JP6095408B2 - Novel photopolymerization initiator and photosensitive resin composition using them - Google Patents
Novel photopolymerization initiator and photosensitive resin composition using them Download PDFInfo
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- JP6095408B2 JP6095408B2 JP2013031159A JP2013031159A JP6095408B2 JP 6095408 B2 JP6095408 B2 JP 6095408B2 JP 2013031159 A JP2013031159 A JP 2013031159A JP 2013031159 A JP2013031159 A JP 2013031159A JP 6095408 B2 JP6095408 B2 JP 6095408B2
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- photopolymerization initiator
- bond
- photosensitive resin
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- 239000011342 resin composition Substances 0.000 title claims description 22
- 239000003999 initiator Substances 0.000 title description 37
- 125000000623 heterocyclic group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 description 24
- -1 oxime ester Chemical class 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 150000002923 oximes Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 150000003855 acyl compounds Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WAYIQSRQNPHIIA-UHFFFAOYSA-N CCC(C)CCCCC1=C2C(=CC=C1)NC3=C2C4=C(C=C3)C=CC5=C4C6=CC=CC=C6N5CC Chemical compound CCC(C)CCCCC1=C2C(=CC=C1)NC3=C2C4=C(C=C3)C=CC5=C4C6=CC=CC=C6N5CC WAYIQSRQNPHIIA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- WCYJQVALWQMJGE-UHFFFAOYSA-M hydroxylammonium chloride Chemical compound [Cl-].O[NH3+] WCYJQVALWQMJGE-UHFFFAOYSA-M 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IFCJSFUYBBVTMN-UHFFFAOYSA-N C1=CC=C2C(=C1)C3=C4C(=CC=C5C4=C6C=C(C=CC6=N5)[N+](=O)[O-])C=CC3=N2 Chemical class C1=CC=C2C(=C1)C3=C4C(=CC=C5C4=C6C=C(C=CC6=N5)[N+](=O)[O-])C=CC3=N2 IFCJSFUYBBVTMN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AGWBGMDJXORVLE-UHFFFAOYSA-N N1=C2C=CC=CC2=C2C1=CC=C1C=CC3=NC4=CC=CC=C4C3=C12 Chemical class N1=C2C=CC=CC2=C2C1=CC=C1C=CC3=NC4=CC=CC=C4C3=C12 AGWBGMDJXORVLE-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- JMMVHMOAIMOMOF-UHFFFAOYSA-N (4-prop-2-enoyloxyphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=C(OC(=O)C=C)C=C1 JMMVHMOAIMOMOF-UHFFFAOYSA-N 0.000 description 1
- KMTIOQFABYEFRR-UAIGNFCESA-N (Z)-but-2-enedioic acid 2-(2-hydroxyethoxy)ethanol prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCCO.OC(=O)\C=C/C(O)=O KMTIOQFABYEFRR-UAIGNFCESA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- YXNXCFZIHNRZOT-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid;terephthalic acid Chemical compound CC(=C)C(O)=O.OCC(CO)(CO)CO.OC(=O)C1=CC=C(C(O)=O)C=C1 YXNXCFZIHNRZOT-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- UIHRWPYOTGCOJP-UHFFFAOYSA-N 2-(2-fluorophenyl)-4,5-diphenyl-1h-imidazole Chemical class FC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 UIHRWPYOTGCOJP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XIOGJAPOAUEYJO-UHFFFAOYSA-N 2-(2-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 XIOGJAPOAUEYJO-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- FVNIIPIYHHEXQA-UHFFFAOYSA-N 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C12=CC=CC=C2C(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 FVNIIPIYHHEXQA-UHFFFAOYSA-N 0.000 description 1
- SNFCQJAJPFWBDJ-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 SNFCQJAJPFWBDJ-UHFFFAOYSA-N 0.000 description 1
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- QAGHEHQMRFEQMB-UHFFFAOYSA-N 2-ethylidenepropanedioic acid Chemical compound CC=C(C(O)=O)C(O)=O QAGHEHQMRFEQMB-UHFFFAOYSA-N 0.000 description 1
- LETDRANQSOEVCX-UHFFFAOYSA-N 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 LETDRANQSOEVCX-UHFFFAOYSA-N 0.000 description 1
- HDDGHHVNVQKFIB-UHFFFAOYSA-N 2-naphthalen-2-yl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=2C=C3C=CC=CC3=CC=2)=N1 HDDGHHVNVQKFIB-UHFFFAOYSA-N 0.000 description 1
- HAZQZUFYRLFOLC-UHFFFAOYSA-N 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=2C=CC=CC=2)=N1 HAZQZUFYRLFOLC-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- VRBUPQGTJAXZAE-UHFFFAOYSA-N 2-propylidenebutanedioic acid Chemical compound CCC=C(C(O)=O)CC(O)=O VRBUPQGTJAXZAE-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KORJZGKNZUDLII-UHFFFAOYSA-N 9-(4-methylphenyl)acridine Chemical compound C1=CC(C)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 KORJZGKNZUDLII-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RKUMTYGKTTXKGR-UHFFFAOYSA-N CCC(C)CCCCC1=C(C=CC2=C1C3=C(N2)C=CC4=C3C5=C(C=C4)N(C6=CC=CC=C65)CC)[N+](=O)[O-] Chemical compound CCC(C)CCCCC1=C(C=CC2=C1C3=C(N2)C=CC4=C3C5=C(C=C4)N(C6=CC=CC=C65)CC)[N+](=O)[O-] RKUMTYGKTTXKGR-UHFFFAOYSA-N 0.000 description 1
- HYWUYZADRRWZNQ-GWSDYOLYSA-N CCCCC(CC)C[n](c(cc1)c2cc1/C(/C)=N/OC(C)=O)c1c2c2c(c(cc(cc3)/C(/C)=N/OC(C)=O)c3[n]3CC(CC)CCCC)c3ccc2cc1 Chemical compound CCCCC(CC)C[n](c(cc1)c2cc1/C(/C)=N/OC(C)=O)c1c2c2c(c(cc(cc3)/C(/C)=N/OC(C)=O)c3[n]3CC(CC)CCCC)c3ccc2cc1 HYWUYZADRRWZNQ-GWSDYOLYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- DUMSMYVMGHSURZ-UHFFFAOYSA-N bis[2-[4-(2-methylphenyl)sulfanylphenyl]phenyl]methanone Chemical compound CC1=C(C=CC=C1)SC1=CC=C(C=C1)C1=C(C=CC=C1)C(=O)C1=C(C=CC=C1)C1=CC=C(C=C1)SC1=C(C=CC=C1)C DUMSMYVMGHSURZ-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
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Landscapes
- Materials For Photolithography (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、新規な光重合開始剤、さらに、これらを使用する感光性樹脂組成物に関する。 The present invention relates to novel photopolymerization initiators, and further to a photosensitive resin composition using them.
感光性樹脂組成物は、主に、エチレン性不飽和結合を有する重合性化合物と光重合開始剤からなるが、エチレン性不飽和化合物は、一般に紫外線照射を行うことにより硬化させることができる。
重合硬化のためには、それに適した光重合開始剤が必要で、紫外線照射を行うことにより光重合開始剤が活性ラジカルを生じ、エチレン性不飽和化合物が反応して重合する。
The photosensitive resin composition mainly comprises a polymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator, and the ethylenically unsaturated compound can generally be cured by irradiation with ultraviolet rays.
For polymerization and curing, a suitable photopolymerization initiator is necessary, and by performing ultraviolet irradiation, the photopolymerization initiator generates active radicals, and the ethylenically unsaturated compound reacts and polymerizes.
重合により微細なライン等を得るための光源としては、３６５ｎｍや４０５ｎｍの光が主に用いられる。そして、短波長の光源に感度を持つ感光性樹脂組成物を用いることにより、微細な印刷等が可能であるため、特に３６５ｎｍ、４０５ｎｍの光源に優れた感度を有する光重合開始剤が望まれている。 As a light source for obtaining a fine line or the like by polymerization, 365 nm or 405 nm light is mainly used. In addition, since a fine printing or the like is possible by using a photosensitive resin composition having sensitivity to a light source having a short wavelength, a photopolymerization initiator having excellent sensitivity particularly to a 365 nm or 405 nm light source is desired. Yes.
これらの短波長の光源に感度を持つ感光性樹脂組成物は、光硬化性インキ、感光性印刷版、ドライフィルムレジスト、カラーフィルター等さまざまな分野に用いられている。
特許文献１〜４には、オキシムエステル誘導体が記載されており、これらのオキシムエステル誘導体は、光重合開始剤として用いられることが知られている。
These photosensitive resin compositions having sensitivity to a light source having a short wavelength are used in various fields such as photocurable ink, photosensitive printing plate, dry film resist, and color filter.
Patent Documents 1 to 4 describe oxime ester derivatives, and these oxime ester derivatives are known to be used as photopolymerization initiators.
また、特許文献５及び６には、より高感度のｏ−アシルオキシム開始剤が記載されている。しかしながら、これらのｏ−アシルオキシム光開始剤も、３６５ｎｍ、４０５ｎｍを光源とする光重合開始剤としては未だ満足いくものではなく、さらに高感度のものが望まれている。 Patent Documents 5 and 6 describe a more sensitive o-acyloxime initiator. However, these o-acyloxime photoinitiators are not yet satisfactory as photopolymerization initiators using 365 nm and 405 nm as light sources, and those with higher sensitivity are desired.
これまでのオキシムエステル系光重合開始剤は、３６５ｎｍ及び、特に４０５ｎｍに大きな吸収を持っておらず、求められる感度が十分に得られないことから、本発明は、この課題を解決するためのものである。 Conventional oxime ester photopolymerization initiators do not have large absorption at 365 nm and particularly at 405 nm, and the required sensitivity cannot be obtained sufficiently. Therefore, the present invention is intended to solve this problem. It is.
そのため、本発明の目的は、従来のものよりも３６５ｎｍだけでなく４０５ｎｍ付近において大きな光吸収能があり、かつ高感度の光重合開始剤を得ること、及び、これを含む感光性樹脂組成物を得ることである。 Therefore, an object of the present invention is to obtain a photopolymerization initiator having a large light absorption ability not only at 365 nm but also around 405 nm as compared with the conventional one and having high sensitivity, and a photosensitive resin composition containing the same. Is to get.
本発明は、下記一般式（Ｉ）で表される新規な光重合開始剤を提供することにより、上
記目的を達成した。
すなわち、本発明は、以下の点を特徴とする。
The present invention has achieved the above object by providing a novel photopolymerization initiator represented by the following general formula (I).
That is, the present invention is characterized by the following points.
１．下記一般式（Ｉ）で表される光重合開始剤。
Ｘは骨格Ｄ、骨格Ｅ、またはニトロ基
Ａｒはアリール基又は複素環基を表し、かつ、その環はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ'、ＣＮ、ＮＯ2又はハロゲン原子で一つ以上置換されていてもよく、
Ｒ1はＲa、ＯＲa、ＣＯＲa、ＳＲa、ＮＲaＲa'又はＣＯＮＲaＲa'を表し、
Ｒ2はＲb、ＯＲb、ＣＯＲb、ＳＲb、ＣＯＮＲbＲb'又はＣＮを表し、
Ｒ3はＲc、ＯＲc、ＣＯＲc、ＳＲc又はＮＲcＲc'を表し、
Ｒ、Ｒ'、Ｒa、Ｒa'、Ｒb、Ｒb'、Ｒc及びＲc'は、直鎖又は枝分かれ構造を有するア
ルキル基、アリール基、アラルキル基又は複素環基を示し、これらはハロゲン原子、アルコキシ基及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合及び／又はエステル結合により中断されていてもよく、また、
Ｒ及びＲ'、Ｒa及びＲa'、Ｒb及びＲb'、Ｒc及びＲc'はそれぞれ一緒になって環を形成していてもよい。）
２．Ｒ1がエチルヘキシル基を表わす、上記１記載の光重合開始剤。
３．Ｒ2がメチル基を表わす、上記１または２記載の光重合開始剤。
４．Ｒ3がメチル基を表わす、上記１〜３のいずれかに記載の光重合開始剤。
５．Ａｒがフェニル基又はチエニル基を表わす、上記１〜４のいずれかに記載の光重合開始剤。
６．Ｒ1がエチルヘキシル基を表し、Ｒ2がメチル基を表し、Ｒ3がメチル基又はフェニル基を表し、Ａｒがフェニル基、ナフチル基又はチエニル基を表す、上記１記載の光重合開始剤。
７．エチレン性不飽和結合を有する重合性化合物と、上記１〜６のいずれかに記載の光重合開始剤とを含有する感光性樹脂組成物。
1. The photoinitiator represented by the following general formula (I).
X is skeleton D, skeleton E, or nitro group
Ar represents an aryl group or a heterocyclic group, and the ring may be substituted with one or more of R, OR, COR, SR, CONRR ′, CN, NO 2 or a halogen atom;
R 1 represents R a , OR a , COR a , SR a , NR a R a ′ or CONR a R a ′;
R 2 represents R b , OR b , COR b , SR b , CONR b R b ′ or CN;
R 3 represents R c , OR c , COR c , SR c or NR c R c ′;
R, R ′, R a , R a ′, R b , R b ′, R c and R c ′ each represents an alkyl group, aryl group, aralkyl group or heterocyclic group having a linear or branched structure, May be substituted with a halogen atom, an alkoxy group and / or a heterocyclic group, among which the alkyl group and the alkylene part of the aralkyl group are interrupted by an unsaturated bond, an ether bond, a thioether bond and / or an ester bond. May be, and
R and R ′, R a and R a ′, R b and R b ′, R c and R c ′ may be combined to form a ring. )
2. 2. The photopolymerization initiator according to 1 above, wherein R 1 represents an ethylhexyl group.
3. 3. The photopolymerization initiator according to 1 or 2 above, wherein R 2 represents a methyl group.
4). 4. The photopolymerization initiator according to any one of 1 to 3 above, wherein R 3 represents a methyl group.
5. 5. The photopolymerization initiator according to any one of 1 to 4 above, wherein Ar represents a phenyl group or a thienyl group.
6). 2. The photopolymerization initiator according to 1 above, wherein R 1 represents an ethylhexyl group, R 2 represents a methyl group, R 3 represents a methyl group or a phenyl group, and Ar represents a phenyl group, a naphthyl group, or a thienyl group.
7). The photosensitive resin composition containing the polymeric compound which has an ethylenically unsaturated bond, and the photoinitiator in any one of said 1-6.
本発明の光重合開始剤は、感光性、解像性、経時安定性に優れており、３６５ｎｍから４０５ｎｍ付近における吸光度が、これまでのものよりも高いため、３６５ｎｍ及び４０５ｎｍの波長を光源として使用する光重合開始剤、あるいは感光性樹脂組成物として有用
なものである。
The photopolymerization initiator of the present invention is excellent in photosensitivity, resolution, and stability over time, and the absorbance in the vicinity of 365 nm to 405 nm is higher than the conventional one, so that wavelengths of 365 nm and 405 nm are used as a light source. It is useful as a photopolymerization initiator or a photosensitive resin composition.
以下、本発明の光重合開始剤、及びこれらを含有する感光性樹脂組成物について詳細に説明する。
本発明の光重合開始剤は、以下の一般式（Ｉ）で表わされるものである。
Ｘは骨格Ｄ、骨格Ｅ、またはニトロ基
Ａｒはアリール基又は複素環基を表し、かつ、その環はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ'、ＣＮ、ＮＯ2又はハロゲン原子で一つ以上置換されていてもよく、
Ｒ1はＲa、ＯＲa、ＣＯＲa、ＳＲa、ＮＲaＲa'又はＣＯＮＲaＲa'を表し、
Ｒ2はＲb、ＯＲb、ＣＯＲb、ＳＲb、ＣＯＮＲbＲb'又はＣＮを表し、
Ｒ3はＲc、ＯＲc、ＣＯＲc、ＳＲc又はＮＲcＲc'を表し、
Ｒ、Ｒ'、Ｒa、Ｒa'、Ｒb、Ｒb'、Ｒc及びＲc'は、直鎖又は枝分かれ構造を有するア
ルキル基、アリール基、アラルキル基又は複素環基を示し、これらはハロゲン原子、アルコキシ基及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合及び／又はエステル結合により中断されていてもよく、また、
Ｒ及びＲ'、Ｒa及びＲa'、Ｒb及びＲb'、Ｒc及びＲc'はそれぞれ一緒になって環を形
成していてもよい。）
上記において、「直鎖又は枝分かれ構造を有するアルキル基」とは、直鎖状あるいは分枝鎖状の飽和脂肪族炭化水素基を意味する。アルキル基の炭素数は特に限定されないが、通常１〜２０、より好ましくは１〜１０の範囲である。
Hereinafter, the photoinitiator of this invention and the photosensitive resin composition containing these are demonstrated in detail.
The photopolymerization initiator of the present invention is represented by the following general formula (I).
X is skeleton D, skeleton E, or nitro group
Ar represents an aryl group or a heterocyclic group, and the ring may be substituted with one or more of R, OR, COR, SR, CONRR ′, CN, NO 2 or a halogen atom;
R 1 represents R a , OR a , COR a , SR a , NR a R a ′ or CONR a R a ′;
R 2 represents R b , OR b , COR b , SR b , CONR b R b ′ or CN;
R 3 represents R c , OR c , COR c , SR c or NR c R c ′;
R, R ′, R a , R a ′, R b , R b ′, R c and R c ′ each represents an alkyl group, aryl group, aralkyl group or heterocyclic group having a linear or branched structure, May be substituted with a halogen atom, an alkoxy group and / or a heterocyclic group, among which the alkyl group and the alkylene part of the aralkyl group are interrupted by an unsaturated bond, an ether bond, a thioether bond and / or an ester bond. May be, and
R and R ′, R a and R a ′, R b and R b ′, R c and R c ′ may be combined to form a ring. )
In the above, “an alkyl group having a linear or branched structure” means a linear or branched saturated aliphatic hydrocarbon group. Although carbon number of an alkyl group is not specifically limited, Usually, it is 1-20, More preferably, it is the range of 1-10.
「アルコキシ基」とは、エーテル結合を介して脂肪族炭化水素基が結合した官能基を意味する。アルコキシ基の炭素数は特に限定されないが、通常、１〜２０、より好ましくは１〜１０の範囲である。
「ハロゲン原子」とは、フッ素、塩素、臭素、ヨウ素を意味する。
「アリール基」とは、芳香族炭化水素基を意味する。アリール基の炭素数は特に限定されないが、通常、６〜１８の範囲である。好ましいアリール基としては、フェニル、ナフチル、アントラニル、フェナントリル等が挙げられる。
「複素環基」とは、窒素、酸素、硫黄等の炭素以外のヘテロ原子を一個または複数個環
内に有する、飽和、部分飽和又は完全不飽和の環を意味する。好ましい「複素環基」としては、チエニル、フラニル、イミダゾリル、オキサゾリル、チアゾリル、トリアゾリル、ベンゾフラニル、ジュロリジニル、ベンゾイミダゾリル、ベンゾオキサゾリル、ベンゾチアゾリル、ベンゾトリアゾリル等が挙げられる。
「アラルキル基」とは、アルキル基における一個または複数個の水素原子が、アリール基で置換された基を意味し、アラルキル基を構成するアルキル基、アリール基は、上記で定義したものである。
The “alkoxy group” means a functional group in which an aliphatic hydrocarbon group is bonded through an ether bond. Although carbon number of an alkoxy group is not specifically limited, Usually, it is 1-20, More preferably, it is the range of 1-10.
“Halogen atom” means fluorine, chlorine, bromine or iodine.
“Aryl group” means an aromatic hydrocarbon group. Although carbon number of an aryl group is not specifically limited, Usually, it is the range of 6-18. Preferred aryl groups include phenyl, naphthyl, anthranyl, phenanthryl and the like.
“Heterocyclic group” means a saturated, partially saturated or fully unsaturated ring having one or more heteroatoms other than carbon such as nitrogen, oxygen and sulfur in the ring. Preferable “heterocyclic group” includes thienyl, furanyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, benzofuranyl, julolidinyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl and the like.
The “aralkyl group” means a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group, and the alkyl group and aryl group constituting the aralkyl group are as defined above.
Ｒ及びＲ'、Ｒa及びＲa'、Ｒb及びＲb'、Ｒc及びＲc'により構成される環は、それら
が結合している窒素原子と一緒になって形成される環を意味する。ここで、前記環は、Ｒ、Ｒ'、Ｒa、Ｒa'、Ｒb、Ｒb'、Ｒc、Ｒc'が結合している窒素原子に加えて、窒素、酸素、硫黄等の炭素以外のヘテロ原子を一個または複数個環内に有してもよい、飽和、部分飽和又は完全不飽和の環である。上記環の具体例としては、ピロリジニル、ピペリジニル、ピペラジニル、モルホリニル、チオモルホリニル、ピリジニル、ピリミジニル等が挙げられる。
The ring constituted by R and R ′, R a and R a ′, R b and R b ′, R c and R c ′ is a ring formed together with the nitrogen atom to which they are bonded. means. Here, in addition to the nitrogen atom to which R, R ′, R a , R a ′, R b , R b ′, R c , R c ′ are bonded, the ring includes nitrogen, oxygen, sulfur, etc. A saturated, partially saturated or fully unsaturated ring which may have one or more heteroatoms other than carbon in the ring. Specific examples of the ring include pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, pyridinyl, pyrimidinyl and the like.
本発明の上記一般式（Ｉ）で表される化合物において、Ｒ1がエチルヘキシル基を表し、Ｒ2がメチル基を表し、Ｒ3がメチル基を表し、Ａｒがフェニル基、ナフチル基又はチエニル基を有するものが好ましい。 In the compound represented by the above general formula (I) of the present invention, R 1 represents an ethylhexyl group, R 2 represents a methyl group, R 3 represents a methyl group, Ar represents a phenyl group, a naphthyl group, or a thienyl group. Those having the following are preferred.
さらに、本発明の光重合開始剤の中でも、特に、上記一般式（Ｉ）において、Ｒ1がエチルヘキシル基を表わすもの、Ｒ2がメチル基を表わすもの、Ｒ3がメチル基を表わすもの、Ｘが骨格Ｄを表すものが、良好な、感光性、解像性、経時安定性の点において好ましい。 Further, among the photopolymerization initiators of the present invention, in particular, in the general formula (I), R 1 represents an ethylhexyl group, R 2 represents a methyl group, R 3 represents a methyl group, X Is preferable in terms of good photosensitivity, resolution, and stability over time.
［本発明の化合物の製造方法］
本発明の中間体であるオキシムを得るためには、一般的に次に示す反応が好適である。
アルデヒド又はケトンと、塩酸ヒドロキシルアミンとを、酢酸ナトリウム又はピリジンのような塩基の存在下、エタノールのような極性溶媒中で反応させることで合成することができる。
上記一般式（Ｉ）で表される本発明の光重合開始剤は、一般的に、次のようにして製造することができる。
[Method for producing compound of the present invention]
In order to obtain the oxime which is an intermediate of the present invention, the following reaction is generally preferred.
It can be synthesized by reacting an aldehyde or ketone with hydroxylamine hydrochloride in a polar solvent such as ethanol in the presence of a base such as sodium acetate or pyridine.
The photopolymerization initiator of the present invention represented by the above general formula (I) can be generally produced as follows.
まず、下記一般式（II）
いてもよい。）
で表されるカルバゾロ［３，４−ｃ］カルバゾール系化合物と、下記一般式（III）
Ｒb及びＲb'は、直鎖又は枝分かれ構造を有するアルキル基、アリール基、アラルキル基又は複素環基を示し、これらはハロゲン原子、アルコキシ基及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合及び／又はエステル結合により中断されていてもよく、また、Ｒb及びＲb'は一緒になって環を形成していてもよい。）で表される酸塩化物とを、塩化アルミニウムの様な金属塩化物の存在下に反応させることにより、下記一般式（Ｖ）
で表されるアシル体を得る。
First, the following general formula (II)
And a carbazolo [3,4-c] carbazole compound represented by the following general formula (III)
R b and R b ′ represent an alkyl group, aryl group, aralkyl group or heterocyclic group having a straight chain or branched structure, and these may be substituted with a halogen atom, an alkoxy group and / or a heterocyclic group Among these, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond and / or an ester bond, and R b and R b ′ are combined to form a ring. May be formed. ) In the presence of a metal chloride such as aluminum chloride, the following general formula (V)
Is obtained.
次いで、上記一般式（Ｖ）を塩酸ヒドロキシルアミン、ピリジン等の塩基の存在下に反応させることにより、下記一般式（VI）
で表されるオキシム化合物を得る。
Next, by reacting the above general formula (V) in the presence of a base such as hydroxylamine hydrochloride and pyridine, the following general formula (VI)
The oxime compound represented by this is obtained.
次いで、上記一般式（VI）と、下記一般式（VII）
で表される酸塩化物等とを用いて、下記一般式（Ｉ）
で表される本発明の光重合開始剤を得る。
Next, the above general formula (VI) and the following general formula (VII)
And an acid chloride represented by the following general formula (I)
The photoinitiator of this invention represented by these is obtained.
本発明の光重合開始剤は、ラジカル重合が可能なエチレン性不飽和結合を有する化合物の光重合開始剤として有用である。 The photopolymerization initiator of the present invention is useful as a photopolymerization initiator for compounds having an ethylenically unsaturated bond capable of radical polymerization.
〔本発明の光重合開始剤を含有する感光性樹脂組成物〕
次に、本発明の感光性樹脂組成物について説明する。
感光性樹脂組成物はエチレン性不飽和結合を有する化合物、バインダー等に、本発明の光重合開始剤を含有させてなる成分である。また、必要に応じて、熱重合禁止剤や可塑剤等の添加剤を混合することによって調製される。
[Photosensitive resin composition containing the photopolymerization initiator of the present invention]
Next, the photosensitive resin composition of the present invention will be described.
The photosensitive resin composition is a component obtained by adding the photopolymerization initiator of the present invention to a compound having an ethylenically unsaturated bond, a binder, or the like. Moreover, it prepares by mixing additives, such as a thermal-polymerization inhibitor and a plasticizer, as needed.
本発明のエチレン性不飽和二重結合を有する化合物としては、例えば、不飽和カルボン酸、不飽和カルボン酸と脂肪族ポリヒドロキシ化合物とのエステル、不飽和カルボン酸と芳香族ポリヒドロキシ化合物とのエステル、不飽和カルボン酸と多価カルボン酸とポリヒドロキシ化合物とのエステル化反応により得られるエステル等があげられる。 Examples of the compound having an ethylenically unsaturated double bond of the present invention include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and an aliphatic polyhydroxy compound, and an ester of an unsaturated carboxylic acid and an aromatic polyhydroxy compound. And esters obtained by esterification reaction of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound.
本発明の不飽和カルボン酸と脂肪族ポリヒドロキシ化合物とのエステルとしては、例えば、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等のアクリル酸エステル、トリエチレングリコールジメタクリレート、トリメチロールエタントリメタクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールジメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールジメタクリレート、ジペンタエリスリトールトリメタクリレート、ジペンタエリスリトールテトラメタクリレート等のメタクリル酸エステル、脂肪族ポリヒドロキシ化合物のイタコン酸エステル、クロトン酸エステル、マレイン酸エステル等があげられる。 Examples of the ester of the unsaturated carboxylic acid and the aliphatic polyhydroxy compound of the present invention include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, pentaerythritol diacrylate, penta Acrylic esters such as erythritol triacrylate, pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, triethylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate , Pentaerythritol tetrameta Relate, dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, methacrylic acid esters such as dipentaerythritol tetramethacrylate, itaconic acid esters of aliphatic polyhydroxy compounds, crotonic acid esters, maleic acid esters and the like.
本発明の不飽和カルボン酸と芳香族ポリヒドロキシ化合物とのエステルとしては、例えば、ヒドロキノンジアクリレート、ヒドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート等があげられる。 Examples of the ester of the unsaturated carboxylic acid and the aromatic polyhydroxy compound of the present invention include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate and the like.
不飽和カルボン酸と多価カルボン酸とポリヒドロキシ化合物とのエステル化反応により得られるエステルとしては、例えば、アクリル酸−フタル酸−エチレングリコールの縮合物、アクリル酸−マレイン酸−ジエチレングリコールの縮合物、メタクリル酸−テレフタル酸−ペンタエリスリトールの縮合物、アクリル酸−アジピン酸−ブタンジオール−グリセリンの縮合物等があげられる。 Examples of the ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polyvalent carboxylic acid and a polyhydroxy compound include acrylic acid-phthalic acid-ethylene glycol condensate, acrylic acid-maleic acid-diethylene glycol condensate, Examples include a condensate of methacrylic acid-terephthalic acid-pentaerythritol, a condensate of acrylic acid-adipic acid-butanediol-glycerin, and the like.
その他本発明に用いられるエチレン性不飽和二重結合を有する化合物の例としては、エチレンビスアクリルアミド等のアクリルアミド類、フタル酸ジアリル等のアリルエステル、ジビニルフタレート等のビニル基含有化合物等があげられる。主鎖にエチレン性不飽和二重結合を有する重合体としては、例えば不飽和二価カルボン酸とジヒドロキシ化合物との重縮合反応により得られるポリエステル、不飽和二価カルボン酸とジアミンとの重縮合反応により得られるポリエステル、不飽和二価カルボン酸とジアミンとの重縮合反応により得られるポリアミド等があげられる。 Other examples of the compound having an ethylenically unsaturated double bond used in the present invention include acrylamides such as ethylene bisacrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate. Examples of the polymer having an ethylenically unsaturated double bond in the main chain include polyester obtained by polycondensation reaction of unsaturated divalent carboxylic acid and dihydroxy compound, polycondensation reaction of unsaturated divalent carboxylic acid and diamine. And a polyester obtained by a polycondensation reaction of an unsaturated divalent carboxylic acid and a diamine.
本発明の側鎖にエチレン性不飽和二重結合を有する重合体としては、側鎖に不飽和結合をもつ二価カルボン酸、例えば、イタコン酸、プロピリデンコハク酸、エチリデンマロン酸等とジヒドロキシ又はジアミン化合物との縮合重合体等があげられる。また、側鎖にヒドロキシ基やハロゲン化メチル基の如き官能基をもつ重合体、例えば、ポリジビニルアルコール、ポリ（２−ヒドロキシエチルメタクリレート）、エポキシ樹脂、フェノキシ樹脂ポリエピクロルヒドリン等とアクリル酸、メタクリル酸、クロトン酸の様な不飽和カルボン酸との高分子反応により得られるポリマーも使用できる。 Examples of the polymer having an ethylenically unsaturated double bond in the side chain of the present invention include a divalent carboxylic acid having an unsaturated bond in the side chain, such as itaconic acid, propylidene succinic acid, ethylidene malonic acid and the like and dihydroxy or Examples thereof include condensation polymers with diamine compounds. Polymers having a functional group such as a hydroxy group or a methyl halide group in the side chain, such as polydivinyl alcohol, poly (2-hydroxyethyl methacrylate), epoxy resin, phenoxy resin polyepichlorohydrin, acrylic acid, methacrylic acid, etc. A polymer obtained by polymer reaction with an unsaturated carboxylic acid such as crotonic acid can also be used.
バインダーは、重合性の単量体をラジカル重合させることにより得られる。単量体としては、例えば、スチレン、ビニルトルエン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−エチルスチレン等のスチレン誘導体、アクリルアミド、アクリロニトリル等のビニルアルコールエステル類、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸ペンチル、メタクリル酸ヘキシル等のメタクリル酸アルキルエステル等、マレイン酸、無水マレイン酸、桂皮酸、イタコン酸、クロトン酸等があげられる。 The binder is obtained by radical polymerization of a polymerizable monomer. Examples of the monomer include styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene, vinyl alcohol esters such as acrylamide and acrylonitrile, methyl methacrylate, ethyl methacrylate, Examples thereof include methacrylic acid alkyl esters such as propyl methacrylate, butyl methacrylate, pentyl methacrylate and hexyl methacrylate, maleic acid, maleic anhydride, cinnamic acid, itaconic acid, crotonic acid and the like.
本発明のバインダーの使用量は、エチレン性化合物１００重量部に対して３０〜１０００重量部、さらに好ましくは５０〜１５０重量部である。
また、本発明のオキシムエステル化合物は、下記に示すような公知の光重合開始剤と併用して使用することができる。
The usage-amount of the binder of this invention is 30-1000 weight part with respect to 100 weight part of ethylenic compounds, More preferably, it is 50-150 weight part.
Further, the oxime ester compound of the present invention can be used in combination with known photopolymerization initiators as shown below.
これら光重合開始剤としては、例えば、アセトフェノン、ベンゾフェノン、４，４’−ビス（ジエチルアミノ）−ベンゾフェノン、４−（メチルフェニルチオ）−フェニルフェニルケトン、ベンジルジメチルケタール、２−メチル−１−メチルチオフェニル−２−モルフォリのプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン、ｐ−ジエチルアミノ安息香酸エチル、チオキサントン、２，５−ジエチルチオキサントン、２−クロロキサントン、イソプロピルチオキサントン、１−クロロ−４−プロポキシ−チオキサントン、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−フルオロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−クロロフェニル）−４，５−ジ（ｏ−メトキシフェニル）イミダゾール二量体、９−フェニルアクリジン、９−（ｐ−トルイル）アクリジン、１，７−ビス（９，９’−アクリジニル）ヘプタン、Ｎ−フェニルグリシン、ビス（η5−シクロペンタジエニル）ビス［２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）フェニル］チタニウム
、２−エチルアントラキノン、１−クロロアントラキノン、２−フェニル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（４−メトキシフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−ナフチル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（４−メトキシナフチル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−メチル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン等があげられる。
Examples of these photopolymerization initiators include acetophenone, benzophenone, 4,4′-bis (diethylamino) -benzophenone, 4- (methylphenylthio) -phenylphenylketone, benzyldimethylketal, 2-methyl-1-methylthiophenyl. 2-morpholin propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, ethyl p-diethylaminobenzoate, thioxanthone, 2,5-diethylthioxanthone 2-chloroxanthone, isopropylthioxanthone, 1-chloro-4-propoxy-thioxanthone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazole dimer, 2- ( o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (o) -Methoxyphenyl) imidazole dimer, 9-phenylacridine, 9- (p-toluyl) acridine, 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine, bis (η 5 -cyclopenta Dienyl) bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium, 2-ethylanthraquinone, 1-chloroanthraquinone, 2-phenyl-4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6 Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine Etc.
本発明の感光性樹脂組成物は、通常、オキシムエステル化合物、エチレン性不飽和結合を有する重合性化合物を溶解又は分散させて使用される。
使用される溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、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、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、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プロピルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチルエーテル、ｔ−ブチルメチルエーテル、ｔ−ブチルエチルエーテル、ヘキサン、ヘプタン、オクタン、シクロヘキサン、ベンゼン、トルエン、キシレン、メタノール、エタノール、イソプロパノール、１−ブタノール、クロロホルム、Ｎ，Ｎ’−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン等を加えた溶液状組成物として用いられる。
The photosensitive resin composition of the present invention is usually used by dissolving or dispersing an oxime ester compound and a polymerizable compound having an ethylenically unsaturated bond.
Examples of the solvent used include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl. Ether, diethylene glycol monopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethyl ether, t-butyl methyl ether, t-butyl ethyl ether, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol 1-butanol, chlorofo Beam, N, N'-dimethylformamide is used as a solution-like composition was added N- methyl-2-pyrrolidone.
本発明の感光性樹脂組成物は、各種印刷インキ、印刷版、塗料、接着剤、ドライフィルムレジスト、カラーフィルター、ブラックマトリクス等の用途に広く使用することができ、その用途に特に制限はない。 The photosensitive resin composition of the present invention can be widely used for various printing inks, printing plates, paints, adhesives, dry film resists, color filters, black matrices, and the like, and there is no particular limitation on the applications.
また本発明で露光に用いられる光源としては、ハロゲンランプ、キセノンランプ、タングステンランプ、メタルハライドランプ、超高圧水銀灯、高圧水銀灯、中圧水銀灯、低圧水銀灯、発光ダイオード、レーザーダイオード、Ｆ2エキシマレーザー、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー等を用いることができる。 The light sources used for exposure in the present invention include halogen lamps, xenon lamps, tungsten lamps, metal halide lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, light emitting diodes, laser diodes, F 2 excimer lasers, KrF. An excimer laser, an ArF excimer laser, or the like can be used.
本発明の感光性樹脂組成物において、光重合開始剤の添加量は特に限定されるものではないが、本発明の光重合開始剤は、エチレン性不飽和結合を有する上記重合性化合物１００重量部に対して、通常０.１〜５０重量部、より好ましくは、感度及び解像度等を考慮して１〜４０重量部である。
次に、本発明の光重合開始剤を用いた実施例を示すが、本発明は以下の実験例に限定されるものではない。
In the photosensitive resin composition of the present invention, the addition amount of the photopolymerization initiator is not particularly limited, but the photopolymerization initiator of the present invention is 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond. On the other hand, it is usually 0.1 to 50 parts by weight, and more preferably 1 to 40 parts by weight in consideration of sensitivity and resolution.
Next, although the Example using the photoinitiator of this invention is shown, this invention is not limited to the following experiment examples.
〔実施例１〕光重合開始剤の合成
ａ．カルバゾロ［３，４−ｃ］カルバゾール誘導体（アシル体の合成）
クロロベンゼン７５部中に５，１０−ジエチルヘキシル−カルバゾロ［３，４−ｃ］カルバゾール７.５部を加え氷冷し、塩化アルミニウム４.７部及び塩化アセチル３.３部を加えた。この反応混合物を氷冷で２時間攪拌した。次いで反応混合物を氷水に注いだ。生成物をクロロベンゼンで抽出した。食塩水で洗浄し、その後無水硫酸マグネシウムで乾燥した。溶媒を濃縮後、褐色タールを得た。得られたタールをヘキサン／酢酸エチル（７：１〜２：１）を用いてシリカゲルカラムクロマトグラフィーにより精製して、淡黄緑色粉末５.５部（６３.３％）を得た。 In 75 parts of chlorobenzene, 7.5 parts of 5,10-diethylhexyl-carbazolo [3,4-c] carbazole was added and cooled on ice, and 4.7 parts of aluminum chloride and 3.3 parts of acetyl chloride were added. The reaction mixture was stirred on ice for 2 hours. The reaction mixture was then poured into ice water. The product was extracted with chlorobenzene. The extract was washed with brine and then dried over anhydrous magnesium sulfate. After concentrating the solvent, a brown tar was obtained. The obtained tar was purified by silica gel column chromatography using hexane / ethyl acetate (7: 1 to 2: 1) to obtain 5.5 parts (63.3%) of pale yellowish green powder.
ｂ．オキシム体の合成
ＤＭＦ３１.５部中のａ．で得られたアシル体３.５部に塩化ヒドロキシルアンモニウム１.９５部、酢酸ナトリウム３水和物３.８５部、水３.８５部で調整した溶液を加え、還流下４時間攪拌した後、反応混合物を氷水に注いだ。得られた個体を濾取し、水で洗浄し、酢酸エチルに溶解した。無水硫酸マグネシウムで乾燥した後、濃縮し、黄色固体２.３部（６２.６％）を得た。この固体を未精製のまま、次の反応に用いた。 A. In 31.5 parts of DMF. A solution prepared with 1.95 parts of hydroxylammonium chloride, 3.85 parts of sodium acetate trihydrate, and 3.85 parts of water was added to 3.5 parts of the acyl compound obtained in Step 3, and the mixture was stirred for 4 hours under reflux. The reaction mixture was poured into ice water. The obtained solid was collected by filtration, washed with water, and dissolved in ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated to obtain 2.3 parts (62.6%) of a yellow solid. This solid was used in the next reaction without purification.
ｃ．オキシムエステル体の合成
ｂ．で得られたオキシム体２.０部をＤＭＦ１２部に溶解した。この溶液にトリエチルアミン１.８８部、無水酢酸１.９部加え、室温で６時間攪拌した後、反応混合物を水に注ぎ、析出固体を濾過した。濾物を、クロロホルムを用いてシリカゲルカラムクロマトグラフィーにより精製して、黄色固体１.６部（７０.７％）を得た。λｍａｘは３９４.０ｎｍ、融点は６３〜６５℃であった。 b. 2.0 parts of the oxime obtained in the above was dissolved in 12 parts of DMF. To this solution, 1.88 parts of triethylamine and 1.9 parts of acetic anhydride were added and stirred at room temperature for 6 hours. Then, the reaction mixture was poured into water, and the precipitated solid was filtered. The residue was purified by silica gel column chromatography using chloroform to obtain 1.6 parts (70.7%) of a yellow solid. λmax was 394.0 nm and the melting point was 63 to 65 ° C.
〔実施例２〕光重合開始剤の合成
ａ．カルバゾロ［３，４−ｃ］カルバゾール誘導体（アシル体の合成）
クロロベンゼン５３部中に５，１０−ジエチルヘキシル−カルバゾロ［３，４−ｃ］カルバゾール７.５部、塩化アルミニウム１.６６部、ベンゾイルクロリド１.２６部を加え、６０℃で２時間攪拌した。次いで反応混合物を氷冷し、塩化アルミニウム１.６６部及び塩化アセチル０.８６部を加えた。この反応混合物を室温で２時間攪拌した。次いで反応混合物を氷水に注いだ。生成物をクロロベンゼンで抽出した。食塩水で洗浄し、その後無水硫酸マグネシウムで乾燥した。溶媒を濃縮後、褐色タールを得た。得られたタールをクロロホルムを用いてシリカゲルカラムクロマトグラフィーにより精製して、褐色粉末４.６部（６８.０％）を得た。 7.5 parts of 5,10-diethylhexyl-carbazolo [3,4-c] carbazole, 1.66 parts of aluminum chloride and 1.26 parts of benzoyl chloride were added to 53 parts of chlorobenzene, and the mixture was stirred at 60 ° C. for 2 hours. The reaction mixture was then ice-cooled and 1.66 parts of aluminum chloride and 0.86 parts of acetyl chloride were added. The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was then poured into ice water. The product was extracted with chlorobenzene. The extract was washed with brine and then dried over anhydrous magnesium sulfate. After concentrating the solvent, a brown tar was obtained. The obtained tar was purified by silica gel column chromatography using chloroform to obtain 4.6 parts (68.0%) of a brown powder.
ｂ．オキシム体の合成
ＤＭＦ３４.２部中にａ．で得られたアシル体３.８部に塩化ヒドロキシルアンモニウム１.０部、酢酸ナトリウム３水和物１.９部、水１.９部で調整した溶液を加え、還流下４時間攪拌した後、反応混合物を氷水に注いだ。得られた個体を濾取し、水で洗浄し、酢酸エチルに溶解した。無水硫酸マグネシウムで乾燥した後、濃縮し、褐色固体３.６部（９２.７％）を得た。この固体を未精製のまま、次の反応に用いた。 In 34.2 parts of DMF a. A solution adjusted with 1.0 part of hydroxylammonium chloride, 1.9 parts of sodium acetate trihydrate, and 1.9 parts of water was added to 3.8 parts of the acyl compound obtained in the above and stirred for 4 hours under reflux. The reaction mixture was poured into ice water. The obtained solid was collected by filtration, washed with water, and dissolved in ethyl acetate. After drying over anhydrous magnesium sulfate, the mixture was concentrated to obtain 3.6 parts (92.7%) of a brown solid. This solid was used in the next reaction without purification.
ｃ．オキシムエステル体の合成
ｂ．で得られたオキシム体３部をＤＭＦ３０部に溶解した。この溶液にトリエチルアミン１.３２部、無水酢酸１.３２部を加え、室温で６時間攪拌した後、反応混合物を水に注ぎ、析出固体を濾過した。濾物を、クロロホルムを用いてシリカゲルカラムクロマトグラフィーにより精製して、褐色固体２.５部（７８.５％）を得た。λｍａｘは３９７.０ｎｍ、融点は６８〜７０℃であった。 b. 3 parts of the oxime obtained in the above was dissolved in 30 parts of DMF. To this solution were added 1.32 parts of triethylamine and 1.32 parts of acetic anhydride, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into water, and the precipitated solid was filtered. The residue was purified by silica gel column chromatography using chloroform to obtain 2.5 parts (78.5%) of a brown solid. λmax was 397.0 nm and the melting point was 68-70 ° C.
〔実施例３〕光重合開始剤の合成
ａ．２−ニトロ−カルバゾロ［３，４−ｃ］カルバゾール誘導体（ニトロ体の合成）
酢酸１８０部中に５，１０−ジエチルヘキシル−カルバゾロ［３，４−ｃ］カルバゾール６部を加え、加熱完溶後、６０％硝酸１.０２部を加え ８０℃で１時間攪拌した。次いで反応混合物を氷水に注ぎ、析出固体を濾過した。濾物を乾燥させ黄色個体６部（９２.３％）を得た。この個体を未精製のまま次の反応に用いた。 6 parts of 5,10-diethylhexyl-carbazolo [3,4-c] carbazole was added to 180 parts of acetic acid, and after complete heating, 1.02 part of 60% nitric acid was added and stirred at 80 ° C. for 1 hour. The reaction mixture was then poured into ice water and the precipitated solid was filtered. The filtrate was dried to obtain 6 parts (92.3%) of a yellow solid. This individual was used in the next reaction without purification.
ｂ． ２−ニトロ−カルバゾロ［３，４−ｃ］カルバゾール誘導体（アシル体の合成）
クロロベンゼン１２０部中に５，１０−ジエチルヘキシル−２−ニトロ−カルバゾロ［３，４−ｃ］カルバゾール６部を加え氷冷し、塩化アルミニウム１.９８部及び塩化アセチル０.９９部を加えた。この反応混合物を室温で１時間攪拌した。次いで反応混合物を氷水に注いだ。生成物をクロロベンゼンで抽出した。食塩水で洗浄し、その後無水硫酸マグネシウムで乾燥した。溶媒を濃縮後、褐色タールを得た。得られたタールをヘキサン／酢酸エチル（１９：１〜７：１）を用いてシリカゲルカラムクロマトグラフィーにより精製して、褐色粉末３.３部（６８.０％）を得た。 In 120 parts of chlorobenzene, 6 parts of 5,10-diethylhexyl-2-nitro-carbazolo [3,4-c] carbazole was added and ice-cooled, and 1.98 parts of aluminum chloride and 0.99 parts of acetyl chloride were added. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then poured into ice water. The product was extracted with chlorobenzene. The extract was washed with brine and then dried over anhydrous magnesium sulfate. After concentrating the solvent, a brown tar was obtained. The obtained tar was purified by silica gel column chromatography using hexane / ethyl acetate (19: 1 to 7: 1) to obtain 3.3 parts (68.0%) of a brown powder.
ｃ．オキシム体の合成
ＤＭＦ２７部中にｂ．で得られたアシル体３部に塩化ヒドロキシルアンモニウム０.８４部、酢酸ナトリウム３水和物１.６５部、水１.６５部で調整した溶液を加え、還流下４時間攪拌した後、反応混合物を氷水に注いだ。得られた個体を濾取し、水で洗浄し、酢酸エチルに溶解した。無水硫酸マグネシウムで乾燥した後、濃縮し、褐色固体２.７６部（８９.８％）を得た。この固体を未精製のまま、次の反応に用いた。 In 27 parts of DMF b. A solution prepared with 0.84 parts of hydroxylammonium chloride, 1.65 parts of sodium acetate trihydrate and 1.65 parts of water was added to 3 parts of the acyl compound obtained in the above and stirred for 4 hours under reflux. Was poured into ice water. The obtained solid was collected by filtration, washed with water, and dissolved in ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated to obtain 2.76 parts (89.8%) of a brown solid. This solid was used in the next reaction without purification.
ｄ．オキシムエステル体の合成
ｃ．で得られたオキシム体２.７部をＤＭＦ２７部に溶解した。この溶液にトリエチルアミン１.２９部、無水酢酸１.２９部を加え、室温で６時間攪拌した後、反応混合物を水に注ぎ、析出固体を濾過した。濾物を、ヘキサン／酢酸エチル（１９：１〜７：１）を用いてシリカゲルカラムクロマトグラフィーにより精製して、褐色固体１.９部（６５.９％）を得た。λｍａｘは４１８.０ｎｍ、融点は６２〜６５℃であった。 c. 2.7 parts of the oxime obtained in the above was dissolved in 27 parts of DMF. To this solution, 1.29 parts of triethylamine and 1.29 parts of acetic anhydride were added and stirred at room temperature for 6 hours, and then the reaction mixture was poured into water and the precipitated solid was filtered. The residue was purified by silica gel column chromatography using hexane / ethyl acetate (19: 1-7: 1) to give 1.9 parts (65.9%) of a brown solid. λmax was 418.0 nm, and the melting point was 62 to 65 ° C.
〔実施例４〜１３〕
同様の方法によって合成した、下記一般式（Ｉ）で表される、本発明の様々な化合物の具体的な構造及び測定結果を表１に示す。
Specific structures and measurement results of various compounds of the present invention represented by the following general formula (I) synthesized by the same method are shown in Table 1.
〔実施例１４〜１６〕感光性樹脂組成物の製造
表２に示す材料を配合し、感光性樹脂組成物を得た。
[Examples 14 to 16] Production of photosensitive resin composition The materials shown in Table 2 were blended to obtain a photosensitive resin composition.
〔比較例１〕
商品名：ＯＸＥ−０１（ＢＡＳＦ製）
Product Name: OXE-01 (BASF)
〔比較例２〕
商品名：ＯＸＥ−０２（ＢＡＳＦ製）
Product name: OXE-02 (BASF)
次いで、ガラス基板上に、上記表２に示すそれぞれの感光性樹脂組成物を、回転塗布機を用いて膜厚を３μｍとなるように塗布し、オーブンで８０℃で３分間乾燥させた。その後、超高圧水銀ランプを用いて露光量を変えて露光を行った。次に、１.０重量％炭酸ナトリウム水溶液を３０℃で３分間スプレーし、未露光部分の除去を行った。 Next, each photosensitive resin composition shown in Table 2 was applied on a glass substrate using a spin coater so as to have a film thickness of 3 μm, and dried in an oven at 80 ° C. for 3 minutes. Thereafter, exposure was performed by changing the exposure amount using an ultra-high pressure mercury lamp. Next, a 1.0 wt% aqueous sodium carbonate solution was sprayed at 30 ° C. for 3 minutes to remove unexposed portions.
実施例１〜８及び比較例１〜２についての結果を表３に示す。
ここに示された感度は、２５μｍのレジストパターンを寸法通り形成できる露光量をも
って表示した。
表３においては、露光量が少ないものほど高感度であることを示すが、本発明の感光性樹脂組成物は、比較例のものと比べると、優れた感度及び解像度を示している。
The results for Examples 1-8 and Comparative Examples 1-2 are shown in Table 3.
The sensitivity shown here is indicated by the exposure amount that can form a 25 μm resist pattern according to the dimensions.
In Table 3, the smaller the exposure amount, the higher the sensitivity. However, the photosensitive resin composition of the present invention shows superior sensitivity and resolution as compared with the comparative example.
本発明の光重合開始剤は、従来のものよりも３６５ｎｍから４０５ｎｍ付近における光吸収能が優れている。また、エチレン性不飽和結合を有する重合性化合物と本発明の光重合開始剤を用いた感光性樹脂組成物は、上記波長域において優れた感光性及び解像度、保存安定性等を有する。 The photopolymerization initiator of the present invention is more excellent in light absorption in the vicinity of 365 nm to 405 nm than the conventional one. Moreover, the photosensitive resin composition using the polymerizable compound having an ethylenically unsaturated bond and the photopolymerization initiator of the present invention has excellent photosensitivity, resolution, storage stability, and the like in the above wavelength range.
そして本発明の感光性樹脂組成物は、上記波長域の紫外線照射を行うことにより光重合開始剤が活性ラジカルを生じ、エチレン性不飽和化合物が反応して効率よく重合することから、光硬化性インキ、感光性印刷版、ドライフィルムレジスト、カラーフィルター、ブラックマトリクス等の様々な分野に用いることができる。 The photosensitive resin composition of the present invention is photocurable because the photopolymerization initiator generates active radicals by performing ultraviolet irradiation in the above wavelength range, and the ethylenically unsaturated compound reacts and efficiently polymerizes. It can be used in various fields such as ink, photosensitive printing plate, dry film resist, color filter, and black matrix.
Claims (2)
Ｘは骨格Ｄ、骨格Ｅ、またはニトロ基
Ａｒはアリール基又は複素環基を表し、かつ、その環はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ'、ＣＮ、ＮＯ2又はハロゲン原子で一つ以上置換されていてもよく、
Ｒ1はＲa、ＯＲa、ＣＯＲa、ＳＲa、ＮＲaＲa'又はＣＯＮＲaＲa'を表し、
Ｒ2はＲb、ＯＲb、ＣＯＲb、ＳＲb、ＣＯＮＲbＲb'又はＣＮを表し、
Ｒ3はＲc、ＯＲc、ＣＯＲc、ＳＲc又はＮＲcＲc'を表し、
Ｒ、Ｒ'、Ｒa、Ｒa'、Ｒb、Ｒb'、Ｒc及びＲc'は、直鎖又は枝分かれ構造を有するア
ルキル基、アリール基、アラルキル基又は複素環基を示し、これらはハロゲン原子、アルコキシ基及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合及び／又はエステル結合により中断されていてもよく、また、
Ｒ及びＲ'、Ｒa及びＲa'、Ｒb及びＲb'、Ｒc及びＲc'はそれぞれ一緒になって環を形成していてもよい。） The photoinitiator represented by the following general formula (I).
X is skeleton D, skeleton E, or nitro group
Ar represents an aryl group or a heterocyclic group, and the ring may be substituted with one or more of R, OR, COR, SR, CONRR ′, CN, NO 2 or a halogen atom;
R 1 represents R a , OR a , COR a , SR a , NR a R a ′ or CONR a R a ′;
R 2 represents R b , OR b , COR b , SR b , CONR b R b ′ or CN;
R 3 represents R c , OR c , COR c , SR c or NR c R c ′;
R, R ′, R a , R a ′, R b , R b ′, R c and R c ′ each represents an alkyl group, aryl group, aralkyl group or heterocyclic group having a linear or branched structure, May be substituted with a halogen atom, an alkoxy group and / or a heterocyclic group, among which the alkyl group and the alkylene part of the aralkyl group are interrupted by an unsaturated bond, an ether bond, a thioether bond and / or an ester bond. May be, and
R and R ′, R a and R a ′, R b and R b ′, R c and R c ′ may be combined to form a ring. )
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