22
- 239000003086 colorant Substances 0.000 claims description 22
- 239000003085 diluting agent Substances 0.000 claims description 22
- 150000002430 hydrocarbons Chemical group 0.000 claims description 22
- 239000000049 pigment Substances 0.000 claims description 22
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 13
- 239000000975 dye Substances 0.000 claims description 13
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- 235000010290 biphenyl Nutrition 0.000 claims description 12
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
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- 125000003118 aryl group Chemical group 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
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- 229930195733 hydrocarbon Natural products 0.000 description 9
- 238000005979 thermal decomposition reaction Methods 0.000 description 9
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- 230000001965 increasing effect Effects 0.000 description 8
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- 238000001879 gelation Methods 0.000 description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
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- 238000011161 development Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 4
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 4
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
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- 229910052746 lanthanum Inorganic materials 0.000 description 1
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- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 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
- 238000000691 measurement method Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- YSGBMDFJWFIEDF-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbutanoate Chemical compound COC(=O)C(O)C(C)C YSGBMDFJWFIEDF-UHFFFAOYSA-N 0.000 description 1
- PPIQQNDMGXNRFA-UHFFFAOYSA-N methyl 2-phenylbutanoate Chemical compound COC(=O)C(CC)C1=CC=CC=C1 PPIQQNDMGXNRFA-UHFFFAOYSA-N 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- NRMSDBSOGLOCJI-UHFFFAOYSA-N n-(4-ethenylphenyl)acetamide Chemical compound CC(=O)NC1=CC=C(C=C)C=C1 NRMSDBSOGLOCJI-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- JMXROTHPANUTOJ-UHFFFAOYSA-H naphthol green b Chemical compound [Na+].[Na+].[Na+].[Fe+3].C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21 JMXROTHPANUTOJ-UHFFFAOYSA-H 0.000 description 1
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- WNBDFALPKHFDJO-UHFFFAOYSA-N pentadec-3-ene Chemical compound CCCCCCCCCCCC=CCC WNBDFALPKHFDJO-UHFFFAOYSA-N 0.000 description 1
- IYDCZCBVYAESDR-UHFFFAOYSA-N pentadec-4-ene Chemical compound CCCCCCCCCCC=CCCC IYDCZCBVYAESDR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 235000012739 red 2G Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- COEZWFYORILMOM-UHFFFAOYSA-M sodium 4-[(2,4-dihydroxyphenyl)diazenyl]benzenesulfonate Chemical compound [Na+].OC1=CC(O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 COEZWFYORILMOM-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AXMCIYLNKNGNOT-UHFFFAOYSA-M sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfonatophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 AXMCIYLNKNGNOT-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- JOHIXGUTSXXADV-UHFFFAOYSA-N undec-2-ene Chemical compound CCCCCCCCC=CC JOHIXGUTSXXADV-UHFFFAOYSA-N 0.000 description 1
- NVPYPLODXLUCNR-UHFFFAOYSA-N undec-3-ene Chemical compound [CH2]CCCCCCC=CCC NVPYPLODXLUCNR-UHFFFAOYSA-N 0.000 description 1
- BQGFQLZEZOPJFT-UHFFFAOYSA-N undec-4-ene Chemical compound [CH2]CCC=CCCCCCC BQGFQLZEZOPJFT-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Definitions
- the present invention relates to an ethylenically unsaturated resin composition and a photosensitive resin composition.
- the present application claims priority based on Japanese Patent Application No. 2018-222730 filed in Japan on November 28, 2018, and the content thereof is incorporated herein.
- Acrylic resins are used in various fields due to their excellent transparency, weather resistance, and well-balanced mechanical properties. Recently, it is disclosed that a photosensitive resin composition including a resin having an ethylenically unsaturated group is used to form a black column spacer or the like as a member for a display through a coating/exposure/development process.
- Patent Document 1 As a method of introducing an ethylenically unsaturated group into a resin, a method of reacting a resin containing an epoxy group with an ethylenically unsaturated compound containing a carboxy group in the presence of a polymerization inhibitor and a catalyst is disclosed.
- the present invention has been made to solve the above problems, and an ethylenically unsaturated resin composition can be obtained by efficiently synthesizing even with a small amount of carbon clusters. That is, the present invention is intended to submit an ethylenically unsaturated resin composition containing a small amount of carbon clusters, further, high heat yellowing resistance, high dispersibility of fine particles containing a coloring material, excellent pattern shape. It is an object to provide a photosensitive resin composition from which a resist can be obtained.
- the carbon cluster (c) is at least one of fullerene and soot-like substance, and the content thereof is 0.00001 to 10 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated resin (A).
- the ethylenically unsaturated resin (A) is obtained by ring-opening addition of a carboxyl group-containing ethylenically unsaturated compound (m-2) to the epoxy group of the epoxy group-containing copolymer (P1), and further, An ethylenically unsaturated resin (A1) obtained by adding a polybasic acid anhydride (d) to a hydroxy group formed by ring opening of an epoxy group,
- the epoxy group-containing copolymer (P1) is Structural unit derived from epoxy group-containing (meth)acrylate (m-1) and structural unit derived from polymerizable monomer (m-3) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and the following chemical formula (1) And at least one selected from the group consisting of structural units derived from the polymerizable monomer (m-4)
- the ethylenically unsaturated resin composition according to [1] which is a copolymer containing a.
- X and X′ in the formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 each independently.
- the ethylenically unsaturated resin (A) is a hydroxy group formed by ring-opening addition of the carboxyl group-containing copolymer (P2) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1).
- An unsaturated group-containing ethylenically unsaturated resin (A2) having The carboxy group-containing copolymer (P2) is A structural unit derived from a carboxy group-containing ethylenically unsaturated compound (m-2), Consisting of a structural unit derived from a polymerizable monomer (m-3) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a structural unit derived from a polymerizable monomer (m-4) represented by the following chemical formula (1) At least one selected from the group; The ethylenically unsaturated resin composition according to [1], which is a copolymer containing.
- X and X′ in the formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 each independently.
- the ethylenically unsaturated resin (A) is obtained by ring-opening addition of a carboxy group-containing ethylenically unsaturated compound (m-2) to the epoxy group of the epoxy resin (P3), and further opening of the epoxy group.
- An ethylenically unsaturated resin (A3) obtained by adding a polybasic acid anhydride (d) to a hydroxy group formed by cyclization The epoxy resin (P3) is At least one selected from the group consisting of a novolac type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3) [1] The ethylenically unsaturated resin composition described. [5] The ethylenically unsaturated resin (A) has a hydroxy group formed by ring-opening addition of the carboxy group-containing resin (P4) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1).
- the carboxy group-containing resin (P4) is a resin having a carboxy group formed by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e),
- the epoxy resin (P3) is At least one selected from the group consisting of a novolac type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3) [1] The ethylenically unsaturated resin composition described.
- the ethylenically unsaturated resin (A) is The ethylenic unsaturated resin (A5) obtained by adding the polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A2) described in [3], or the ethylenic resin described in [5].
- [11] further contains a colorant (F), The photosensitive resin composition according to [10], wherein the colorant (F) is at least one selected from the group consisting of dyes and pigments.
- an ethylenically unsaturated resin composition containing a small amount of carbon clusters, having high transparency, high heat yellowing resistance, and high dispersibility of fine particles containing a coloring material, and a photosensitive resin composition using the same are provided.
- the ethylenically unsaturated resin composition of the present invention contains an ethylenically unsaturated resin (A), a carbon cluster (c), and a solvent (B).
- the carbon cluster (c) is at least one of fullerene and soot-like substance.
- the content of the carbon cluster (c) is 0.00001 to 10 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated resin (A).
- the carbon cluster (c) is preferably an unsubstituted fullerene.
- the ethylenically unsaturated resin composition of the present invention does not have to contain a polymerization inhibitor other than the carbon cluster (c) substantially.
- the term "substantially free from” means that the polymerization inhibitor other than the carbon cluster (c) is preferably 0.05 parts by mass or less, more preferably 0 parts by mass, relative to 100 parts by mass of the ethylenically unsaturated resin (A). It is meant to include not more than 0.01 part by mass.
- the resin composition of the present invention may further contain a reactive diluent (D).
- D reactive diluent
- the ethylenically unsaturated resin composition of the present invention prevents gelation of the ethylenically unsaturated resin (A) due to polymerization of double bonds and enhances storage stability. You can Further, by using the carbon clusters (c) in the photosensitive resin composition containing the photopolymerization initiator (E) described below, heat-resistant yellowing and fine particle dispersibility including a coloring material are exerted without adversely affecting curability. It is possible to obtain a photosensitive resin composition which can obtain a resist excellent in excellent pattern shape.
- the carbon cluster (c) is a group or fine particles formed by aggregating several to several hundred atoms or molecules.
- the maximum size of the carbon cluster (c) is preferably 300 nm or less, and more preferably 100 nm or less.
- the primary particles may be aggregated, but the size of the primary particle affects the dispersion of the carbon cluster (c), so the maximum diameter here is the maximum diameter of the primary particle.
- the carbon cluster (c) of the present invention is a fullerene or soot-like substance.
- fullerene used in the present invention those having about 60 to 120 carbon atoms such as 60, 70, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96 carbon atoms are known. There is.
- the carbon number is not particularly limited, but 60 carbon atoms (C60) and 70 carbon atoms (C70) are preferable from the viewpoints of easy availability and excellent dispersibility.
- fullerenes containing different kinds of atoms such as scandium (Sc), lanthanum (La), cerium (Ce), titanium (Ti) and nitrogen (N) can also be used.
- fullerene oxides (C60) 2 O in which fullerene oxides are added to each other, and addition products of fullerenes (C60-C60, C70-C60, C70-C70, etc.) can also be used.
- the soot-like substance used in the present invention is preferably soot produced as a by-product during the production of fullerenes. It is included in the crude fullerenes produced during the fullerene production process. After removing the fullerenes from the crude fullerenes by solvent extraction, the residue is richer in its soot-like substances.
- This soot-like carbon material has a structure in which a 5-membered ring and a 6-membered ring are bonded to each other like fullerene, and includes an amorphous carbon molecule having no closed shell.
- Examples of a method for producing fullerene that produces a soot-like substance include a resistance heating method, an arc discharge method, a microwave method, a high frequency heating method, a CVD method, a thermal plasma method, a combustion method, a laser method, and a thermal decomposition method. Both are manufactured under an environment of a pressure of 800 hPa or less.
- the soot-like carbon material can be obtained by firing a hydrocarbon raw material and an oxygen-containing gas under a reduced pressure environment.
- the hydrocarbon raw material for example, an aromatic hydrocarbon such as toluene or benzene can be used.
- the reduced pressure condition is preferably 3 to 800 hPa, and the heating condition is preferably 1600° C. to 2000° C.
- Calcination of the hydrocarbon raw material and the oxygen-containing gas under the above-mentioned reduced pressure environment causes hydrogen to escape from the hydrocarbon raw material.
- the mixing ratio of the hydrocarbon raw material and the oxygen-containing gas is preferably 2.5 to 3.5 in terms of an equivalent ratio, and the amount of the hydrocarbon raw material is preferably increased.
- the reaction can be incomplete combustion.
- carbon in the hydrocarbon raw material is combined with oxygen and is discharged as carbon monoxide or carbon dioxide, which may make it difficult for the carbons to be bonded to each other.
- the equivalence ratio is 1 where the ratio of the amount of hydrocarbon raw material that completely burns to the amount of oxygen is exactly 1.
- the hydrocarbon raw material from which hydrogen has been released is unstable and is likely to aggregate with the surrounding carbons. At this time, a part reacts and chemically bonds.
- the carbon compounds obtained in this process include soot-like substances and other carbon compounds.
- the soot-like substance includes an amorphous carbon molecule such as fullerene, which has a plurality of carbons bonded to each other due to the progress of bonding between molecules, but cannot reach a predetermined spherical molecular structure.
- Such an amorphous carbon molecule has the same structure as the partial structure of fullerene, and has an intermediate produced in the process of producing fullerene, a part of spherical fullerene, or a structure in which the shell is not closed. Examples include carbon molecules.
- This amorphous carbon molecule may form a cluster structure in which a plurality of these carbon molecules are collected.
- the cluster structure includes a nested structure in which a carbon molecule having a large size unclosed structure is configured to enclose a carbon molecule having a small size unclosed structure.
- the carbon cluster (c) may have a substituent as long as the effects such as dispersibility and radical scavenging ability are not impaired.
- substituents include indene, malonic acid, methyl phenylbutyrate, etc.
- derivatives of fullerene include ICBA (indene bis adduct), ICMA (indene adduct), PCBM (phenyl-C61-butyric acid methyl ester, etc.),
- Examples include SAM (1-methyl-1H-pyrrolobenzoic acid adduct) and the like.
- the amount of the carbon cluster (c) added is 0.00001 to 10 parts by mass, preferably 0.0001 to 5 parts by mass, and 0.1 to 100 parts by mass of the ethylenically unsaturated resin (A). It is more preferably 005 to 1 part by mass.
- the amount is 0.00001 parts by mass or more, it is possible to prevent the double bond of the ethylenically unsaturated resin (A) from polymerizing and gelling the composition. If the amount is 10 parts by mass or less, the curability is not adversely affected even when photocured as the photosensitive resin composition described below. If the carbon cluster (c) is finally contained in the ethylenically unsaturated resin composition, the effect of the present invention can be obtained.
- the carbon cluster (c) when the carbon cluster (c) is added from the stage of synthesizing the ethylenically unsaturated resin (A), the carbon cluster (c) can be more efficiently dispersed in the ethylenically unsaturated resin composition.
- the addition amount of the carbon cluster (c) used in the synthesis of the ethylenically unsaturated resin (A) is preferably 0.0001 to 0.1 part by mass with respect to 100 parts by mass of the total of the polymer and the monomer as the material, and 0 More preferably 0.005 to 0.05 parts by mass.
- the amount of carbon cluster (c) added during the reaction is 0.1 part by mass or less, the reaction is not hindered even when radically curing the ethylenically unsaturated resin (A).
- the amount is 0.0001 parts by mass or more, radicals generated during the reaction when the ethylenically unsaturated resin (A) is obtained can be sufficiently trapped, and gelation of the ethylenically unsaturated resin (A) can be prevented.
- the carbon cluster (c) is used in a small amount, it is preferable to use an unsubstituted fullerene for the carbon cluster (c) from the viewpoint of availability, and it is preferable to use a mixed fullerene containing C60 and C70 and other higher fullerenes. More preferably, a substituted fullerene is used.
- nanomix ST C60 is about 60%, C70 is about 25%, and other higher fullerenes
- Frontier Carbon Co. which is a mixture of fullerenes
- Polymerization inhibitor other than carbon cluster (c) A polymerization inhibitor other than the carbon cluster (c) is usually added to prevent gelation due to polymerization of the double bond introduced into the ethylenically unsaturated resin (A) except for the carbon cluster (c) according to the present invention.
- the type of the polymerization inhibitor is not particularly limited, and specific examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene.
- the ethylenically unsaturated resin (A) of the present invention is not particularly limited as long as it is a resin containing an ethylenically unsaturated group, but preferably an epoxy group-containing compound (a) is reacted with a carboxy group-containing compound (b). It is a resin obtained by allowing at least one of the epoxy group-containing compound (a) and the carboxy group-containing compound (b) to contain an ethylenically unsaturated group.
- a resin containing an epoxy group and an unsaturated compound containing a carboxy group are reacted in the presence of a carbon cluster (c) and a catalyst as a polymerization inhibitor.
- a method of reacting an unsaturated compound containing an epoxy group with a resin containing a carboxy group in the presence of a carbon cluster (c) and a catalyst as a polymerization inhibitor can be obtained.
- the epoxy group-containing compound (a) according to the present invention is not particularly limited as long as it is a compound having an epoxy group.
- the epoxy resin (P3) in the embodiment may be mentioned.
- the carboxy group-containing compound (b) according to the present invention is not particularly limited as long as it is a compound having a carboxy group.
- the carboxy group-containing resin (P4) in the embodiment is exemplified.
- the amount of the carbon cluster (c) used is, for example, 0.00001 to 10 parts by mass with respect to 100 parts by mass of the total of the epoxy group-containing compound and the carboxy group-containing compound, the ethylenically unsaturated compound finally obtained.
- the resin composition contains 0.00001 to 10 parts by mass of the carbon cluster (c) with respect to 100 parts by mass of the ethylenically unsaturated resin (A).
- the ethylenically unsaturated resin (A1) of the present embodiment has the epoxy group of the epoxy group-containing compound (a), the epoxy group-containing copolymer (P1), and the carboxy group-containing ethylene of the carboxy group-containing compound (b). Ring-opening addition of a polyunsaturated compound (m-2) and, if necessary, further addition of a polybasic acid anhydride (d) to the hydroxy group formed by ring-opening of the epoxy group. It is a resin having a saturated group.
- the epoxy group-containing copolymer (P1) is a polymerizable monomer having a structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms ( A copolymer containing a structural unit derived from (m-3) and at least one selected from the group consisting of structural units derived from the polymerizable monomer (m-4) represented by the chemical formula (1).
- the ethylenically unsaturated resin (A1) may further contain a structural unit derived from the aromatic ring-containing polymerizable monomer (m-5).
- the ethylenically unsaturated resin (A1) according to the present embodiment contains a structural unit derived from the addition reaction of the carboxy group-containing ethylenically unsaturated compound (m-2), a double bond having excellent photosensitivity is introduced. At the same time, a hydroxy group having excellent alkali developability can be obtained by ring opening of the epoxy group. Furthermore, if a carboxylic acid is introduced by adding the polybasic acid anhydride (d) to the obtained hydroxy group, the alkali developability can be enhanced. With this constitutional unit, sufficient hardness of the cured product is exhibited and high solvent resistance is exhibited. Further, curability by heat can be simultaneously expressed by leaving the whole amount of the epoxy group without reacting with the carboxyl group-containing ethylenically unsaturated compound (m-2).
- Epoxy group-containing copolymer (P1) The monomer (M1) forming the epoxy group-containing copolymer (P1) (hereinafter sometimes simply referred to as “copolymer (P1)”) related to the ethylenically unsaturated resin (A1) of the present embodiment is , An epoxy group-containing ethylenically unsaturated compound (m-1), a polymerizable monomer (m-3) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and a polymerizable compound represented by the above chemical formula (1) And at least one selected from the group consisting of monomers (m-4).
- the monomer (M1) may further contain an aromatic ring-containing polymerizable monomer (m-5) and other polymerizable monomers (m-6).
- an aromatic ring-containing polymerizable monomer (m-5) By further including the aromatic ring-containing polymerizable monomer (m-5), the epoxy group-containing copolymer (P1) having more excellent colorant dispersibility can be obtained.
- Epoxy group-containing ethylenically unsaturated compound (m-1) The epoxy group-containing ethylenically unsaturated compound (m-1) (hereinafter sometimes simply referred to as "monomer (m-1)”) does not have a carboxy group and contains an epoxy group and an ethylenically unsaturated group. It is not particularly limited as long as it has a monomer.
- glycidyl (meth)acrylate 2-glycidyloxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, and lactone adducts thereof (for example, , Cyclomer (registered trademark) A200, M100 manufactured by Daicel Chemical Industries, Ltd., mono(meth)acrylic acid ester of 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, dicyclopentenyl ( Examples thereof include an epoxidized product of (meth)acrylate and an epoxidized product of dicyclopentenyloxyethyl (meth)acrylate.
- These epoxy group-containing ethylenically unsaturated compounds (m-1) may be used alone or in combination of two or more kinds.
- glycidyl (meth)acrylate
- the structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) and the carboxy group-containing ethylenically unsaturated compound (m-2) described later impart a photosensitive group that exhibits photocurability
- the ethylenically unsaturated resin (A1) of one aspect of the invention it is an essential origin configuration. By introducing a photosensitive group exhibiting photocurability, a cured film exhibits sufficient hardness and high solvent resistance.
- the polymerizable monomer (m-3) (hereinafter sometimes simply referred to as “monomer (m-3)”) has a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.
- the bridged cyclic hydrocarbon means one having a structure represented by the following formula (2) or (3) represented by adamantane and norbornane, and the bridged cyclic hydrocarbon group is , Refers to a group corresponding to the rest of the structure except for some hydrogen.
- the polymerizable monomer (m-3) does not include the polymerizable monomer (m-4) described later.
- a and B each represent a linear or branched alkylene group (including cyclic group), R3 represents a hydrogen atom or a methyl group.
- a and B may be the same or different. , Or the branches of A and B may be connected to form a ring.
- A', B', and D each represent a linear or branched alkylene group (including cyclic group), and R4 represents a hydrogen atom or a methyl group.
- A', B', and D. May be the same or different, and the branches of A′, B′, and D may be connected to form a ring.
- a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is preferable, and an adamantyl (meth)acrylate or a structure represented by the following formula (4) ( More preferred is (meth)acrylate. ..
- R5 to R7 each represent a hydrogen atom or a methyl group.
- R8 and R9 may be a hydrogen atom or a methyl group, or may be bonded to each other to form a saturated or unsaturated ring.
- the ring is preferably a 5-membered ring or a 6-membered ring.* represents a bond linked to the (meth)acryloyloxy group.
- Examples of (m-3) include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate and adamantyl (meth)acrylate. These may be used alone or in combination of two or more.
- polymerizable monomer (m-4) The polymerizable monomer (m-4) (hereinafter sometimes simply referred to as “monomer (m-4)”) is a monomer represented by the following general formula (1).
- X and X′ in the formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 each independently.
- the monomer (m-4) is not particularly limited as long as it has the chemical structure represented by the general formula (1).
- examples of X and X'representing a linear or branched hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Group, isobutyl group, t-butyl group and the like.
- examples of the substituent of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, which is represented by R1 and R2 include an alkoxy group and an aryl group.
- R1 and R2 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group.
- a linear or branched alkyl group such as; cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group, etc.
- Examples thereof include a cyclic group; an alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group and a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a phenylaralkyl group.
- Examples of the monomer (m-4) having the chemical structure represented by the general formula (1) include norbornene (bicyclo[2.2.1]hept-2-ene) and 5-methylbicyclo[2.2.1]. ] Hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 2,5 . 1 7,10 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 2,5 . 1 7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .
- Use of the above-mentioned monomer (m-3) and/or the above-mentioned monomer (m-4) contributes to smooth coatability of the cured film, high thermal decomposition resistance, and high heat yellowing.
- One of the monomer (m-3) and the monomer (m-4) may be used, or both of them may be used.
- the aromatic ring-containing polymerizable monomer (m-5) (hereinafter sometimes simply referred to as “monomer (m-5)”) is a monomer having no carboxy group or epoxy group and having an aromatic ring.
- styrene ⁇ -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p -Aromatic vinyl compounds such as methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene; benzyl (meth)acrylate, rosin (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, Phenoxyethyl (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate (trade name: Light acrylate P-200A, manufactured by Kyoei Chemical Co.
- the ethylenically unsaturated resin (A1) used in the present invention is at least selected from the group consisting of benzyl (meth)acrylate, styrene, biphenyl skeleton, naphthalene skeleton and anthracene skeleton. It is more preferable to introduce a structural unit having one kind.
- the epoxy group-containing copolymer (P1) is a polymerizable monomer (m-6) other than the monomers (m-1) to (m-5) (hereinafter, simply referred to as “monomer (m- 6)” in some cases.)) may be copolymerized.
- Other polymerizable monomers (m-6) are the same as the monomers (m-1), (m-3), (m-4), (m-5) and the monomers (m-2) described later. Is a copolymerizable monomer of.
- This monomer (m-6) is generally a radically polymerizable compound having an ethylenically unsaturated group.
- this monomer (m-6) examples include (meth)acrylic acid esters, (meth)acrylic acid amides, maleimides, unsaturated dicarboxylic acid diesters, and dienes such as butadiene.
- Specific examples of (meth)acrylic acid esters include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, iso-propyl(meth)acrylate, n-butyl(meth)acrylate, sec.
- the (meth)acrylic acid amide include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N- It includes dipropylamide, (meth)acrylic acid N,N-di-iso-propylamide, (meth)acrylic acid anthracenylamide and the like.
- maleimides include vinyl compounds such as (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone and vinyl acetate; N- Cyclohexyl maleimide, N-lauryl maleimide and the like are included.
- unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate and the like. These may be used alone or in combination of two or more, if necessary.
- the monomer (M1) contains the monomer (m-1), and if necessary, for example, the monomer (m-3), the monomer (m-4) or When the monomer (m-5) is included, the ratio of the structure derived from each monomer is the value of the molar ratio of each polymerizable monomer added for the copolymerization reaction.
- the mixing ratio (molar ratio) of each monomer is not particularly limited, but the mixing ratio of the monomer (m-1) is preferably 9 to 70 mol%, more preferably 13 to 65 mol%.
- the blending ratio of the monomer (m-1) is 9 mol% or more, sufficient curability can be exhibited in the photosensitive resin composition.
- the blending ratio of the monomer (m-1) is 70 mol% or less, the blending ratio of the monomer (m-3) and/or the monomer (m-4) becomes sufficiently high, and the desired thermal decomposition resistance and refractive index can be obtained.
- An ethylenically unsaturated resin (A1) having is obtained.
- the mixing ratio is 0 mol based on 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1). % To more than 40 mol %, and more preferably more than 0 to 30 mol %. When the blending ratio is more than 0 mol%, desired thermal decomposition resistance, thermal yellowing resistance, and good solubility in a solvent can be obtained. When the monomer (m-5) is used, its mixing ratio should be more than 0 mol% to 50 mol% based on 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1).
- the monomer (m-6) is used, its blending ratio is more than 0 mol% to 10 mol% with respect to 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1). Is preferable, and more than 0 mol% to 5 mol% is more preferable.
- the epoxy group-containing copolymer (P1) according to the present invention can be produced by using the copolymerization reaction of the monomer (M1).
- the copolymerization reaction carried out in the present invention can be carried out according to a radical polymerization method known in the art. For example, after dissolving a monomer used for copolymerization in a solvent, a polymerization initiator is added to the solution, and the temperature is 50 to 140° C., more preferably 60 to 130° C., 1 to 20 hours, more preferably 1 to 12 hours. All you have to do is react. Further, the monomer used for the copolymerization and the polymerization initiator may be added dropwise to the solvent adjusted to 50 to 140° C. for the reaction.
- the solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
- a commonly used organic solvent can be used as the copolymerization reaction solvent.
- the copolymerization reaction solvent the solvent for addition reaction described below can be used.
- the amount of the solvent used in the copolymerization reaction is not particularly limited, but is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, when the total amount of the monomers used in the copolymerization is 100 parts by mass.
- the solvent in an amount of 1000 parts by mass or less it is possible to suppress the decrease in the molecular weight of the copolymer (P1) due to the chain transfer action, and to control the viscosity of the copolymer (P1) within an appropriate range. be able to.
- the solvent in an amount of 30 parts by mass or more an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably carried out, and coloring and gelation of the copolymer (P1) can be prevented. You can also
- the polymerization initiator that can be used in this copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound can be used.
- the amount of the polymerization initiator used in this copolymerization reaction is not particularly limited, but is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass when the total amount of the monomers used in the copolymerization is 100 parts by mass. 10 parts by mass.
- Carboxy-containing ethylenically unsaturated compound (m-2) The carboxy group-containing ethylenically unsaturated compound (m-2) (hereinafter sometimes simply referred to as "monomer (m-2)”) has no epoxy group and reacts with an epoxy group among acid groups. There is no particular limitation as long as it is a monomer having a carboxy group and an ethylenically unsaturated group having good properties. For example, unsaturated monobasic acid or unsaturated dibasic acid monoester may be mentioned.
- unsaturated dibasic acid monoesters examples include monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate.
- carboxy group-containing ethylenically unsaturated compounds (m-2) may be used alone or in combination of two or more.
- (meth)acrylic acid is preferable from the viewpoint of easy availability and reactivity.
- the reaction ratio of the carboxyl group-containing ethylenically unsaturated compound (m-2) is preferably 10 to 70 mol% when the total amount of the monomers (M1) of the epoxy group-containing copolymer (P1) is 100 mol%. , And more preferably 15 to 65 mol %.
- the blending ratio of the carboxy group-containing ethylenically unsaturated compound (m-2) is 10 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared.
- the content is 70 mol% or less, the mixing ratio of the monomer (M1) is sufficiently secured, and the ethylenically unsaturated resin (A1) having desired thermal decomposition resistance and the like can be obtained.
- the proportion of the carboxy group-containing ethylenically unsaturated compound (m-2) to be added to the number of moles of the epoxy group of the epoxy group-containing copolymer (P1) is preferably 90 to 100%. , And more preferably 95 to 100%.
- the addition ratio of the carboxy group-containing ethylenically unsaturated compound (m-2) is 90% or more, sufficient curability can be exhibited in the photosensitive resin composition. ..
- the polybasic acid anhydride (d) is not particularly limited as long as it has an acid anhydride structure having a good reactivity with a hydroxy group, but a polybasic acid anhydride (d) having a ring structure in which by-products are not generated after the reaction is preferable. is there.
- 1,2,3,6-tetrahydrophthalic anhydride hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride , Methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid anhydride, succinic anhydride, octenylsuccinic anhydride and the like.
- the reaction ratio of the polybasic acid anhydride (d) is preferably 10 to 70 mol %, more preferably 15 when the total amount of the monomers (M1) of the epoxy group-containing copolymer (P1) is 100 mol %. ⁇ 65 mol %. It is preferably 20 to 100 mol %, and more preferably 30 to 90 mol% with respect to the number of moles to which the carboxy group-containing ethylenically unsaturated compound (m-2) is added.
- the ethylenically unsaturated resin (A1) is obtained, for example, by adding a polymerization inhibitor and a catalyst to a solution of the epoxy group-containing copolymer (P1), and then adding a carboxy group-containing ethylenically unsaturated compound (m- 2) is added, and the epoxy group is subjected to a ring-opening addition reaction under the conditions of 50 to 150° C., preferably 80 to 130° C., and then a polybasic acid anhydride (d) is added, if necessary, to carry out the addition reaction. Can be manufactured. It is preferable to use the carbon cluster (c) as the polymerization inhibitor.
- catalyst used in this embodiment examples include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelate compounds. .. These catalysts may be used alone or in combination of two or more.
- the amount of the catalyst used in this embodiment is not particularly limited, but generally 0.01 to 5 parts by mass when the resin precursor (epoxy group-containing copolymer (P1)) is 100 parts by mass. Parts, preferably 0.1 to 2 parts by mass, more preferably 0.2 to 1 part by mass.
- the solvent used in this embodiment is not particularly limited, and known solvents can be appropriately used.
- ether compounds, ketone compounds, ester compounds, aromatic hydrocarbon compounds, and carboxylic acid amide compounds can be used.
- the ether compound include (poly)alkylene glycol monoalkyl ether; (poly)alkylene glycol monoalkyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran.
- (poly)alkylene glycol monoalkyl ether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene.
- Glycol monomethyl ether triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- It includes n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like.
- the (poly)alkylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.
- Specific examples of the ketone compound include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like.
- Specific examples of the ester compound include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and methyl 3-methoxypropionate.
- aromatic hydrocarbon compounds include toluene, xylene and the like.
- carboxylic acid amide compound include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and the like. These solvents may be used alone or in combination of two or more.
- glycol ether solvents are preferable. That is, it is preferable to use (poly)alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether and (poly)alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate as the solvent.
- the amount of the solvent used for producing the resin of the present embodiment is not particularly limited, but is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass when the resin precursor is 100 parts by mass. It is a mass part.
- the amount of the above solvent used is 1000 parts by mass or less, the viscosity of the resin can be controlled in an appropriate range, which is preferable.
- the amount of the above-mentioned solvent used is 30 parts by mass or more, it is possible to prevent image sticking from occurring during the reaction and to carry out the synthesis reaction stably, which is preferable. Further, when the amount of the solvent used is 30 parts by mass or more, coloring and gelation of the resin can be prevented.
- the ethylenically unsaturated resin (A2) has the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1), which is the epoxy group-containing compound (a), and the carboxy group-containing compound (b). It is a resin containing a hydroxy group formed by ring-opening addition of a carboxy group-containing copolymer (P2) and an ethylenically unsaturated group.
- the carboxy group-containing copolymer (P2) contains at least a constitutional unit derived from a carboxy group-containing ethylenically unsaturated compound (m-2), and, if necessary, a bridged cyclic hydrocarbon having 10 to 20 carbon atoms.
- a structural unit derived from the polymerizable monomer (m-3) having a group, a structural unit derived from the polymerizable monomer (m-4) represented by the general formula (1), and an aromatic ring-containing polymerizable monomer (m-5). ) Is a copolymer containing a structural unit derived from the above.
- the ethylenically unsaturated resin (A2) contains a structural unit derived from the addition reaction of the epoxy group-containing ethylenically unsaturated compound (m-1), a double bond having excellent photosensitivity is introduced. At the same time, a hydroxy group can be obtained by ring opening of the epoxy group. This makes it possible to develop curability by light and heat and also develop alkali developability. With this structural unit, sufficient hardness of the cured product is exhibited, and high solvent resistance is exhibited.
- the carboxylic acid can be introduced at the same time by leaving the whole amount of the carboxy group of the carboxy group-containing copolymer (P2) with the epoxy group of the monomer (m-1) and leaving a part thereof.
- the epoxy group-containing ethylenically unsaturated compound (m-1) As the epoxy group-containing ethylenically unsaturated compound (m-1) according to this embodiment, the one according to the first embodiment can be used.
- the addition ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) to the number of moles of carboxy contained in the carboxy group-containing copolymer (P2) is preferably 90 to 100 mol%, more preferably Is 95 to 100 mol %.
- the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably 10 when the total amount of all monomers (M2) used in the epoxy group-containing copolymer (P2) is 100 mol %.
- Carboxy group-containing copolymer (P2) All the monomers (M2) of the carboxy group-containing copolymer (P2) (hereinafter sometimes simply referred to as “copolymer (P2)”) related to the ethylenically unsaturated resin (A2) of the present embodiment, A polymerizable monomer (m-3) containing at least a carboxy group-containing ethylenically unsaturated compound (m-2) and, if necessary, further having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms;
- the polymerizable monomer (m-4) represented by the chemical formula (1), the aromatic ring-containing polymerizable monomer (m-5), other polymerizable monomer (m-6), and the like can be contained.
- the polymerizable monomer (m-6) is the same as that described in the first embodiment, and the description is omitted.
- the mixing ratio (molar ratio) of each monomer is not particularly limited, but the mixing ratio of the monomer (m-2) is preferably 9 to 70 mol% when the total of all monomers (M2) is 100 mol %. , And more preferably 13 to 65 mol %.
- the blending ratio of the monomer (m-2) is 9 mol% or more, sufficient curability can be exhibited in the photosensitive resin composition. If the blending ratio of the monomer (m-2) is 70 mol% or less, the blending ratio of the monomer (m-3), the monomer (a-4) and the monomer (m-5) will be sufficiently high, and the desired amount will be obtained.
- An ethylenically unsaturated resin (A2) having thermal decomposition resistance is obtained.
- the mixing ratio thereof is a total amount based on 100 mol% of the total amount of all the monomers (M2) of the carboxy group-containing copolymer (P2). It is preferably more than 0 mol% to 40 mol%, more preferably more than 0 mol% to 30 mol%.
- the blending ratio is 1 mol% or more, desired thermal decomposition resistance, thermal yellowing resistance, and good solubility in a solvent can be obtained.
- the mixing ratio thereof is more than 0 mol% to 50 mol% based on 100 mol% of the total amount of the carboxy group-containing ethylenically unsaturated compound (m-2). More preferably, it is more than 0 mol% to 40 mol%.
- the mixing ratio thereof is more than 0 mol% to 10 mol% based on 100 mol% of the total amount of the monomer (M2) of the epoxy group-containing copolymer (P2). Is preferable, and more than 0 mol% to 5 mol% is more preferable.
- the carboxy group-containing copolymer (P2) according to the present invention can be produced by using a copolymerization reaction, like the copolymer (P1) according to the first embodiment.
- the ethylenically unsaturated resin (A2) is produced by reacting an epoxy group-containing ethylenically unsaturated compound (m-1) with a carboxy group-containing copolymer (P2) in the presence of a polymerization inhibitor and a catalyst. It is a method for producing a polyunsaturated resin (A2), and the polymerization inhibitor is preferably the above-mentioned carbon cluster (c).
- the ethylenically unsaturated resin (A2) according to the present embodiment is obtained by adding a carbon cluster (c) as a polymerization inhibitor to a solution of the above-mentioned carboxy group-containing copolymer (P2). It can be produced by adding the epoxy group-containing ethylenically unsaturated compound (m-1) and reacting the epoxy group of the first embodiment under the same conditions as in the ring-opening addition reaction.
- the carbon cluster (c) and the solvent used are the same as in the first embodiment.
- the ethylenically unsaturated resin (A3) used in this embodiment is a carboxy group-containing ethylenically unsaturated compound which is a carboxy group-containing compound (b) in the epoxy group of the epoxy resin (P3) which is an epoxy group-containing compound (a).
- (M-2) is obtained by ring-opening addition, preferably a polybasic acid anhydride (d) is further added to the hydroxy group formed by ring-opening of the epoxy group, and a carboxy group and an ethylenic group are added. It is a resin containing a saturated group.
- the epoxy resin (P3) may be selected from the group consisting of novolac type epoxy resin (P3-1), bisphenol type epoxy resin (P3-2), and bifunctional epoxy resin having a biphenyl skeleton (P3-3). preferable. That is, as the ethylenically unsaturated resin (A3) used in the embodiment of the present invention, a novolac type epoxy resin (P3-1) to which a carboxy group-containing ethylenically unsaturated compound (m-2) is added may be added as necessary.
- the carboxy group-containing ethylenically unsaturated compound (m-2), carbon cluster (c), catalyst, solvent used and the like used in the embodiment of this example can be those of the first embodiment.
- the ethylenically unsaturated resin (A3-1) is necessary after adding a carboxy group-containing ethylenically unsaturated compound (m-2) in order to introduce a double bond into the novolac type epoxy resin (P3-1). According to the above, it can be produced by adding a polybasic acid anhydride (d) to introduce a carboxy group.
- novolac type epoxy resin examples include cresol novolac type epoxy resin and phenol novolac type epoxy resin. These novolac type epoxy resins may be used alone or in combination of two or more kinds.
- the ethylenically unsaturated resin (A3-2) is necessary after adding a carboxy group-containing ethylenically unsaturated compound (m-2) in order to introduce a double bond into the bisphenol type epoxy resin (P3-2). According to the above, it can be produced by adding a polybasic acid anhydride (d) to introduce a carboxy group.
- Examples of the bisphenol type epoxy resin (P3-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin. These bisphenol type epoxy resins may be used alone or in combination of two or more. Among these, the bisphenol A type epoxy resin is preferable from the viewpoint of easy availability and reactivity.
- the ethylenically unsaturated resin (A3-3) is a bifunctional epoxy resin (P3-3) having a biphenyl skeleton to which a carboxy group-containing ethylenically unsaturated compound (m-2) is added in order to introduce a double bond. Then, it can be produced by adding a polybasic acid anhydride (d) to introduce a carboxy group, if necessary.
- the bifunctional epoxy resin having a biphenyl skeleton (P3-3) is not particularly limited as long as it has a biphenyl skeleton and has two epoxy groups in the molecule. Examples of the biphenyl skeleton include those represented by the following formula (5).
- R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- E and E′ each independently represent an organic group having an epoxy group.
- bifunctional epoxy resin having a biphenyl skeleton examples include YX4000 (R′ is CH 3 in the following formula (6)) and YX4000K (R′ in the following formula (6)) manufactured by Mitsubishi Chemical Corporation. CH 3 ), YX4000H (in the formula (6) below, R′ is CH 3 ), YL6121HA (in the following formula (6), R′ is H, and R′ is CH 3. And the like) and the like.
- a saturated monobasic acid may be added to the epoxy group of the ethylenically unsaturated resin (A3) together with the carboxy group-containing ethylenically unsaturated compound (m-2).
- the saturated monobasic acid is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, lauric acid, tridecyl acid, palmitic acid, stearic acid and the like.
- the saturated monobasic acid may be used alone or in combination of two or more kinds. Among these, acetic acid and propionic acid are preferable from the viewpoint of boiling point and reactivity.
- polybasic acid anhydride (d) As the polybasic acid anhydride (d), the polybasic acid anhydride (d) described in the first embodiment can be used.
- the ethylenically unsaturated resin (A) used in the present invention is an ethylenically unsaturated compound containing an epoxy group in the carboxyl group derived from the polybasic acid anhydride (d) in the ethylenically unsaturated resin (A3) of the present embodiment ( m-1) may be further added.
- the epoxy group-containing ethylenically unsaturated compound (m-1) described in the first embodiment can be used as the epoxy group-containing ethylenically unsaturated compound.
- the reaction conditions for obtaining the ethylenically unsaturated resin (A3) or epoxy resin (P3) used in the present invention may be appropriately set according to a conventional method.
- the addition reaction of the carboxy group-containing ethylenically unsaturated compound (m-2) and the optionally used saturated monobasic acid is preferably carried out, for example, by adding each raw material, a polymerization inhibitor and an addition reaction catalyst to a solvent, It may be carried out in an atmosphere having an oxygen gas concentration of 2 to 10% by volume, more preferably 5 to 7% by volume, preferably 100 to 140° C., more preferably 110 to 130° C., for 2 to 12 hours.
- the addition reaction of the epoxy group-containing ethylenically unsaturated compound is preferably carried out in an atmosphere having an oxygen gas concentration of 2 to 10% by volume, more preferably 5 to 7% by volume, preferably 100 to 140° C., more preferably 110. It may be carried out at a temperature of up to 130°C for 2 to 10 hours.
- the preferred constitutional unit ratio of the ethylenically unsaturated resin (A3) used in the present invention is as follows.
- the constitutional unit derived from the epoxy resin (P3) is 40 to 70% by mass
- the constitutional unit derived from the carboxy group-containing ethylenically unsaturated compound (m-2) is 5 to 35% by mass.
- the structural unit derived from the polybasic acid anhydride (d) is 10 to 40% by mass.
- the constituent unit derived from the saturated monobasic acid is more than 0 mol% to 20% by mass.
- the constituent unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) is from more than 0 mol% to 10% by mass.
- a carboxy group-containing ethylenically unsaturated compound (to the epoxy group contained in the constitutional unit derived from the epoxy resin (P3) (The total addition rate of the constituent units derived from m-2) and a saturated monobasic acid used as necessary is preferably 90 to 100% in total with respect to the epoxy group, and a carboxy group-containing ethylenically unsaturated compound
- the addition ratio of the structural unit derived from the polybasic acid anhydride to the hydroxy group generated by the addition of the structural unit derived from (m-2) and a saturated monobasic acid used as needed is 5 to 80%.
- the addition ratio of the structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) to the carboxy group generated by the addition of the structural unit derived from the polybasic acid anhydride (d) is 10 to 50%. Is preferred.
- the ethylenically unsaturated resin (A3) is produced by reacting an epoxy resin (P3) with a carboxy group-containing ethylenically unsaturated compound (m-2) in the presence of a polymerization inhibitor and a catalyst. It is a method for producing (A3), and the polymerization inhibitor is preferably the above-mentioned carbon cluster (c).
- the ethylenically unsaturated resin (A4) has the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1), which is the epoxy group-containing compound (a), and the carboxy group-containing compound (b). It is an ethylenically unsaturated resin having a hydroxy group formed by ring-opening addition of a certain carboxy group-containing resin (P4).
- the epoxy group-containing ethylenically unsaturated compound (m-1) used in this embodiment those of the first embodiment can be used.
- the addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably more than 0 parts by mass to 10 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (P4).
- P4 carboxy group-containing resin
- the addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) is 10 parts by mass or less, the elastic recovery rate and the developability can be maintained, which is preferable.
- the molar ratio of the added epoxy group-containing ethylenically unsaturated compound (m-1) to the constitutional unit derived from the carboxy group-containing resin (P4) in the ethylenically unsaturated resin (A4) is 0.05 to 0.3. Is preferred.
- the carboxy group-containing resin (P4) used in this embodiment is a resin having a carboxy group obtained by reacting the epoxy resin (P3) with the polyfunctional carboxylic acid (e).
- the epoxy resin (P3) the epoxy resin (P3) used in the third embodiment can be used.
- the polyfunctional carboxylic acid (e) is not particularly limited. It may be either a saturated or unsaturated polyfunctional carboxylic acid. Specific examples thereof include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid and sebacic acid.
- the dibasic acids may be used alone or in combination of two or more. Among these, adipic acid and itaconic acid are preferable from the viewpoint of reactivity.
- the carboxy group-containing resin (P4) preferably contains 30 to 80% by mass of the structural unit derived from the epoxy resin (P3) and 20 to 70% by mass of the structural unit derived from the polyfunctional carboxylic acid (e).
- the molar ratio of the structural unit derived from the polyfunctional carboxylic acid (e) to the structural unit derived from the epoxy resin (P3) in the carboxy group-containing resin (P4) is 0.1 to 0.8. It is more preferably 0.15 to 0.7.
- the carboxy group-containing resin (P4) used in this embodiment can be produced, for example, by subjecting the epoxy resin (P3) and the polyfunctional carboxylic acid (e) to an addition reaction in the presence of an addition catalyst.
- the conditions of the addition reaction for obtaining the carboxy group-containing resin (P4) used in this embodiment may be appropriately set according to a conventional method.
- each raw material and the addition catalyst are added to a solvent, preferably in an atmosphere having an oxygen gas concentration of 2 to 10% by volume, more preferably an oxygen gas concentration of 5 to 7% by volume, preferably 50 to 150° C. More preferably, it may be carried out at 60 to 140° C. for 1 to 12 hours.
- the solvent that can be used in the above addition reaction is not particularly limited, and known solvents can be appropriately used.
- the solvent used for the addition reaction of the first embodiment can be used.
- the polycondensation catalyst that can be used in the above-mentioned addition reaction is not particularly limited, and known ones can be appropriately used.
- the catalyst used in the addition reaction of the first embodiment can be used.
- the ethylenically unsaturated resin (A4) is produced by reacting an epoxy group-containing ethylenically unsaturated compound (m-1) with a carboxy group-containing resin (P4) in the presence of a polymerization inhibitor and a catalyst. It is a method for producing a saturated resin (A4), and the polymerization inhibitor is preferably a carbon cluster (c).
- the carboxy group-containing resin (P4) is a resin having a carboxy group formed by reacting the epoxy resin (P3) with the polyfunctional carboxylic acid (e).
- the ethylenically unsaturated resin (A4) according to this embodiment is obtained by adding a carbon cluster (c) and a catalyst as a polymerization inhibitor to a solution of the above-mentioned carboxy group-containing resin (P4). It can be produced by adding the epoxy group-containing ethylenically unsaturated compound (m-1) and reacting under the same conditions as the ring-opening addition reaction of the epoxy group of the first embodiment.
- the carbon cluster (c) and the solvent used are the same as in the first embodiment.
- the ethylenically unsaturated resin (A5) of the present embodiment is an ethylenically unsaturated resin (A5) obtained by further adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A2) of the second embodiment. It is a resin containing a saturated group.
- the hydroxy group is a hydroxy group formed by ring-opening addition of the carboxyl group-containing copolymer (P2) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1).
- the ethylenically unsaturated resin (A5) of the present embodiment contains a structural unit derived from the addition reaction of the epoxy group-containing ethylenically unsaturated compound (m-1) and the polybasic acid anhydride (d), and thus is photosensitive. It is possible to obtain a hydroxy group having excellent alkali developability by ring opening of the epoxy group while introducing a double bond excellent in With this constitutional unit, sufficient hardness of the cured product is exhibited and high solvent resistance is exhibited. Furthermore, by introducing an acidic group or a hydroxy group as an alkali developing group, the affinity of the copolymer with the alkali developing solution is increased, and a highly precise curing pattern can be formed, achieving strict dimensional accuracy. To do.
- the carboxylic acid can be introduced at the same time by not reacting the entire amount of the carboxy group of the carboxy group-containing copolymer (P2) with the epoxy group and leaving a part thereof. Further, the amount of carboxylic acid introduced can be increased by adding a polybasic acid anhydride to the obtained hydroxyl group.
- the reaction rate of the epoxy group-containing ethylenically unsaturated compound (m-1) is the same as the reaction rate of the epoxy group-containing ethylenically unsaturated compound (m-1) of the ethylenically unsaturated resin (A2) of the second embodiment. Is. ..
- the ratio of the polybasic acid anhydride (d) to the number of moles of the epoxy group-containing ethylenically unsaturated compound (m-1) in the ethylenically unsaturated resin (A2) is preferably 10 to 90 mol%. , And more preferably 30 to 70 mol %.
- the proportion of the polybasic acid anhydride (d) is 10 mol% or more, further curability can be exhibited in the photosensitive resin composition.
- it is 90 mol% or less the unreacted product of the polybasic acid anhydride (d) does not remain and the desired ethylenically unsaturated resin (A5) is obtained.
- the reaction ratio of the polybasic acid anhydride (d) is such that the monomer (m-1), the monomer (m-2) constituting the carboxy group-containing copolymer (P2), and the arbitrary monomer (m-3) And/or, when the total of the monomer (m-4) and the optional monomer (m-5) is 100 mol %, it is preferably 5 to 65 mol %, more preferably 5 to 50 mol %.
- the blending ratio of the polybasic acid anhydride (d) is 5 mol% or more, further curability can be exhibited in the photosensitive resin composition.
- the blending ratio of the polybasic acid anhydride (d) is 65 mol% or less, a copolymer having a desired refractive index can be obtained.
- the ethylenically unsaturated resin (A5) is prepared by preparing the ethylenically unsaturated resin (A2) and then adding the polybasic acid anhydride (d) under the condition of 50 to 150° C., preferably 80 to 130° C. It can be produced by reacting a hydroxy group with a polybasic acid anhydride (d).
- the ethylenically unsaturated resin (A6) of the present embodiment is an ethylenically unsaturated resin (A6) obtained by further adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A4) of the fourth embodiment. It is a resin containing a saturated group.
- the hydroxy group is a hydroxy group formed by ring-opening addition of the carboxy group-containing resin (P4) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1).
- the ethylenically unsaturated resin (A6) of the present embodiment contains a structural unit derived from the addition reaction of the epoxy group-containing ethylenically unsaturated compound (m-1) and the polybasic acid anhydride (d), It is possible to obtain a hydroxy group having excellent alkali developability by ring opening of the epoxy group while introducing a double bond having excellent With this constitutional unit, sufficient hardness of the cured product is exhibited and high solvent resistance is exhibited. Furthermore, by introducing an acidic group or a hydroxy group as an alkali developing group, the affinity of the copolymer with the alkali developing solution is increased, and a highly precise curing pattern can be formed, achieving strict dimensional accuracy. To do.
- the carboxylic acid can be introduced at the same time by leaving the whole amount of the carboxy group of the carboxy group-containing resin (P4) with the epoxy group and leaving a part thereof. Further, the amount of carboxylic acid introduced can be increased by adding a polybasic acid anhydride to the obtained hydroxyl group.
- the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is the same as the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) of the ethylenically unsaturated resin (A4) of the fourth embodiment. Is. ..
- the ratio of the polybasic acid anhydride (d) to the number of moles of the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably 10 to 90 mol%, more preferably 30 to 70 mol%. Is.
- the proportion of the polybasic acid anhydride (d) is 10% mol or more, further curability can be exhibited when the photosensitive resin composition is prepared.
- it is 90 mol% or less, the unreacted product of the polybasic acid anhydride (d) does not remain and the desired ethylenically unsaturated resin (A6) is obtained.
- the reaction ratio of the polybasic acid anhydride (d) is preferably more than 0% by mass to 10% by mass with respect to the ethylenically unsaturated resin (A6).
- the addition amount of the polybasic acid anhydride (d) is more than 0% by mass, the sensitivity can be increased, which is preferable.
- the addition amount of the polybasic acid anhydride (d) is 10 mass% or less, the elastic recovery rate and the developability can be maintained, which is preferable.
- the ethylenically unsaturated resin (A6) is prepared by producing the ethylenically unsaturated resin (A4) and then adding the polybasic acid anhydride (d) under the condition of 50 to 150° C., preferably 80 to 130° C. It can be produced by reacting a hydroxy group with a polybasic acid anhydride (d).
- the molecular weight (polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC)) of the ethylenically unsaturated resin (A) obtained in the first to sixth embodiments of the present invention is preferably from 1,000 to 50,000. It is preferably 3000 to 40,000. When this molecular weight is 1,000 or more, the solvent resistance and thermal decomposition resistance of the cured film can be sufficiently secured. On the other hand, when the molecular weight is 50,000 or less, the molecular weight and the viscosity can be controlled in an appropriate range, which is practical. From the viewpoint of elastic recovery rate, the weight average molecular weight is preferably 3,000 to 30,000.
- the acid value (JIS K6901 5.3) of the ethylenically unsaturated resin (A) is usually 20 to 300 KOHmg/g, preferably 30 to 200 KOHmg/g. If the acid value is 20 KOHmg/g or more, the developability will be good, which is preferable. On the other hand, when the acid value is 300 KOHmg/g or less, the exposed portion (photocured portion) becomes difficult to dissolve in the alkali developing solution, which is preferable. From the viewpoint of elastic recovery rate, the acid value of the ethylenically unsaturated resin (A) is preferably 30 to 200 KOHmg/g.
- the hydroxyl equivalent of the ethylenically unsaturated resin (A) is usually 200 to 4000 g/mol, preferably 200 to 2500 g/mol.
- the hydroxyl equivalent is usually 200 to 4000 g/mol, preferably 200 to 2500 g/mol.
- the hydroxyl equivalent is usually 200 to 4000 g/mol or less, more preferably 2500 g/mol or less, the water repellency of the alkaline developer can be suppressed and good developability can be realized.
- the hydroxyl group equivalent is less than 200 g/mol, the amount of other substituents necessary for the present invention is reduced, and desired curability, heat decomposition resistance, heat yellowing and refractive index may not be obtained. .
- the hydroxyl equivalent in this specification is the mass of the ethylenically unsaturated resin (A) per the number of moles of the hydroxy group, and is a theoretical value calculated from the charged amount of the raw material with a reaction rate of 100%.
- the unsaturated group equivalent of the ethylenically unsaturated resin (A) is not limited as long as the desired effects of the present invention are exhibited, but is usually 100 to 4000 g/mol, preferably 200 to 2000 g/mol, More preferably, it is 300 to 500 g/mol.
- the unsaturated group equivalent is 100 g/mol or more, it is effective in improving the physical properties of the coating film and the alkali developability, which is preferable.
- the unsaturated group equivalent is 4000 g/mol or less, it is effective in further increasing the sensitivity, which is preferable.
- an unsaturated group equivalent of 100 g/mol or more is more effective for further enhancing the thermal decomposition resistance and the thermal yellowing resistance.
- the unsaturated group equivalent of the ethylenically unsaturated resin (A) is preferably 200 to 2000 g/mol.
- the unsaturated group equivalent is a theoretical value calculated from the charged amount when it is assumed that all the raw materials used for introducing the unsaturated group have reacted.
- the epoxy equivalent of the ethylenically unsaturated resin (A) used in the present invention is not limited as long as the desired effects of the present invention are exhibited, but is usually 100 to 4000 g/mol, preferably 200 to 2000 g/mol, It is more preferably 300 to 500 g/mol.
- the epoxy equivalent is 100 g/mol or more, it is effective and preferable for enhancing the physical properties and storage stability of the coating film.
- the epoxy equivalent is 4000 g/mol or less, it is effective in further improving the solvent resistance.
- the said epoxy equivalent is the mass of the polymer per 1 mol of epoxy groups of a polymer.
- This value can be determined by dividing the mass of the polymer by the amount of epoxy groups in the polymer (g/mol).
- the "epoxy equivalent” is a theoretical value calculated from the charged amount of the raw material used for introducing the epoxy group and the charged amount of the carboxy group-containing compound (b) to be subjected to the addition reaction as a reaction rate of 100%. ..
- the solvent (B) of the ethylenically unsaturated resin composition is not particularly limited as long as it is a solvent that does not react with the ethylenically unsaturated resin (A).
- the solvent (B) the same solvent as used in the production of the ethylenically unsaturated resin (A) can be used, and the solvent contained after the reaction can be used as it is or can be further added. it can. In addition, when other components are added, they may coexist there.
- the solvent (B) examples include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol.
- examples thereof include monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate and diethylene glycol ethyl ether acetate.
- glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate used in producing the ethylenically unsaturated resin (A) are preferable.
- the blending amount of the solvent (B) in the resin composition of the present embodiment is generally 30 to 1000 parts by mass, preferably 50 to 100 parts by mass, when the total amount of the components excluding the solvent (B) in the composition is 100 parts by mass. It is 800 parts by mass, more preferably 100 to 700 parts by mass. When the compounding amount is within this range, the resin composition has an appropriate viscosity.
- the reactive diluent (D) is not particularly limited, but one containing an ethylenically unsaturated double bond, preferably a vinyl group or a (meth)acryloyloxy group is preferable.
- Specific examples include aromatic vinyl-based monomers such as styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate and diallylbenzenephosphonate; polycarboxylic acids such as vinyl acetate and vinyl adipate.
- Monomers methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ⁇ -hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate , Diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Examples thereof include (meth)acrylic monomers such as dipentaerythritol hexa(meth)acrylate and tri(meth)acrylate of tris(hydroxyethyl)isocyanurate; and triallyl cyanurate. These can be used alone or in combination of two or more.
- the blending amount of the reactive diluent (D) in the resin composition of the present embodiment is generally 10 to 90 parts by mass, preferably 100 parts by mass when the total of the components excluding the solvent (B) in the composition is 100 parts by mass. Is 20 to 80 parts by mass, more preferably 25 to 70 parts by mass. When the amount is within this range, the resin composition has an appropriate viscosity, and the photosensitive resin composition using the resin composition has an appropriate photocurability.
- Photosensitive resin composition of the present invention comprises an ethylenically unsaturated resin (A), a carbon cluster (c), a solvent (B), a reactive diluent (D) and a photopolymerization initiator (E). including.
- Photosensitive resin composition of the present invention may further contain a coloring agent (F).
- the photosensitive resin composition of the present invention does not have to contain a polymerization inhibitor other than the carbon cluster (c) substantially.
- substantially free means that, with respect to 100 parts by mass of the ethylenically unsaturated resin (A), a polymerization inhibitor other than the carbon cluster (c) is 0.010 parts by mass or less, preferably 0.05 parts by mass. It is meant to include the following parts.
- the blending amount of the solvent (B) in the photosensitive resin composition of the present embodiment is generally 30 to 1000 parts by mass, preferably 100 parts by mass, when the total of the components excluding the solvent (B) in the composition is 100 parts by mass.
- the amount is 50 to 800 parts by mass, more preferably 100 to 700 parts by mass. A blending amount within this range results in a photosensitive resin composition having an appropriate viscosity.
- the blending amount of the reactive diluent (D) in the photosensitive resin composition of the present embodiment is generally 10 to 90 mass% when the total amount of the components excluding the solvent (B) in the composition is 100 mass %. , Preferably 20 to 80% by mass, more preferably 25 to 70% by mass. If it is the compounding quantity of this range, it will become a photosensitive resin composition which has suitable viscosity, and a photosensitive resin composition has suitable photocurability.
- the photopolymerization initiator (E) is not particularly limited, but specific examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1 ,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone and other acetophenones; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal
- the blending amount of the photopolymerization initiator (E) in the photosensitive resin composition of the present embodiment is generally 0.1 when the total amount of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. To 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass. A blending amount within this range results in a photosensitive resin composition having appropriate photocurability.
- the colorant (F) is not particularly limited as long as it can be dissolved or dispersed in the solvent (B), and known dyes or pigments can be used.
- a dye is used as the colorant (F)
- a pigment is used as the colorant (F)
- the heat resistance of the coloring pattern is higher than when a dye is used.
- Dyes and pigments may be used in combination depending on the required performance and the intended pixel color.
- dye an acidic dye having an acidic group such as a carboxy group or an acidic dye, from the viewpoint of solubility in a solvent (B) or an alkali developing solution, interaction with other components in the photosensitive resin composition, heat resistance, and the like. It is preferable to use a salt of a dye with a nitrogen compound, a sulfonamide body of an acid dye, or the like. Specific examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90.
- azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These dyes can be used alone or in combination of two or more, depending on the intended color of the pixel.
- Pigment Specific examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like; orange pigments such as C.I. I.
- the blending amount is generally 5 when the total amount of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. To 80 parts by mass, preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass.
- a known dispersant may be added to the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment.
- the dispersant it is preferable to use a polymer dispersant having excellent dispersion stability over time.
- polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. Examples include a system dispersant.
- EFKA manufactured by EFKA CHEMICALS BV (EFKA)
- Disperbyk manufactured by Big Chemie
- DISPARON manufactured by Kusumoto Kasei Co., Ltd.
- SOLSPERSE manufactured by Zeneca
- the blending amount of the dispersant in the photosensitive resin composition of the present embodiment may be appropriately set according to the type of pigment used.
- the blending amount of the ethylenically unsaturated resin (A), the carbon cluster (c) and the solvent (B) is the sum of the components excluding the solvent (B) in the resin composition.
- the ethylenically unsaturated resin (A) is preferably 50 to 99.9 parts by mass;
- the carbon cluster (c) is preferably 0.00001 to 10 parts by mass;
- the solvent ( B) is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, further preferably 100 to 700 parts by mass.
- the resin composition of the present embodiment contains the reactive diluent (D), the blending amount of the ethylenically unsaturated resin (A), the carbon cluster (c), the solvent (B) and the reactive diluent (D). Is 10 to 90 parts by mass of the ethylenically unsaturated resin (A) and 0.00001 to 10 parts by mass of the carbon cluster (c) when the total amount of the components excluding the solvent (B) in the resin composition is 100 parts by mass.
- the solvent (B) is 30 to 1000 parts by mass
- the reactive diluent (D) is 10 to 90 parts by mass
- the ethylenically unsaturated resin (A) is 20 to 80 parts by mass
- the carbon cluster ( c) is 0.0001 to 0.10 parts by mass
- the solvent (B) is 50 to 800 parts by mass
- the reactive diluent (D) is 20 to 80 parts by mass.
- the ethylenically unsaturated resin ( A) is 30 to 75 parts by mass
- carbon cluster (c) is 0.0005 to 0.05 parts by mass
- solvent (B) is 100 to 700 parts by mass
- reactive diluent (D) is 25 to 70 parts by mass. is there.
- ethylenically unsaturated resin (A), carbon cluster (c), solvent (B), reactive diluent (D), and photopolymerization initiator (E) in the photosensitive resin composition of the present embodiment
- the total amount of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass, preferably the ethylenically unsaturated resin (A) is 5 to 80 parts by mass and the carbon cluster (c) is 0.
- the solvent (B) is 30 to 1000 parts by mass
- the reactive diluent (D) is 10 to 90 parts by mass
- the photopolymerization initiator (E) is 0.1 to 30 parts by mass
- the ethylenically unsaturated resin (A) is 8 to 70 parts by mass
- the carbon cluster (c) is 0.0001 to 5 parts by mass
- the solvent (B) is 50 to 800 parts by mass
- the photopolymerization initiator (E) is 0.5 to 20 parts by mass
- more preferably the ethylenically unsaturated resin (A) is 10 to 60 parts by mass
- the solvent (B) is 100 to 700 parts by mass
- the reactive diluent (D) is 25 to 70 parts by mass
- the photopolymerization initiator (E) is 1 to 15 parts by mass.
- the photosensitive resin composition of the present embodiment contains a colorant (F), the ethylenically unsaturated resin (A), carbon cluster (c), solvent (B), reactive diluent (D), photopolymerization
- the amount of the initiator (E) and the colorant (F) compounded is generally 5 parts by weight of the ethylenically unsaturated resin (A) when the total amount of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass.
- the agent (F) is 5 to 70 parts by mass, more preferably the ethylenically unsaturated resin (A) is 10 to 60 parts by mass, the carbon cluster (c) is 0.0005 to 0.5 parts by mass, and the solvent ( B) is 100 to 700 parts by mass, reactive diluent (D) is 25 to 70 parts by mass, photopolymerization initiator (E) is 1 to 15 parts by mass, and colorant (F) is 10 to 60 parts by mass. ..
- the photosensitive resin composition of the present embodiment in addition to the above components, in order to impart predetermined characteristics, known additives such as known coupling agents, leveling agents, thermal polymerization inhibitors, and known You may mix
- the blending amount of these additives is not particularly limited as long as the effects of the present invention are not impaired.
- the photosensitive resin composition of the present embodiment can be produced by mixing the above components using a known mixing device.
- the photosensitive resin composition of the present embodiment is prepared by first preparing a resin composition containing the ethylenically unsaturated resin (A) and the solvent (B), and then reacting with the reactive diluent (D) and photopolymerization. It is also possible to mix and manufacture the agent (E).
- the resin composition can be used for preparing the photosensitive resin composition of the present embodiment, and can also be used for other purposes.
- the photosensitive resin composition of the present embodiment contains the resin of the present embodiment, a cured film having excellent developability, good colorant dispersibility and solvent resistance, and a high elastic recovery rate is obtained. Be done. Therefore, the photosensitive resin composition of the present embodiment is suitable as a material for the black matrix, color filter and black column spacer. Further, the photosensitive resin composition of the present embodiment has a good colorant dispersibility, and even if it contains a sufficient amount of a black colorant, it can sufficiently satisfy general characteristics such as developability, It is possible to form a cured resin film having good adhesion to the formation surface. Therefore, according to the photosensitive resin composition of the present embodiment, it is possible to form a black pattern having good adhesion to the formation surface and having sufficient light shielding properties.
- the resin cured film of the present embodiment can be manufactured, for example, by the method described below.
- the photosensitive resin composition is applied onto the surface of the cured resin film to be formed to form a resin layer (coating film).
- the resin layer is exposed through a mask having a predetermined pattern, and the exposed portion is photocured.
- the unexposed portion of the resin layer is developed with a developing solution to form a resin cured film having a predetermined pattern.
- post-baking heat treatment
- a halftone mask having a predetermined pattern may be used when exposing the resin layer. In this case, the unexposed portion and the semi-exposed portion are developed with a developing solution to form a resin cured film having a predetermined pattern.
- the method of applying the photosensitive resin composition is not particularly limited, and examples thereof include a screen printing method, a roll coating method, a curtain coating method, a spray coating method and a spin coating method.
- the solvent (B) contained in the resin layer is volatilized by heating with a heating means such as a circulation oven, an infrared heater, or a hot plate, if necessary. Good.
- the heating condition after coating is not particularly limited and may be appropriately set according to the composition of the photosensitive resin composition.
- the heating temperature after coating can be 50° C. to 120° C.
- the heating time can be 30 seconds to 30 minutes.
- the method of exposing the resin layer is not particularly limited, and examples thereof include a method of irradiating with active energy rays such as ultraviolet rays and excimer laser light.
- the energy dose with which the resin layer is irradiated may be appropriately set according to the composition of the photosensitive resin composition.
- the energy dose applied to the resin layer can be 30 to 2000 mJ/cm 2 , but is not limited to this range.
- the light source used for exposure is not particularly limited, but a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be arbitrarily selected and used.
- the developing solution used for the development it is preferable to use an alkaline developing solution because excellent developing properties can be obtained.
- the alkaline developer include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine; tetramethylammonium, 3-methyl.
- the cured resin film After development with a developing solution, it is preferable to wash the resin cured film having a predetermined pattern with water and dry it. Further, it is preferable to perform post-baking (heat treatment) of the resin cured film having a predetermined pattern after the development with the developing solution. By performing the post-baking, the cured resin film can be further cured.
- the conditions for post-baking are not particularly limited and can be arbitrarily selected, and may be appropriately set depending on the composition of the photosensitive resin composition.
- the heating temperature of the post bake can be 130°C to 250°C.
- the heating time for post-baking is preferably 10 minutes to 4 hours, more preferably 20 minutes to 2 hours.
- the image display device of the present embodiment includes the resin cured film of the present embodiment.
- Specific examples of the image display device include a liquid crystal display device and an organic EL display device.
- the image display device for example, one or more members selected from a black matrix, a color filter, and a black column spacer are preferably formed of the resin cured film of the present embodiment.
- the material of the substrate forming the formation surface of the resin cured film is not particularly limited, for example, glass, silicon, polycarbonate, polyester, polyamide, polyamideimide, polyimide, aluminum, on the surface of the printed wiring board and the like.
- Examples include a substrate on which a wiring pattern is formed, an array substrate, and the like.
- the method for manufacturing the image display device of the present embodiment may include the step of forming the resin cured film of the present embodiment by the above-described manufacturing method, and for members other than the member formed of the resin cured film, It can be manufactured by a conventional method.
- the resin cured film obtained by curing the photosensitive resin composition of the present embodiment has excellent developability, good colorant dispersibility and solvent resistance, and a high elastic recovery rate. Therefore, it is suitable as a material for a black matrix, a color filter, and a black column spacer included in an image display device.
- Example 1 137.5 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the mixture was stirred while substituting with nitrogen and heated to 120°C.
- Example 2 to 4 and Comparative Examples 1 to 3 In Examples 2 to 3, the addition amount of the fullerene solution was changed, and in Example 4, a solution of an indene adduct of fullerene (manufactured by Frontier Carbon Co., nanom (registered trademark) spectrum NPQ3000) (concentration 0) was used instead of the fullerene solution. 0.02% by mass), and a solution containing an ethylenically unsaturated resin in the same manner as in Example 1 except that BHT (di-t-butylhydroxytoluene) was used instead of the fullerene solution in Comparative Examples. A composition was obtained. The results are shown in Table 1.
- Example 5 an ethylenically unsaturated resin solution was obtained in the same manner as in Example 1, except that the polymerization inhibitor was changed to 0.02% by mass of soot-like substance.
- the soot-like substance the one obtained by the following method was used. Toluene and pure oxygen gas were supplied to the reaction tube at a ratio of 3:1 and mixed, and heated under the conditions of 67 hPa and 180° C. to obtain soot. Then, it was washed twice with toluene to obtain a soot-like substance. The results are shown in Table 1.
- Example 6 185.6 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while substituting with nitrogen and heated to 120°C.
- the acid value was 72.0 KOHmg/g or less
- the ethylenically unsaturated resin composition (solid) was a solution containing the ethylenically unsaturated resin (A2) having a solid content concentration of 28.6% by mass.
- An acid value of 196.8 KOHmg/g and a weight average molecular weight of 18500) were obtained.
- the reaction rate of the acid and the epoxy was calculated by measuring the acid value in the reaction solution, and it was 97.8%.
- Example 7 to 10 and Comparative Examples 4 to 6 In Examples 6 to 8, the addition amount of the fullerene solution was changed, in Example 9, the polymerization inhibitor was changed to an indene adduct of fullerene, and in Example 10, the polymerization inhibitor was changed to a soot-like substance, In Comparative Example, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 1 except that BHT was used instead of the fullerene solution. The results are shown in Table 2.
- Example 11 In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 224.1 g of cresol novolac epoxy N-695 (epoxy equivalent 215) manufactured by DIC Corporation, which is an epoxy resin (P3), and PGMEA94. 5 g is added and the temperature is raised to 120° C. while blowing low oxygen air into which nitrogen gas is injected so that the oxygen concentration becomes 4 to 7% by volume.
- cresol novolac epoxy N-695 epoxy equivalent 215
- P3 epoxy resin
- PGMEA94 PGMEA94
- the acid value was 42.0 KOHmg/g or less, and 75.1 g (1.04 mol) of acrylic acid as a monomer (m-2) was added to fullerene (manufactured by Frontier Carbon Co., nanom (registered trademark) mix ST).
- a solution of 8 g of a trimethylbenzene solution containing 3% by mass and 0.9 g of triphenylphosphine was added dropwise over 10 minutes. Then, the reaction is continued until the acid value becomes 1 or less, 33.4 g of succinic anhydride is charged as the polybasic acid anhydride (d), and the mixture is reacted at 110° C.
- An ethylenically unsaturated resin composition (solid content acid value 60.8 KOHmg/g, weight average molecular weight 5900) was obtained as a solution containing the unsaturated resin (A3-1).
- the reaction rate was calculated by measuring the acid value (monomer residual rate) in the reaction solution, it was 99.1%.
- Example 12 to 15 and Comparative Examples 7 to 9 In Examples 12 to 13, the addition amount of the fullerene solution was changed, in Example 14, the polymerization inhibitor was changed to an indene adduct of fullerene, and in Example 15, the polymerization inhibitor was changed to a soot-like substance, In Comparative Example, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 9 except that BHT was used instead of the fullerene solution. The results are shown in Table 3.
- Example 16 In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 64.3 g (0.30 mol) of 1,2,4-cyclohexanetricarboxylic acid as a polyfunctional carboxylic acid (e) and an epoxy resin were added. Asahi Kasei's AER-2603 (epoxy equivalent 188) 67.1 g, triphenylphosphine 0.54 g, PGMEA 88.1 g were added, and while blowing low oxygen air into which nitrogen gas was injected so that the oxygen concentration was 4 to 7% by volume. The temperature is raised to 120°C.
- An ethylenically unsaturated resin composition (solid content acid value 107.8 KOH mg/g, weight average molecular weight 6100), which is a solution containing the ethylenically unsaturated resin (A6), was obtained.
- the reaction rate was calculated by measuring the acid value (monomer residual rate) in the reaction solution, it was 95.4%.
- Example 17 to 20 and Comparative Examples 10 to 12 In Examples 17 to 18, the addition amount of the fullerene solution was changed, in Example 19, the polymerization inhibitor was changed to an indene adduct of fullerene, and in Example 20, the polymerization inhibitor was changed to a soot-like substance, In Comparative Example, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 13 except that BHT was used instead of the fullerene solution. The results are shown in Table 4.
- the acid value and the molecular weight of the ethylenically unsaturated resin contained in the synthesized ethylenically unsaturated resin composition were measured by the following methods.
- Method of measuring acid value According to JIS K6901 5.3.2, it was measured using a mixed indicator of bromothymol blue and phenollet. It means the mg number of potassium hydroxide required to neutralize the acidic component contained in 1 g of the ethylenically unsaturated resin (A) which is a solid content. As the solid content, the heating residue when the sample was heated at 130° C. for 2 hours was measured.
- Examples 21 to 52, Comparative Examples 13 to 20 Using the resins of Examples 1 to 20 and Comparative Examples 1, 4, 7, and 10, respectively, photosensitive resin compositions having the compositions shown in Tables 5 to 8 were prepared. In addition, the compounding amount of the resin in the table is described by the value of the solid content, and the solvent contained in the synthesis of the resin is described by being added to the item of “solvent” in the table.
- a coating film with a film thickness of 2.5 ⁇ m is prepared by the same method as the evaluation of the OD value, and the coating film is covered with a mask of a line and space pattern with a line width of 20 ⁇ m and irradiated with Multi Light ML-251D/B manufactured by Ushio Inc. Exposure (exposure amount: 50 mJ/cm2) was performed using an optical unit PM25C-100, and photocuring was performed. After irradiation, it was developed with a 0.2 mass% potassium hydroxide aqueous solution for 120 seconds and post-baked at 230° C. for 30 minutes to obtain a target pattern. The ratio of the area at the height of 5% from the bottom to the top of the pattern is T/B, and the results are shown in Table 9. The closer the T/B is to 1, the closer to the target pattern shape the better.
- the photosensitive resin containing the carbon cluster (c) has excellent dispersibility of the colorant, and a cured product excellent in pattern shape and heat yellowing can be obtained. Further, as shown in Tables 11 and 12, it is found that the photosensitive resin using the ethylenically unsaturated resin synthesized using the carbon cluster (c) has improved transparency.
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Abstract
Description
本願は、2018年11月28日に、日本に出願された特願2018-222730号に基づき優先権を主張し、その内容をここに援用する。
[1] エチレン性不飽和樹脂(A)と、
炭素クラスター(c)と、
溶剤(B)と
を含有し、
前記炭素クラスター(c)は、フラーレンおよびすす状物質のうちの少なくとも1つであり、その含有量は、前記エチレン性不飽和樹脂(A)100質量部に対して0.00001~10質量部であることを特徴とするエチレン性不飽和樹脂組成物。
[2] 前記エチレン性不飽和樹脂(A)は、エポキシ基含有共重合体(P1)のエポキシ基に、カルボキシ基含有エチレン性不飽和化合物(m-2)が開環付加し、さらに、前記エポキシ基が開環して生じたヒドロキシ基に多塩基酸無水物(d)が付加してなるエチレン性不飽和樹脂(A1)であって、
前記エポキシ基含有共重合体(P1)は、
エポキシ基含有(メタ)アクリレート(m-1)由来の構成単位と
炭素数10~20の橋かけ環式炭化水素基を有する重合性モノマー(m-3)由来の構成単位および下記化学式(1)で示される重合性モノマー(m-4)由来の構成単位からなる群から選択される少なくとも1種と、
を含有する共重合体である[1]に記載のエチレン性不飽和樹脂組成物。
[3] 前記エチレン性不飽和樹脂(A)は、エポキシ基含有エチレン性不飽和化合物(m-1)のエポキシ基に、カルボキシ基含有共重合体(P2)が開環付加してなるヒドロキシ基を有する不飽和基含有エチレン性不飽和樹脂(A2)であって、
前記カルボキシ基含有共重合体(P2)は、
カルボキシ基含有エチレン性不飽和化合物(m-2)由来の構成単位と、
炭素数10~20の橋かけ環式炭化水素基を有する重合性モノマー(m-3)由来の構成単位および下記化学式(1)で示される重合性モノマー(m-4)由来の構成単位からなる群から選択される少なくとも1種と、
を含有する共重合体である、[1]に記載のエチレン性不飽和樹脂組成物。
[4] 前記エチレン性不飽和樹脂(A)は、エポキシ樹脂(P3)のエポキシ基に、カルボキシ基含有エチレン性不飽和化合物(m-2)が開環付加し、さらに、前記エポキシ基が開環して生じたヒドロキシ基に多塩基酸無水物(d)が付加してなるエチレン性不飽和樹脂(A3)であって、
前記エポキシ樹脂(P3)は、
ノボラック型エポキシ樹脂(P3-1)、ビスフェノール型エポキシ樹脂(P3-2)、及びビフェニル骨格を有する2官能エポキシ樹脂(P3-3)からなる群から選択される少なくとも1種である[1]に記載のエチレン性不飽和樹脂組成物。
[5] 前記エチレン性不飽和樹脂(A)は、エポキシ基含有エチレン性不飽和化合物(m-1)のエポキシ基に、カルボキシ基含有樹脂(P4)が開環付加してなるヒドロキシ基を有するエチレン性不飽和樹脂(A4)であって、
前記カルボキシ基含有樹脂(P4)は、エポキシ樹脂(P3)と多官能カルボン酸(e)とを反応させてなるカルボキシ基を有する樹脂であり、
前記エポキシ樹脂(P3)は、
ノボラック型エポキシ樹脂(P3-1)、ビスフェノール型エポキシ樹脂(P3-2)、及びビフェニル骨格を有する2官能エポキシ樹脂(P3-3)からなる群から選択される少なくとも1種である[1]に記載のエチレン性不飽和樹脂組成物。
[6]前記エチレン性不飽和樹脂(A)は、
[3]に記載のエチレン性不飽和樹脂(A2)のヒドロキシ基に、多塩基酸無水物(d)が付加してなるエチレン性不飽和樹脂(A5)、又は
[5]に記載のエチレン性不飽和樹脂(A4)のヒドロキシ基に、多塩基酸無水物(d)が付加してなるエチレン性不飽和樹脂(A6)である[1]に記載のエチレン性不飽和樹脂組成物。
[7] 前記炭素クラスター(c)が、無置換のフラーレンである[1]~[6]のいずれかに記載のエチレン性不飽和樹脂組成物。
[8] 炭素クラスター(c)以外の重合禁止剤を実質的に含まない[1]~[7]のいずれかに記載のエチレン性不飽和樹脂組成物。
[9] 更に反応性希釈剤(D)を含有する[1]~[8]のいずれかに記載のエチレン性不飽和樹脂組成物。
[10][1]~[9]のいずれかに記載のエチレン性不飽和樹脂組成物と、光重合開始剤(E)とを含有する感光性樹脂組成物。
[11] さらに着色剤(F)を含有し、
前記着色剤(F)が染料および顔料からなる群から選択される少なくとも1種である、[10]に記載の感光性樹脂組成物。
[12] 炭素クラスター(c)以外の重合禁止剤を実質的に含まない[10]又は[11]に記載の感光性樹脂組成物。
[13] [10]~[12]の何れかに記載の感光性樹脂組成物を用いたレジスト。
[エチレン性不飽和樹脂組成物]
本発明のエチレン性不飽和樹脂組成物は、エチレン性不飽和樹脂(A)と、炭素クラスター(c)と、溶剤(B)とを含有する。前記炭素クラスター(c)は、フラーレンおよびすす状物質のうちの少なくとも1つである。前記炭素クラスター(c)の含有量は、前記エチレン性不飽和樹脂(A)100質量部に対して0.00001~10質量部である。前記炭素クラスター(c)が無置換のフラーレンであることが好ましい。また、本発明のエチレン性不飽和樹脂組成物が、炭素クラスター(c)以外の重合禁止剤を実質的に含まなくてもよい。「実質的に含まない」とは、前記エチレン性不飽和樹脂(A)100質量部に対して、炭素クラスター(c)以外の重合禁止剤を好ましくは0.05質量部以下、より好ましくは0.01質量部以下含む意味である。
本発明のエチレン性不飽和樹脂組成物は、炭素クラスター(c)を含有することにより、エチレン性不飽和樹脂(A)の二重結合の重合によるゲル化を防止し、保存安定性を高めることができる。また、後述する光重合開始剤(E)を含有する感光性樹脂組成物に炭素クラスター(c)を用いることで、硬化性に悪影響を与えることなく、耐熱黄変性や色材を含む微粒子分散性に優れ、パターン形状に優れたレジストが得られる感光性樹脂組成物が得られる。
本発明の炭素クラスター(c)は、フラーレンまたはすす状物質である。
すす状物質を副生するフラーレンの製造方法は、例えば抵抗加熱法、アーク放電法、マイクロ波法、高周波加熱法、CVD法、熱プラズマ法、燃焼法、レーザー法、熱分解法が挙げられる。いずれも圧力800hPa以下の環境下で製造される。すす状炭素物質は、例えばガス燃焼法の場合、炭化水素原料と酸素含有ガスとを減圧環境下で焼成することで得ることができる。炭化水素原料としては、例えばトルエン、ベンゼン等の芳香族炭化水素等を用いることができる。減圧条件としては、3~800hPa、加熱条件としては、1600℃~2000℃が好ましい。
すす状物質は、分子同士の結合が進み複数の炭素が結合しているが、フラーレンのように所定の球状の分子構造にまでは至ることができなかった無定形状炭素分子を含む。このような無定形状炭素分子としては、フラーレンの部分構造と同一の構造であり、フラーレンの製造過程で生じる中間体や、球状のフラーレンの一部が欠けたり、閉殻していない構造等を有する炭素分子が挙げられる。この無定形状炭素分子は、これらの炭素分子が複数集まったクラスター構造を形成していても良い。クラスター構造は、サイズの大きな閉殻していない構造を有する炭素分子が、サイズの小さな閉殻していない構造を有する炭素分子を内包するように構成された入れ子状の構造を含む。
炭素クラスター(c)は、エチレン性不飽和樹脂組成物に最終的に含有されていれば、本発明の効果が得られる。また、エチレン性不飽和樹脂(A)を合成する段階から炭素クラスター(c)を添加すると、より効率よくエチレン性不飽和樹脂組成物中に炭素クラスター(c)を分散させることができる。
エチレン性不飽和樹脂(A)の合成の際に用いる炭素クラスター(c)の添加量は材料となるポリマーとモノマーの合計100質量部に対して0.0001~0.1質量部が好ましく、0.005~0.05質量部がより好ましい。
反応の際に添加する炭素クラスター(c)の量が0.1質量部以下であれば、エチレン性不飽和樹脂(A)をラジカル硬化させる際にもその反応を阻害することがない。0.0001質量部以上であれば、エチレン性不飽和樹脂(A)を得る際の反応中に生じるラジカルを十分にトラップして、エチレン性不飽和樹脂(A)のゲル化を防止できる。
炭素クラスター(c)以外の重合禁止剤は、本発明に係る炭素クラスター(c)を除く、通常、エチレン性不飽和樹脂(A)に導入した二重結合の重合によるゲル化を防ぐために添加される重合禁止剤であれば、種類としては特に限定されないが、具体的には、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、ジブチルヒドロキシトルエン等が挙げられる。
本発明のエチレン性不飽和樹脂(A)は、エチレン性不飽和基を含有する樹脂であれば特に限定されないが、好ましくはエポキシ基含有化合物(a)とカルボキシ基含有化合物(b)とを反応させることにより得られる樹脂であり、前記エポキシ基含有化合物(a)と前記カルボキシ基含有化合物(b)の少なくとも一方の化合物が、エチレン性不飽和基を含有する。例えば、エポキシ基を含有する樹脂とカルボキシ基を含有する不飽和化合物とを重合禁止剤として炭素クラスター(c)及び触媒存在下で反応させる方法で得られる。あるいは、例えば、エポキシ基を含有する不飽和化合物とカルボキシ基を含有する樹脂とを重合禁止剤として炭素クラスター(c)及び触媒存在下で反応させる方法でも得られる。
本発明に係るカルボキシ基含有化合物(b)は、カルボキシ基を有する化合物であれば特に限定されない。好ましくは、後述する第一実施態様および第三実施態様におけるカルボキシ基含有エチレン性不飽和化合物(m-2)、後述する第二実施態様におけるカルボキシ基含有共重合体(P2)、後述する第四実施態様におけるカルボキシ基含有樹脂(P4)が挙げられる。
[エチレン性不飽和樹脂(A1)]
本実施態様のエチレン性不飽和樹脂(A1)は、エポキシ基含有化合物(a)であるエポキシ基含有共重合体(P1)のエポキシ基に、カルボキシ基含有化合物(b)であるカルボキシ基含有エチレン性不飽和化合物(m-2)が開環付加し、必要に応じてさらに、前記エポキシ基が開環して生じたヒドロキシ基に多塩基酸無水物(d)が付加してなるエチレン性不飽和基を有する樹脂である。前記エポキシ基含有共重合体(P1)は、エポキシ基含有エチレン性不飽和化合物(m-1)由来の構成単位と、炭素数10~20の橋かけ環式炭化水素基を有する重合性モノマー(m-3)由来の構成単位及び上記化学式(1)で示される重合性モノマー(m-4)由来の構成単位からなる群から選択される少なくとも1種と、を含有する共重合体である。エチレン性不飽和樹脂(A1)は、更に芳香環含有重合性モノマー(m-5)由来の構成単位などを含むことができる。
また、エポキシ基の全量をカルボキシ基含有エチレン性不飽和化合物(m-2)と反応させず一部を残すことで、熱による硬化性を同時に発現させることもできる。
本実施態様のエチレン性不飽和樹脂(A1)に係るエポキシ基含有共重合体(P1)(以後、単に「共重合体(P1)」と言う場合もある。)を形成するモノマー(M1)は、エポキシ基含有エチレン性不飽和化合物(m-1)と、炭素数10~20の橋かけ環式炭化水素基を有する重合性モノマー(m-3)及び上記化学式(1)で示される重合性モノマー(m-4)からなる群から選択される少なくとも1種と、を含有する。モノマー(M1)は、芳香環含有重合性モノマー(m-5)や、その他の重合性モノマー(m-6)などを更に含有することができる。芳香環含有重合性モノマー(m-5)を更に有することにより、着色剤分散性のより優れたエポキシ基含有共重合体(P1)を得ることができる。
エポキシ基含有エチレン性不飽和化合物(m-1)(以後、単に「モノマー(m-1)」と言う場合もある。)は、カルボキシ基を有さず、エポキシ基とエチレン性不飽和基を有するモノマーであれば、特に限定されない。具体例としては、グリシジル(メタ)アクリレート、2-グリシジルオキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートグリシジルエーテル、3,4-エポキシシクロヘキシルメチル(メタ)アクリレート、そのラクトン付加物(例えば、ダイセル化学工業(株)製サイクロマー(登録商標)A200、M100)、3,4-エポキシシクロヘキシルメチル-3’,4’-エポキシシクロヘキサンカルボキシレートのモノ(メタ)アクリル酸エステル、ジシクロペンテニル(メタ)アクリレートのエポキシ化物、ジシクロペンテニルオキシエチル(メタ)アクリレートのエポキシ化物等が挙げられる。これらのエポキシ基含有エチレン性不飽和化合物(m-1)は、単独で用いてもよいし、又は2種以上を用いてもよい。特に、入手のし易さおよび反応性の良さの観点から、グリシジル(メタ)アクリレートが好適である。
光硬化性を発現する感光性基の導入により、硬化膜の十分な硬度を発現するとともに、高い耐溶剤性を発現する。
重合性モノマー(m-3)(以後、単に「モノマー(m-3)」と言う場合もある。)は、炭素数10~20の橋かけ環式炭化水素基を有する。ここで、橋かけ環式炭化水素とは、アダマンタン、ノルボルナンに代表される、下記式(2)または(3)で表される構造を有するものを意味し、橋かけ環式炭化水素基とは、当該構造における一部の水素を除いた残りの部分に相当する基をいう。また、重合性モノマー(m-3)は、後述の重合性モノマー(m-4)を含まないものとする。
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重合性モノマー(m-4)(以後、単に「モノマー(m-4)」と言う場合もある。)は、下記の一般式(1)で示されるモノマーである。
芳香環含有重合性モノマー(m-5)(以後、単に「モノマー(m-5)」と言う場合もある。)は、カルボキシ基、エポキシ基を有さず、芳香環を有するモノマーである。例えば、スチレン、α-メチルスチレン、o-ビニルトルエン、m-ビニルトルエン、p-ビニルトルエン、o-クロロスチレン、m-クロロスチレン、p-クロロスチレン、o-メトキシスチレン、m-メトキシスチレン、p-メトキシスチレン、p-ニトロスチレン、p-シアノスチレン、p-アセチルアミノスチレン等の芳香族ビニル化合物;ベンジル(メタ)アクリレート、ロジン(メタ)アクリレート、フェニル(メタ)アクリレート、クミル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェノキシ-ポリエチレングリコール(メタ)アクリレート(商品名:ライトアクリレートP-200A、共栄化学社製)、ノニルフェノキシポリエチレングリコールモノ(メタ)アクリレート、o-フェノキシベンジル(メタ)アクリレート、m-フェノキシベンジル(メタ)アクリレート、p-フェノキシベンジル(メタ)アクリレート、4-フェノキシフェニル(メタ)アクリレート、ビフェニルオキシエチル(メタ)アクリレート、エトキシ化o-フェニルフェノール(メタ)アクリレート、ナフタレン(メタ)アクリレート、アントラセン(メタ)アクリレート等が挙げられる。これらの中でも、弾性回復率の観点から、本発明で用いるエチレン性不飽和樹脂(A1)には、ベンジル(メタ)クリレート、スチレン、ビフェニル骨格、ナフタレン骨格及びアントラセン骨格からなる群から選択される少なくとも1種を有する構成単位を導入することがより好ましい。
本実施態様にかかるエポキシ基含有共重合体(P1)は、モノマー(m-1)~(m-5)以外の、その他の重合性モノマー(m-6)(以後、単に「モノマー(m-6)」と言う場合もある。)が共重合されていても良い。その他の重合性モノマー(m-6)は、前記モノマー(m-1)、(m-3)、(m-4)、(m-5)、後述のモノマー(m-2)に示した以外の共重合可能なモノマーである。このモノマー(m-6)は、一般にエチレン性不飽和基を有するラジカル重合性化合物である。例えば、このモノマー(m-6)としては、(メタ)アクリル酸エステル類、(メタ)アクリル酸アミド、マレイミド類、不飽和ジカルボン酸ジエステル、ブタジエン等のジエン類などが挙げられる。(メタ)アクリル酸エステル類の具体例は、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソ-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリルレート、sec-ブチル(メタ)アクリレート、イソ-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリルレート、ペンチル(メタ)アクリレート、ネオペンチル(メタ)アクリレート、ベンジル(メタ)アクリレート、イソアミル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ドデシル(メタ)アクリレート、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、メチルシクロヘキシル(メタ)アクリレート、エチルシクロヘキシル(メタ)アクリレート、ロジン(メタ)アクリレート、アリル(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、トリフェニルメチル(メタ)アクリレート、クミル(メタ)アクリレート、3-(N,N-ジメチルアミノ)プロピル(メタ)アクリレート、ナフタレン(メタ)アクリレート、アントラセン(メタ)アクリレート等を含む。(メタ)アクリル酸アミドの具体例は、(メタ)アクリル酸アミド、(メタ)アクリル酸N,N-ジメチルアミド、(メタ)アクリル酸N,N-ジエチルアミド、(メタ)アクリル酸N,N-ジプロピルアミド、(メタ)アクリル酸N,N-ジ-イソ-プロピルアミド、(メタ)アクリル酸アントラセニルアミド等を含む。マレイミド類の具体例は、(メタ)アクリル酸アニリド、(メタ)アクリロイルニトリル、アクロレイン、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、N-ビニルピロリドン、酢酸ビニル等のビニル化合物;N-シクロヘキシルマレイミド、N-ラウリルマレイミド等を含む。不飽和ジカルボン酸ジエステルの具体例は、シトラコン酸ジエチル、マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等を含む。これらは、必要に応じて、単独でまたは2種以上を組み合わせて用いることができる。
本発明に係る共重合体(P1)において、そのモノマー(M1)が、モノマー(m-1)を含み、必要に応じて、例えば、モノマー(m-3)や、モノマー(m-4)や、モノマー(m-5)を含む場合、各モノマー由来構造の割合は、共重合反応ために添加する各重合性モノマーのモル比の値を用いる。各モノマーの配合割合(モル比)について特に制限はないが、モノマー(m-1)の配合割合は、好ましくは9~70モル%、より好ましくは13~65モル%である。モノマー(m-1)の配合割合が9モル%以上であると、感光性樹脂組成物としたときに十分な硬化性を発現することができる。モノマー(m-1)の配合割合が70モル%以下であると、モノマー(m-3)および/またはモノマー(m-4)の配合割合が十分多くなり、所望の耐熱分解性や屈折率を有するエチレン性不飽和樹脂(A1)が得られる。
モノマー(m-5)を用いる場合、その配合割合は、エポキシ基含有共重合体(P1)のモノマー(M1)の合計量100モル%に対して、0モル%超~50モル%であることが好ましく、0モル%超~40モル%であることがより好ましい。
モノマー(m-6)を用いる場合、その配合割合は、エポキシ基含有共重合体(P1)のモノマー(M1)の合計量100モル%に対して、0モル%超~10モル%であることが好ましく、0モル%超~5モル%であることがより好ましい。
本発明に係るエポキシ基含有共重合体(P1)はモノマー(M1)の共重合反応を用いて製造することができる。本発明において行われる共重合反応は、当該技術分野において公知のラジカル重合方法に従って行うことができる。例えば、共重合に用いるモノマーを溶剤に溶解した後、その溶液に重合開始剤を添加し、50~140℃、より好ましくは60~130℃で、1~20時間、より好ましくは1~12時間反応させればよい。また、50~140℃に調整した溶剤に、共重合に用いるモノマーと重合開始剤を滴下しながら反応させてもよい。
共重合反応溶媒は、後述の付加反応用溶媒を用いることができる。
これらは、単独でまたは2種以上を組み合わせて用いることができ、重合温度に応じて適当な半減期のラジカル重合開始剤を選択することが望ましい。
カルボキシ基含有エチレン性不飽和化合物(m-2)(以後、単に「モノマー(m-2)」と言う場合もある。)は、エポキシ基を有さず、酸基の中でもとりわけエポキシ基と反応性の良いカルボキシ基とエチレン性不飽和基を有するモノマーであれば特に限定されない。例えば、不飽和一塩基酸又は不飽和二塩基酸モノエステルが挙げられる。不飽和一塩基酸としては、(メタ)アクリル酸、イタコン酸、クロトン酸、桂皮酸、2-(メタ)アクリロイルオキシエチルコハク酸、2-(メタ)アクリロイルオキシエチルフタル酸、2-(メタ)アクリロイルオキシエチルヘキサヒドロフタル酸、α-ブロモ(メタ)アクリル酸、β-フリル(メタ)アクリル酸、クロトン酸、プロピオール酸、桂皮酸、α-シアノ桂皮酸、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピル、フマル酸モノメチル、イタコン酸モノエチル等の不飽和カルボン酸等が挙げられる。不飽和二塩基酸モノエステルとしては、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピル、フマル酸モノメチル、イタコン酸モノエチル等が挙げられる。これらのカルボキシ基含有エチレン性不飽和化合物(m-2)は、単独で用いてもよいし、又は2種以上を用いてもよい。これらの中でも、入手のし易さ及び反応性の観点から、(メタ)アクリル酸が好ましい。
多塩基酸無水物(d)としては、ヒドロキシ基と反応性の良い酸無水物構造を有するものであれば、特に限定されないが、反応後に副生成物が発生しない環構造を有するものが好適である。具体的には、1,2,3,6-テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、4-メチルヘキサヒドロ無水フタル酸、ビシクロ[2.2.1]ヘプタン-2,3-ジカルボン酸無水物、メチルビシクロ[2.2.1]ヘプタン-2,3-ジカルボン酸無水物、無水コハク酸、オクテニルコハク酸無水物等が挙げられる。
本実施態様に係るエチレン性不飽和樹脂(A1)は、例えば、エポキシ基含有共重合体(P1)の溶液に重合禁止剤および触媒を添加した後、カルボキシ基含有エチレン性不飽和化合物(m-2)を添加し、50~150℃、好ましくは80~130℃の条件下でエポキシ基を開環付加反応させてから、必要に応じて多塩基酸無水物(d)を添加し、付加反応させることで製造することができる。重合禁止剤として炭素クラスター(c)を用いることが好ましい。
本実施形態において用いる触媒としては、例えば、トリエチルアミンのような第3級アミン、トリエチルベンジルアンモニウムクロライドのような第4級アンモニウム塩、トリフェニルホスフィンのようなリン化合物、クロムのキレート化合物等が挙げられる。これらの触媒は、単独で用いてもよいし、2種以上を混合して用いてもよい。
本実施形態において使用する触媒の使用量は、特に限定されないが、樹脂前駆体(エポキシ基含有共重合体(P1))を100質量部とした場合に、一般的には0.01~5質量部であり、好ましくは0.1~2質量部であり、より好ましくは0.2~1質量部である。
本実施形態において使用する溶媒としては、特に限定されず、公知のものを適宜使用できる。溶媒としては、エーテル化合物、ケトン化合物、エステル化合物、芳香族炭化水素化合物、カルボン酸アミド化合物を用いることができる。エーテル化合物としては、(ポリ)アルキレングリコールモノアルキルエーテル;(ポリ)アルキレングリコールモノアルキルエーテルアセテート;ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン等の他のエーテル化合物等が挙げられる。(ポリ)アルキレングリコールモノアルキルエーテルの具体例は、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ-n-プロピルエーテル、ジエチレングリコールモノ-n-ブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、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モノエチルエーテル、ジプロピレングリコールモノ-n-プロピルエーテル、ジプロピレングリコールモノ-n-ブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル等を含む。(ポリ)アルキレングリコールモノアルキルエーテルアセテートの具体例は、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテートを含む。ケトン化合物の具体例は、メチルエチルケトン、シクロヘキサノン、2-ヘプタノン、3-ヘプタノン等を含む。エステル化合物の具体例は、2-ヒドロキシプロピオン酸メチル、2-ヒドロキシプロピオン酸エチル、2-ヒドロキシ-2-メチルプロピオン酸メチル、2-ヒドロキシ-2-メチルプロピオン酸エチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、2-ヒドロキシ-3-メチル酪酸メチル、3-メチル-3-メトキシブチルアセテート、3-メチル-3-メトキシブチルプロピオネート、酢酸エチル、酢酸n-ブチル、酢酸n-プロピル、酢酸i-プロピル、酢酸n-ブチル、酢酸i-ブチル、酢酸n-アミル、酢酸i-アミル、プロピオン酸n-ブチル、酪酸エチル、酪酸n-プロピル、酪酸i-プロピル、酪酸n-ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸n-プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソ酪酸エチル等を含む。芳香族炭化水素化合物の具体例は、トルエン、キシレン等を含む。カルボン酸アミド化合物の具体例は、N-メチルピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等を含む。これらの溶媒は、単独で用いてもよいし、2種以上を混合して用いてもよい。
[エチレン性不飽和樹脂(A2)]
本実施態様にかかるエチレン性不飽和樹脂(A2)は、エポキシ基含有化合物(a)であるエポキシ基含有エチレン性不飽和化合物(m-1)のエポキシ基に、カルボキシ基含有化合物(b)であるカルボキシ基含有共重合体(P2)が開環付加してなるヒドロキシ基とエチレン性不飽和基を含有する樹脂である。カルボキシ基含有共重合体(P2)は、少なくともカルボキシ基含有エチレン性不飽和化合物(m-2)由来の構成単位を含有し、必要に応じて、炭素数10~20の橋かけ環式炭化水素基を有する重合性モノマー(m-3)由来の構成単位や、上記一般式(1)で示される重合性モノマー(m-4)由来の構成単位や、芳香環含有重合性モノマー(m-5)由来の構成単位などを含有する共重合体である。
また、エポキシ基含有エチレン性不飽和化合物(m-1)の反応割合は、エポキシ基含有共重合体(P2)に用いる全モノマー(M2)の合計を100モル%とした場合に、好ましくは10~70モル%、より好ましくは15~65モル%である。エポキシ基含有エチレン性不飽和化合物(m-1)の配合割合が10モル%以上であると、感光性樹脂組成物としたときに十分な硬化性を発現することができる。
本実施態様のエチレン性不飽和樹脂(A2)に係るカルボキシ基含有共重合体(P2)(以後、単に「共重合体(P2)」と言う場合もある。)の全モノマー(M2)は、少なくとも、カルボキシ基含有エチレン性不飽和化合物(m-2)を含有し、必要に応じて、さらに、炭素数10~20の橋かけ環式炭化水素基を有する重合性モノマー(m-3)や、上記化学式(1)で示される重合性モノマー(m-4)や、芳香環含有重合性モノマー(m-5)や、その他の重合性モノマー(m-6)などを含有することができる。
本発明に係る共重合体(P2)において、全モノマー(M2)は、カルボキシ基含有エチレン性不飽和化合物(m-2)を含有し、必要に応じて、さらに、炭素数10~20の橋かけ環式炭化水素基を有する重合性モノマー(m-3)や、上記一般式(1)で示される重合性モノマー(m-4)や、芳香環含有重合性モノマー(m-5)などを含有する場合、各モノマー由来構造の割合は、共重合反応ために添加する各重合性モノマーのモル比の値を用いる。各モノマーの配合割合(モル比)について特に制限はないが、全モノマー(M2)の合計を100モル%とした場合に、モノマー(m-2)の配合割合は、好ましくは9~70モル%、より好ましくは13~65モル%である。モノマー(m-2)の配合割合が9モル%以上であると、感光性樹脂組成物としたときに十分な硬化性を発現することができる。モノマー(m-2)の配合割合が70モル%以下であると、モノマー(m-3)や、モノマー(a-4)や、モノマー(m-5)の配合割合が十分多くなり、所望の耐熱分解性有するエチレン性不飽和樹脂(A2)が得られる。
モノマー(m-6)を用いる場合、その配合割合は、エポキシ基含有共重合体(P2)のモノマー(M2)の合計量100モル%に対して、0モル%超~10モル%であることが好ましく、0モル%超~5モル%であることがより好ましい。
本発明に係るカルボキシ基含有共重合体(P2)は、第一実施態様に係る共重合体(P1)と同様に、共重合反応を用いて製造することができる。
エチレン性不飽和樹脂(A2)の製造方法は、エポキシ基含有エチレン性不飽和化合物(m-1)とカルボキシ基含有共重合体(P2)とを重合禁止剤及び触媒存在下で反応させてエチレン性不飽和樹脂(A2)を製造する方法であり、前記重合禁止剤が、上述の炭素クラスター(c)であることが好ましい。
本実施例態様用いるエチレン性不飽和樹脂(A3)は、エポキシ基含有化合物(a)であるエポキシ樹脂(P3)のエポキシ基にカルボキシ基含有化合物(b)であるカルボキシ基含有エチレン性不飽和化合物(m-2)が開環付加したものに、好ましくはさらに前記エポキシ基が開環して生じたヒドロキシ基に多塩基酸無水物(d)が更に付加してなる、カルボキシ基とエチレン性不飽和基を含む樹脂である。エポキシ樹脂(P3)は、ノボラック型エポキシ樹脂(P3-1)、ビスフェノール型エポキシ樹脂(P3-2)、及びビフェニル骨格を有する2官能エポキシ樹脂(P3-3)からなる群から選択されることが好ましい。
すなわち、本実施例態様用いるエチレン性不飽和樹脂(A3)としては、ノボラック型エポキシ樹脂(P3-1)にカルボキシ基含有エチレン性不飽和化合物(m-2)が付加したものに必要に応じて多塩基酸無水物(d)が更に付加しているエチレン性不飽和樹脂(A3-1)や、ビスフェノール型エポキシ樹脂(P3-2)に二塩基酸及びカルボキシ基含有エチレン性不飽和化合物(m-2)が付加したものに必要に応じて多塩基酸無水物(d)が更に付加しているエチレン性不飽和樹脂(A3-2)や、ビフェニル骨格を有する2官能エポキシ樹脂(P3-3)にカルボキシ基含有エチレン性不飽和化合物(m-2)が付加したものに必要に応じて多塩基酸無水物(d)が更に付加しているエチレン性不飽和樹脂(A3-3)等が挙げられる。
本実施例態様で用いるカルボキシ基含有エチレン性不飽和化合物(m-2)、炭素クラスター(c)、触媒、使用溶媒などは第一実施態様のものを用いることができる。
エチレン性不飽和樹脂(A3-1)は、ノボラック型エポキシ樹脂(P3-1)に二重結合を導入するためにカルボキシ基含有エチレン性不飽和化合物(m-2)を付加させた後、必要に応じてカルボキシ基を導入するために多塩基酸無水物(d)を付加させることにより製造することができる。
エチレン性不飽和樹脂(A3-2)は、ビスフェノール型エポキシ樹脂(P3-2)に二重結合を導入するためにカルボキシ基含有エチレン性不飽和化合物(m-2)を付加させた後、必要に応じてカルボキシ基を導入するために多塩基酸無水物(d)を付加させることにより製造することができる。
エチレン性不飽和樹脂(A3-3)は、ビフェニル骨格を有する2官能エポキシ樹脂(P3-3)に二重結合を導入するためにカルボキシ基含有エチレン性不飽和化合物(m-2)を付加させた後、必要に応じてカルボキシ基を導入するために多塩基酸無水物(d)を付加させることにより製造することができる。
ビフェニル骨格を有する2官能エポキシ樹脂(P3-3)としては、分子中にビフェニル骨格を有し且つ2個のエポキシ基を有するものであれば特に限定されない。ビフェニル骨格の例としては下記式(5)で表されるものが挙げられる。
カルボキシ基含有エチレン性不飽和化合物(m-2)及び必要に応じて用いられる飽和一塩基酸の付加反応は、例えば、溶媒に各原料と重合禁止剤と付加反応触媒とを添加し、好ましくは酸素ガス濃度2~10体積%、より好ましくは酸素ガス濃度5~7体積%の雰囲気で、好ましくは100~140℃、より好ましくは110~130℃で2~12時間行えばよい。
エポキシ基含有エチレン性不飽和化合物の付加反応は、好ましくは酸素ガス濃度2~10体積%、より好ましくは酸素ガス濃度5~7体積%の雰囲気で、好ましくは100~140℃、より好ましくは110~130℃で2~10時間行えばよい。
また、本発明で用いるエチレン性不飽和樹脂(A3)の好ましい構成単位比率を設定するに当たり、エポキシ樹脂(P3)に由来する構成単位に含まれるエポキシ基へのカルボキシ基含有エチレン性不飽和化合物(m-2)及び必要に応じて用いられる飽和一塩基酸に由来する構成単位の合計の付加率がエポキシ基に対して合計90~100%であることが好ましく、カルボキシ基含有エチレン性不飽和化合物(m-2)及び必要に応じて用いられる飽和一塩基酸に由来する構成単位の付加により生じたヒドロキシ基への多塩基酸無水物に由来する構成単位の付加率は5~80%であることが好ましく、10~70%であることがより好ましい。更に、多塩基酸無水物(d)に由来する構成単位の付加により生じたカルボキシ基へのエポキシ基含有エチレン性不飽和化合物(m-1)に由来する構成単位の付加率は10~50%であることが好ましい。
エチレン性不飽和樹脂(A3)の製造方法は、エポキシ樹脂(P3)とカルボキシ基含有エチレン性不飽和化合物(m-2)とを重合禁止剤及び触媒存在下で反応させてエチレン性不飽和樹脂(A3)を製造する方法であり、前記重合禁止剤が、上述の炭素クラスター(c)であることが好ましい。
本実施態様にかかるエチレン性不飽和樹脂(A4)は、エポキシ基含有化合物(a)であるエポキシ基含有エチレン性不飽和化合物(m-1)のエポキシ基に、カルボキシ基含有化合物(b)であるカルボキシ基含有樹脂(P4)が開環付加してなるヒドロキシ基を有するエチレン性不飽和樹脂である。
エポキシ基含有エチレン性不飽和化合物(m-1)の付加量は、カルボキシ基含有樹脂(P4)100質量部に対して、0質量部超~10質量部であることが好ましい。エポキシ基含有エチレン性不飽和化合物(m-1)の付加量が0質量部超であれば、感度を高めることができるため好ましい。一方、エポキシ基含有エチレン性不飽和化合物(m-1)の付加量が10質量部以下であれば、弾性回復率や現像性を維持できるため好ましい。
エチレン性不飽和樹脂(A4)中のカルボキシ基含有樹脂(P4)由来の構成単位に対し、付加したエポキシ基含有エチレン性不飽和化合物(m-1)のモル比は0.05~0.3であることが好ましい。
本実施態様に用いるカルボキシ基含有樹脂(P4)は、エポキシ樹脂(P3)と多官能カルボン酸(e)とを反応させてなるカルボキシ基を有する樹脂である。
エポキシ樹脂(P3)は、第三実施態様に用いるエポキシ樹脂(P3)を用いることができる。
多官能カルボン酸(e)としては、特に限定されない。飽和、不飽和の多官能カルボン酸のいずれであっても良い。具体的には、アジピン酸、イタコン酸、コハク酸、シュウ酸、マロン酸、フタル酸、フマル酸、マレイン酸、グルタル酸、酒石酸、グルタミン酸、セバシン酸等が挙げられる。二塩基酸は、単独で用いてもよいし、又は2種以上を用いてもよい。これらの中でも、反応性の観点から、アジピン酸及びイタコン酸が好ましい。
カルボキシ基含有樹脂(P4)は、エポキシ樹脂(P3)由来の構成単位30~80質量%と、多官能カルボン酸(e)由来の構成単位20~70質量%とを含むことが好ましい。ここで、カルボキシ基含有樹脂(P4)中のエポキシ樹脂(P3)由来の構成単位に対し、多官能カルボン酸(e)由来の構成単位のモル比は0.1~0.8であることが好ましく、0.15~0.7であることがより好ましい。
本実施態様に用いるカルボキシ基含有樹脂(P4)は、例えば、付加触媒の存在下で、エポキシ樹脂(P3)と多官能カルボン酸(e)とを付加反応させて製造することができる。
本実施態様に用いるカルボキシ基含有樹脂(P4)を得るための付加反応の条件は、常法に従って適宜設定すればよい。付加反応は、例えば、溶媒に各原料と付加触媒とを添加し、好ましくは酸素ガス濃度2~10体積%、より好ましくは酸素ガス濃度5~7体積%の雰囲気で、好ましくは50~150℃、より好ましくは60~140℃で1~12時間行えばよい。
上記した付加反応に用いることができる重縮合触媒としては、特に限定されず、公知のものを適宜使用することができる。例えば、第一実施態様の付加反応に用いる触媒を使用することができる。
エチレン性不飽和樹脂(A4)の製造方法は、エポキシ基含有エチレン性不飽和化合物(m-1)とカルボキシ基含有樹脂(P4)とを重合禁止剤及び触媒存在下で反応させてエチレン性不飽和樹脂(A4)を製造する方法であり、前記重合禁止剤が、炭素クラスター(c)であることが好ましい。カルボキシ基含有樹脂(P4)は、エポキシ樹脂(P3)と多官能カルボン酸(e)とを反応させてなるカルボキシ基を有する樹脂である。
[エチレン性不飽和樹脂(A5)]
本実施態様のエチレン性不飽和樹脂(A5)は、第二実施態様における上記エチレン性不飽和樹脂(A2)のヒドロキシ基に、更に多塩基酸無水物(d)が付加してからなるエチレン不飽和基を含有する樹脂である。上記ヒドロキシ基は、エポキシ基含有エチレン性不飽和化合物(m-1)のエポキシ基にカルボキシ基含有共重合体(P2)が開環付加して生じたヒドロキシ基である。
また、カルボキシ基含有共重合体(P2)のカルボキシ基の全量をエポキシ基と反応させず一部を残すことで、カルボン酸も同時に導入することができる。さらに、得られた水酸基に多塩基酸無水物を付加させ、カルボン酸の導入量を増やすこともできる。
また、多塩基酸無水物(d)の反応割合は、モノマー(m-1)、ならびにカルボキシ基含有共重合体(P2)を構成するモノマー(m-2)、任意のモノマー(m-3)および/またはモノマー(m-4)、任意のモノマー(m-5)などの合計を100モル%とした場合に、好ましくは5~65モル%、より好ましくは5~50モル%である。多塩基酸無水物(d)の配合割合が5モル%以上であると、感光性樹脂組成物としたときに、さらなる硬化性を発現することができる。多塩基酸無水物(d)の配合割合が65モル%以下であると、所望の屈折率を有する共重合体が得られる。
エチレン性不飽和樹脂(A5)は、エチレン性不飽和樹脂(A2)を製造した後、多塩基酸無水物(d)を添加し、50~150℃、好ましくは80~130℃の条件下でヒドロキシ基と多塩基酸無水物(d)を反応させることで製造することができる。
[エチレン性不飽和樹脂(A6)]
本実施態様のエチレン性不飽和樹脂(A6)は、第四実施態様における上記エチレン性不飽和樹脂(A4)のヒドロキシ基に、更に多塩基酸無水物(d)が付加してからなるエチレン不飽和基を含有する樹脂である。上記ヒドロキシ基は、エポキシ基含有エチレン性不飽和化合物(m-1)のエポキシ基にカルボキシ基含有樹脂(P4)が開環付加して生じたヒドロキシ基である。
また、カルボキシ基含有樹脂(P4)のカルボキシ基の全量をエポキシ基と反応させず一部を残すことで、カルボン酸も同時に導入することができる。さらに、得られた水酸基に多塩基酸無水物を付加させ、カルボン酸の導入量を増やすこともできる。
多塩基酸無水物(d)の割合が10%モル以上であると、感光性樹脂組成物としたときに、さらなる硬化性を発現することができる。90モル%以下であると、多塩基酸無水物(d)の未反応物が残らず、所望のエチレン性不飽和樹脂(A6)が得られる。
また、多塩基酸無水物(d)の反応割合は、エチレン性不飽和樹脂(A6)に対して、0質量%超~10質量%であることが好ましい。多塩基酸無水物(d)の付加量が0質量%超であれば、感度を高めることができるため好ましい。一方、多塩基酸無水物(d)の付加量が10質量%以下であれば、弾性回復率や現像性を維持できるため好ましい。
エチレン性不飽和樹脂(A6)は、エチレン性不飽和樹脂(A4)を製造した後、多塩基酸無水物(d)を添加し、50~150℃、好ましくは80~130℃の条件下でヒドロキシ基と多塩基酸無水物(d)を反応させることで製造することができる。
本発明第一実施態様~第六実施態様で得られるエチレン性不飽和樹脂(A)の分子量(ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算の重量平均分子量)は、好ましくは1000~50000、より好ましくは3000~40000である。この分子量が1000以上であると、硬化膜の耐溶剤性や耐熱分解性が十分に確保できる。一方、この分子量が50000以下であると、分子量や粘度を適切な範囲に制御することができ、実用的である。また、弾性回復率の観点から、重量平均分子量は3000~30000であることが好ましい。
なお、本明細書における水酸基当量は、ヒドロキシ基のモル数当たりのエチレン性不飽和樹脂(A)の質量であり、反応率100%として原料の仕込み量から計算した理論値である。
なお、本明細書において、不飽和基当量は、不飽和基を導入するために用いられる原料が全量反応したと仮定した時の仕込み量から計算した理論値である。
なお、前記エポキシ当量とは、重合体のエポキシ基1モル当たりの重合体の質量である。この値は、重合体の質量を重合体のエポキシ基量で除することにより求めることが可能である(g/モル)。本明細書において「エポキシ当量」は、エポキシ基を導入するために用いられる原料の仕込み量と付加反応させるカルボキシ基含有化合物(b)の仕込み量から反応率100%として計算した、理論値である。
エチレン性不飽和樹脂組成物の溶剤(B)は、エチレン性不飽和樹脂(A)と反応しない溶剤であれば特に限定されない。溶剤(B)としては、エチレン性不飽和樹脂(A)を製造する際に用いた溶剤と同じものを用いることができ、反応後に含まれている溶剤をそのまま用いることもでき、さらに加えることもできる。また、その他の成分を加える際に、そこに共存しているものでも良い。溶剤(B)の具体例として、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、酢酸エチル、酢酸ブチル、酢酸イソプロピル、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、トリプロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールエチルエーテルアセテート等が挙げられる。これらは、単独で、または2種以上を組み合わせて用いることができる。また、これらの中でも、エチレン性不飽和樹脂(A)を製造する際において使用されるプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコールエーテル系溶剤が好ましい。
反応性希釈剤(D)としては特に限定されないが、エチレン性不飽和二重結合、好ましくは、ビニル基、(メタ)アクリロイルオキシ基を含むものが好ましい。具体例としては、スチレン、α-メチルスチレン、α-クロロメチルスチレン、ビニルトルエン、ジビニルベンゼン、ジアリルフタレート、ジアリルベンゼンホスホネート等の芳香族ビニル系モノマー類;酢酸ビニル、アジピン酸ビニル等のポリカルボン酸モノマー類;メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、β-ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリス(ヒドロキシエチル)イソシアヌレートのトリ(メタ)アクリレート等の(メタ)アクリル系モノマー;トリアリルシアヌレート等が挙げられる。これらは、単独で、または2種以上を組み合わせて用いることができる。
本発明の感光性樹脂組成物本発明は、エチレン性不飽和樹脂(A)と、炭素クラスター(c)と、溶剤(B)と反応性希釈剤(D)と光重合開始剤(E)とを含む。本発明の感光性樹脂組成物本発明は、更に着色剤(F)を含んでもよい。
また、本発明の感光性樹脂組成物が、炭素クラスター(c)以外の重合禁止剤を実質的に含まなくてもよい。「実質的に含まない」とは、前記エチレン性不飽和樹脂(A)100質量部に対して、炭素クラスター(c)以外の重合禁止剤を0.010質量部以下、好ましく、0.05質量部以下含む意味である。
光重合開始剤(E)としては特に限定されないが、具体例として、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等のベンゾインとそのアルキルエーテル類;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、1,1-ジクロロアセトフェノン、4-(1-t-ブチルジオキシ-1-メチルエチル)アセトフェノン等のアセトフェノン類;2-メチルアントラキノン、2-アミルアントラキノン、2-t-ブチルアントラキノン、1-クロロアントラキノン等のアントラキノン類;2,4-ジメチルチオキサントン、2,4-ジイソプロピルチオキサントン、2-クロロチオキサントン等のチオキサントン類;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等のケタール類;ベンゾフェノン、4-(1-t-ブチルジオキシ-1-メチルエチル)ベンゾフェノン、3,3’,4,4’-テトラキス(t-ブチルジオキシカルボニル)ベンゾフェノン等のベンゾフェノン類;2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノ-プロパン-1-オン;2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)ブタノン-1;アシルホスフィンオキサイド類;およびキサントン類等が挙げられる。これらは、単独で、または2種以上を組み合わせて用いることができる。
着色剤(F)としては、溶剤(B)に溶解または分散するものであれば特に限定されず、公知の染料または顔料を用いることができる。着色剤(F)として染料を用いる場合、顔料を用いる場合と比べ高輝度な着色パターンを得ることができ、また良好なアルカリ現像性を示す。一方、着色剤(F)として顔料を用いる場合、染料を用いる場合と比べ着色パターンの耐熱性が高い。求められる性能や目的とする画素の色に応じて、染料と顔料を併用しても良い。
染料としては、溶剤(B)やアルカリ現像液に対する溶解性、感光性樹脂組成物中の他の成分との相互作用、耐熱性等の観点から、カルボキシ基等の酸性基を有する酸性染料、酸性染料の窒素化合物との塩、酸性染料のスルホンアミド体等を用いることが好ましい。このような染料の具体例としては、acid alizarin violet N;acid black1、2、24、48;acid blue1、7、9、25、29、40、45、62、70、74、80、83、90、92、112、113、120、129、147;acid chrome violet K;acid Fuchsin;acid green1、3、5、25、27、50;acid orange6、7、8、10、12、50、51、52、56、63、74、95;acid red1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、69、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、183、198、211、215、216、217、249、252、257、260、266、274;acid violet 6B、7、9、17、19;acid yellow1、3、9、11、17、23、25、29、34、36、42、54、72、73、76、79、98、99、111、112、114、116; food yellow 3およびこれらの誘導体等が挙げられる。
これらの中でも、アゾ系、キサンテン系、アントラキノン系またはフタロシアニン系の酸性染料が好ましい。これらの染料は、目的とする画素の色に応じて、単独で、または2種以上を組み合わせて用いることができる。
顔料の具体例としては、C.I.ピグメントイエロー1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214等の黄色顔料;C.I.ピグメントオレンジ13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等の橙色顔料;C.I.ピグメントレッド9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等の赤色顔料;C.I.ピグメントブルー15、15:3、15:4、15:6、60等の青色顔料;C.I.ピグメントバイオレット1、19、23、29、32、36、38等のバイオレット色顔料;C.I.ピグメントグリーン7、36、58等の緑色顔料;C.I.ピグメントブラウン23、25等の茶色顔料;C.I.ピグメントブラック1、7、カーボンブラック、チタンブラック、酸化鉄等の黒色顔料等が挙げられる。これらの顔料は、目的とする画素の色に応じて、単独で、または2種以上を組み合わせて用いることができる。
本実施の形態の樹脂組成物における、エチレン性不飽和樹脂(A)、炭素クラスター(c)と、溶剤(B)の配合量は、樹脂組成物中の溶剤(B)を除く成分の総和を100質量部とすると、エチレン性不飽和樹脂(A)が、50~99.9質量部であることが好ましく;炭素クラスター(c)が0.00001~10質量部であることが好ましく;溶剤(B)が30~1000質量部であることが好ましく、50~800質量部であることがより好ましく、100~700質量部であることが更に好ましい。
[感光性樹脂組成物の組成]
本実施の形態の感光性樹脂組成物は、公知の混合装置を用い、上記の各成分を混合することによって製造することができる。なお、本実施の形態の感光性樹脂組成物は、先にエチレン性不飽和樹脂(A)および溶剤(B)を含む樹脂組成物を調製した後、反応性希釈剤(D)、光重合開始剤(E)を混合して製造することも可能である。なお、当該樹脂組成物は、本実施の形態の感光性樹脂組成物を調製するために用いることができるほか、他の用途で使用することも可能である。
本実施形態の感光性樹脂組成物は、本実施形態の樹脂を含むため、優れた現像性を有し、かつ着色剤分散性および耐溶剤性が良好で高い弾性回復率を有する硬化膜が得られる。
したがって、本実施形態の感光性樹脂組成物は、ブラックマトリックス、カラーフィルター、ブラックカラムスペーサの材料として好適である。
また、本実施形態の感光性樹脂組成物は、良好な着色剤分散性を有し、黒色の着色剤を十分に含むものであっても、現像性等の一般的特性を十分満足でき、被形成面に対する密着性が良好な樹脂硬化膜を形成できる。このため、本実施形態の感光性樹脂組成物によれば、被形成面に対する密着性が良好で、十分な遮光性を有する黒色パターンを形成できる。
本実施形態の樹脂硬化膜は、例えば、以下に示す方法により製造できる。
まず、樹脂硬化膜の被形成面上に感光性樹脂組成物を塗布し、樹脂層(塗膜)を形成する。次いで、所定のパターンのマスクを介して、樹脂層を露光し、露光部分を光硬化させる。次に、樹脂層の未露光部分を現像液で現像し、所定のパターンを有する樹脂硬化膜とする。その後、必要に応じて、樹脂硬化膜のポストベーク(熱処理)を行う。
樹脂層を露光する際には、所定のパターンのハーフトーンマスクを用いてもよい。この場合、未露光部分及び半露光部分を現像液で現像して、所定のパターンを有する樹脂硬化膜とする。
感光性樹脂組成物を塗布した後には、必要に応じて、循環式オーブン、赤外線ヒーター、ホットプレート等の加熱手段を用いて加熱することにより、樹脂層に含まれる溶剤(B)を揮発させてもよい。塗布後の加熱条件は、特に限定されず、感光性樹脂組成物の組成に応じて適宜設定すればよい。例えば、塗布後の加熱温度は50℃~120℃とすることができ、加熱時間は30秒~30分間とすることができる。
樹脂層に照射するエネルギー線量は、感光性樹脂組成物の組成に応じて適宜設定すればよい。例えば、樹脂層に照射するエネルギー線量は、30~2000mJ/cm2とすることができるが、この範囲に限定されない。
露光に用いる光源としては、特に限定されないが、低圧水銀ランプ、中圧水銀ランプ、高圧水銀ランプ、キセノンランプ、メタルハライドランプ等を任意に選択して用いることができる。
現像液には、必要に応じて、消泡剤、界面活性剤等が含まれていてもよい。
また、現像液で現像した後には、所定のパターンを有する樹脂硬化膜のポストベーク(熱処理)を行うことが好ましい。ポストベークを行うことにより、樹脂硬化膜の硬化をより進めることができる。ポストベークの条件としては、特に限定されず任意に選択でき、感光性樹脂組成物の組成に応じて適宜設定すればよい。例えば、ポストベークの加熱温度は130℃~250℃とすることができる。また、ポストベークの加熱時間は10分~4時間であることが好ましく、より好ましくは20分~2時間である。
本実施形態の画像表示装置は、本実施形態の樹脂硬化膜を備える。画像表示装置の具体例としては、例えば、液晶表示装置、有機EL表示装置等が挙げられる。
画像表示装置としては、例えば、ブラックマトリックス、カラーフィルター、ブラックカラムスペーサから選ばれる1以上の部材が、本実施形態の樹脂硬化膜で形成されていることが好ましい。
[実施例1]
攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート137.5gを加え、窒素置換しながら攪拌し、120℃に昇温した。次いで、グリシジルメタクリレート141.7g(1.00モル)、トリシクロデカニルメタクリレート4.7g(0.02モル)、及びスチレン5.0g(0.05モル)からなる単量体混合物に、13.3gのt-ブチルパーオキシ-2-エチルヘキサノエート(重合開始剤、日油社製、パーブチル(登録商標)O)を添加したものを、滴下ロートから2時間にわたって前記フラスコ中に滴下した。滴下終了後、120℃でさらに2時間攪拌して共重合反応を行い、エポキシ基含有共重合体(P1)溶液を生成させた。そこにモノマー(m-2)としてアクリル酸72.0g、重合禁止剤としてフラーレン(フロンティアカーボン社製、nanom(登録商標) mix ST)3質量%を含むトリメチルベンゼン溶液を6.0g、触媒としてトリフェニルホスフィンを0.67g(0.3質量部)を仕込み、酸素濃度が4~7体積%となるように窒素ガスを注入した低酸素エアーを吹き込みながら110℃で10時間加熱した。
その後、酸価が1.0KOHmg/g以下であることを確認して、多塩基酸無水物(d)としてテトラヒドロフタル酸無水物を15.6g仕込み110℃で2時間反応させ、固形分濃度50質量%のエチレン性不飽和樹脂(A1)を含む溶液であるエチレン性不飽和樹脂組成物(固形分酸価32.4KOHmg/g、重量平均分子量9400)を得た。なお固形分とは、エチレン性不飽和樹脂(A1)溶液を130℃で2時間加熱したときの加熱残分を意味し、エチレン性不飽和樹脂(A1)が主成分となる。
反応溶液中の酸価(単量体残存率)を測定することにより、エポキシ基へのアクリル酸の付加反応率を算出したところ99.1%であった。
実施例2~3においてはフラーレン溶液の添加量を変更し、実施例4においてはフラーレン溶液の代わりにフラーレンのインデン付加体(フロンティアカーボン社製、nanom(登録商標) spectra NPQ3000)の溶液(濃度0.02質量%)に変更し、比較例においてはフラーレン溶液の代わりにBHT(ジ-t-ブチルヒドロキシトルエン)を使用した以外は実施例1と同様にしてエチレン性不飽和樹脂を含む溶液である組成物を得た。結果を表1に示す。
[実施例5]
実施例5においては重合禁止剤をすす状物質0.02質量%に変更した以外は実施例1と同様にしてエチレン性不飽和樹脂溶液を得た。すす状物質は、次の方法で得たものを使用した。トルエンと純酸素ガスを比3:1になるようにして反応管に供給して混合し、67hPa、180℃の条件で加熱して煤を得た。次いで、トルエンで2回洗浄を行い、すす状物質を得た。結果を表1に示す。
攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート185.6gを加え、窒素置換しながら攪拌し、120℃に昇温した。
次いで、メタクリル酸58.5g(0.68モル)、トリシクロデカニルメタクリレート33.7g(0.15モル)及び、ベンジルメタクリレート3.0g(0.02モル)からなる単量体混合物に、2.9gのt-ブチルパーオキシ-2-エチルヘキサノエート(重合開始剤、日油社製、パーブチル(登録商標)O)を添加したものを、滴下ロートから2時間にわたって前記フラスコ中に滴下した。滴下終了後、120℃でさらに2時間攪拌して共重合反応を行い、カルボキシ基含有共重合体(P2)溶液を生成させた。そこにモノマー(m-1)としてグリシジルメタクリレート35g、重合禁止剤としてフラーレン(フロンティアカーボン社製、nanom(登録商標) mix ST)3質量%を含むトリメチルベンゼン溶液を3.5g、触媒としてトリフェニルホスフィン0.39g(0.3質量部)を仕込み、酸素濃度が4%~7%となるように窒素ガスを注入した低酸素エアーを吹き込みながら110℃で10時間加熱した。
その後、酸価が72.0KOHmg/g以下であることを確認して、固形分濃度28.6質量%のエチレン性不飽和樹脂(A2)を含む溶液であるエチレン性不飽和樹脂組成物(固形分酸価196.8KOHmg/g、重量平均分子量18500)を得た。
反応溶液中の酸価を測定することにより、酸とエポキシの反応率を算出したところ97.8%であった。
実施例6~8においてはフラーレン溶液の添加量を変更し、実施例9においては重合禁止剤をフラーレンのインデン付加体に変更し、実施例10においては重合禁止剤をすす状物質に変更し、比較例においてはフラーレン溶液の代わりにBHTを使用した以外は実施例1と同様にしてエチレン性不飽和樹脂組成物を得た。結果を表2に示す。
攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、エポキシ樹脂(P3)であるDIC株式会社製クレゾールノボラック系エポキシN-695(エポキシ当量215)を224.1gとPGMEA94.5gを加え酸素濃度が4~7体積%となるように窒素ガスを注入した低酸素エアーを吹き込みながら120℃へ昇温する。その後酸価が42.0KOHmg/g以下であることを確認しモノマー(m-2)としてアクリル酸75.1g(1.04モル)にフラーレン(フロンティアカーボン社製、nanom(登録商標) mix ST)3質量%を含むトリメチルベンゼン溶液を8g、トリフェニルホスフィン0.9gを溶解させたものを10分間にわたって滴下する。その後酸価が1以下となるまで反応を続け、多塩基酸無水物(d)としてコハク酸無水物を33.4g仕込み110℃で1時間反応させ、固形分濃度38.5重量%のエチレン性不飽和樹脂(A3-1)を含む溶液であるエチレン性不飽和樹脂組成物(固形分酸価60.8KOHmg/g、重量平均分子量5900)を得た。
反応溶液中の酸価(単量体残存率)を測定することにより、反応率を算出したところ99.1%であった。
実施例12~13においてはフラーレン溶液の添加量を変更し、実施例14においては重合禁止剤をフラーレンのインデン付加体に変更し、実施例15においては重合禁止剤をすす状物質に変更し、比較例においてはフラーレン溶液の代わりにBHTを使用した以外は実施例9と同様にしてエチレン性不飽和樹脂組成物を得た。結果を表3に示す。
攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、多官能カルボン酸(e)として1,2,4-シクロヘキサントリカルボン酸64.3g(0.30モル)とエポキシ樹脂として旭化成社製AER-2603(エポキシ当量188)67.1g、トリフェニルホスフィン0.54g、PGMEA88.1gを加え酸素濃度が4~7体積%となるように窒素ガスを注入した低酸素エアーを吹き込みながら120℃まで昇温する。その後酸価が138KOHmg/g以下となるまで反応させ、カルボキシ基含有樹脂(P4)とした後、モノマー(m-1)としてグリシジルメタクリレート50.7gにフラーレン(フロンティアカーボン社製、nanom(登録商標) mix ST)3質量量%を含むトリメチルベンゼン用液を4.9g加えたものを10分間で滴下する。酸価が40KOHmg/g以下となることを確認し、多塩基酸無水物(d)としてコハク酸無水物17.9gを加えて110℃で1時間反応させ、固形分濃度48.5重量%のエチレン性不飽和樹脂(A6)を含む溶液であるエチレン性不飽和樹脂組成物(固形分酸価107.8KOHmg/g、重量平均分子量6100)を得た。
反応溶液中の酸価(単量体残存率)を測定することにより、反応率を算出したところ95.4%であった。
実施例17~18においてはフラーレン溶液の添加量を変更し、実施例19においては重合禁止剤をフラーレンのインデン付加体に変更し、実施例20においては重合禁止剤をすす状物質に変更し、比較例においてはフラーレン溶液の代わりにBHTを使用した以外は実施例13と同様にしてエチレン性不飽和樹脂組成物を得た。結果を表4に示す。
[酸価の測定法]
JIS K6901 5.3.2に従って、ブロモチモールブルーとフェノールレットの混合指示薬を用いて測定した。固形分であるエチレン性不飽和樹脂(A)1g中に含まれる酸性成分を中和するのに要する水酸化カリウムのmg数を意味する。
なお、固形分は、試料を130℃で2時間加熱した時の加熱残分を測定した。
ゲルパーミエーションクロマトグラフィー(GPC)を用いて、下記条件にて測定し、標準ポリスチレン換算した。
カラム:ショウデックス(登録商標) LF-804+LF-804(昭和電工株式会社製)
カラム温度:40℃
試料:共重合体の0.2%テトラヒドロフラン溶液
展開溶媒:テトラヒドロフラン
検出器:示差屈折計(ショウデックス(登録商標) RI-71S)(昭和電工株式会社製)
流速:1mL/min
それぞれ実施例1~20及び比較例1,4,7,10の樹脂を使用し、表5~8に示す配合を組んだ感光性樹脂組成物を作製した。なお、表中の樹脂の配合量は固形分の値で記載し、樹脂の合成の際に含まれていた溶剤は、表中の「溶剤」の項目に合算して記載した。
ガラス基板上に、実施例21~36、比較例13~16の感光性樹脂組成物を使用し、スピンコーターで膜厚1.5μmとなるように塗膜を作製した。その後作製した塗膜を90℃で3分間加熱することにより、塗膜中の溶剤を揮発させた。次に、塗膜の全面をウシオ電機株式会社製マルチライトML-251D/Bと照射光学ユニットPM25C-100を用いて露光(露光量200mJ/cm2)し、光硬化させた。照射後、230℃で30分後硬化を行った膜をX-rite社製OD値計 361Tを用いてOD値を測定した。結果を表9に示す。OD値が大きいほどより光を通さずブラックマトリックスとしては良好である。
OD値の評価と同様な方法で膜厚2.5μmの塗膜を作製し、塗膜に線幅20μmのライン&スペースパターンのマスクを被せウシオ電機株式会社製マルチライトML-251D/Bと照射光学ユニットPM25C-100を用いて露光(露光量50mJ/cm2)し、光硬化させた。照射後0.2質量%の水酸化カリウム水溶液で120秒間現像し、更に230℃で30分間ポストベークすることで、目的とするパターンを得た。パターンの下部と上部から下に5%の高さにおける面積の比をT/Bとし、結果を表9に示す。T/Bが1に近いほど目的のパターン形状に近く良い。
ガラス基板上に、それぞれ実施例37~52、比較例17~20の感光性樹脂組成物を使用し、表6に示す配合を組んだものを作製し、スピンコーターで膜厚2.5μmとなるように塗膜を作製した。その後作製した塗膜を90℃で3分間加熱することにより、塗膜中の溶剤を揮発させた。次に、塗膜の全面をウシオ電機株式会社製マルチライトML-251D/Bと照射光学ユニットPM25C-100を用いて露光(露光量50mJ/cm2)し、光硬化させた。照射後、230℃で30分後硬化を行った膜をSIMAZU社製UVスペクトルメータUV-1650PCを用いて樹脂硬化膜の極大吸収波長の吸光度を測定した。
結果を表10に示す。ΔEabが小さいほど黄変が少なく良い。
耐熱黄変性の評価と同様に塗膜を作製し、波長380nmから780nmまでの透過率を測定した。各波長の透過率の平均値を平均透過率(%)とした。
実施例37~44と比較例17と18の結果を表11に示す。実施例45~52と比較例19と20の結果を表12に示す。
Claims (13)
- エチレン性不飽和樹脂(A)と、
炭素クラスター(c)と、
溶剤(B)と
を含有し、
前記炭素クラスター(c)は、フラーレンおよびすす状物質のうちの少なくとも1つであり、その含有量は、前記エチレン性不飽和樹脂(A)100質量部に対して0.00001~10質量部である
ことを特徴とするエチレン性不飽和樹脂組成物。 - 前記エチレン性不飽和樹脂(A)は、エポキシ基含有共重合体(P1)のエポキシ基に、カルボキシ基含有エチレン性不飽和化合物(m-2)が開環付加し、さらに、前記エポキシ基が開環して生じたヒドロキシ基に多塩基酸無水物(d)が付加してなるエチレン性不飽和樹脂(A1)であって、
前記エポキシ基含有共重合体(P1)は、
エポキシ基含有(メタ)アクリレート(m-1)由来の構成単位と
炭素数10~20の橋かけ環式炭化水素基を有する重合性モノマー(m-3)由来の構成単位および下記化学式(1)で示される重合性モノマー(m-4)由来の構成単位からなる群から選択される少なくとも1種と、
を含有する共重合体である
請求項1に記載のエチレン性不飽和樹脂組成物。
- 前記エチレン性不飽和樹脂(A)は、エポキシ基含有エチレン性不飽和化合物(m-1)のエポキシ基に、カルボキシ基含有共重合体(P2)が開環付加してなるヒドロキシ基を有する不飽和基含有エチレン性不飽和樹脂(A2)であって、
前記カルボキシ基含有共重合体(P2)は、
カルボキシ基含有エチレン性不飽和化合物(m-2)由来の構成単位と、
炭素数10~20の橋かけ環式炭化水素基を有する重合性モノマー(m-3)由来の構成単位および下記化学式(1)で示される重合性モノマー(m-4)由来の構成単位からなる群から選択される少なくとも1種と、
を含有する共重合体である、
請求項1に記載のエチレン性不飽和樹脂組成物。
- 前記エチレン性不飽和樹脂(A)は、エポキシ樹脂(P3)のエポキシ基に、カルボキシ基含有エチレン性不飽和化合物(m-2)が開環付加し、さらに、前記エポキシ基が開環して生じたヒドロキシ基に多塩基酸無水物(d)が付加してなるエチレン性不飽和樹脂(A3)であって、
前記エポキシ樹脂(P3)は、
ノボラック型エポキシ樹脂(P3-1)、ビスフェノール型エポキシ樹脂(P3-2)、及びビフェニル骨格を有する2官能エポキシ樹脂(P3-3)からなる群から選択される少なくとも1種である
請求項1に記載のエチレン性不飽和樹脂組成物。 - 前記エチレン性不飽和樹脂(A)は、エポキシ基含有エチレン性不飽和化合物(m-1)のエポキシ基に、カルボキシ基含有樹脂(P4)が開環付加してなるヒドロキシ基を有するエチレン性不飽和樹脂(A4)であって、
前記カルボキシ基含有樹脂(P4)は、エポキシ樹脂(P3)と多官能カルボン酸(e)とを反応させてなるカルボキシ基を有する樹脂であり、
前記エポキシ樹脂(P3)は、
ノボラック型エポキシ樹脂(P3-1)、ビスフェノール型エポキシ樹脂(P3-2)、及びビフェニル骨格を有する2官能エポキシ樹脂(P3-3)からなる群から選択される少なくとも1種である
請求項1に記載のエチレン性不飽和樹脂組成物。 - 前記エチレン性不飽和樹脂(A)は、
請求項3に記載のエチレン性不飽和樹脂(A2)のヒドロキシ基に、多塩基酸無水物(d)が付加してなるエチレン性不飽和樹脂(A5)、又は
請求項5に記載のエチレン性不飽和樹脂(A4)のヒドロキシ基に、多塩基酸無水物(d)が付加してなるエチレン性不飽和樹脂(A6)である請求項1に記載のエチレン性不飽和樹脂組成物。 - 前記炭素クラスター(c)が、無置換のフラーレンである請求項1~6のいずれか1項に記載のエチレン性不飽和樹脂組成物。
- 炭素クラスター(c)以外の重合禁止剤を実質的に含まない請求項1~7のいずれか1項に記載のエチレン性不飽和樹脂組成物。
- 更に反応性希釈剤(D)を含有する請求項1~8のいずれか1項に記載のエチレン性不飽和樹脂組成物。
- 請求項1~9のいずれか1項に記載のエチレン性不飽和樹脂組成物と、
光重合開始剤(E)と
を含有する感光性樹脂組成物。 - さらに着色剤(F)を含有し、
前記着色剤(F)が染料および顔料からなる群から選択される少なくとも1種である、請求項10に記載の感光性樹脂組成物。 - 炭素クラスター(c)以外の重合禁止剤を実質的に含まない請求項10又は11に記載の感光性樹脂組成物。
- 請求項10~12のいずれか1項に記載の感光性樹脂組成物を用いたレジスト。
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JP2008076860A (ja) * | 2006-09-22 | 2008-04-03 | Showa Highpolymer Co Ltd | 感光性樹脂組成物 |
JP2011093970A (ja) * | 2009-10-28 | 2011-05-12 | Showa Denko Kk | 感光性樹脂 |
WO2012141000A1 (ja) * | 2011-04-11 | 2012-10-18 | 昭和電工株式会社 | 共重合体、その共重合体を含む樹脂組成物及び感光性樹脂組成物、並びにカラーフィルター |
JP2015067734A (ja) * | 2013-09-30 | 2015-04-13 | 昭和電工株式会社 | 感光性樹脂の製造方法及びカラーフィルター |
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JPWO2020111022A1 (ja) | 2021-10-21 |
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