JP2005097141A - Dimer oxime ester compound and photopolymerization initiator comprising the same compound as active ingredient - Google Patents
Dimer oxime ester compound and photopolymerization initiator comprising the same compound as active ingredient Download PDFInfo
- Publication number
- JP2005097141A JP2005097141A JP2003330877A JP2003330877A JP2005097141A JP 2005097141 A JP2005097141 A JP 2005097141A JP 2003330877 A JP2003330877 A JP 2003330877A JP 2003330877 A JP2003330877 A JP 2003330877A JP 2005097141 A JP2005097141 A JP 2005097141A
- Authority
- JP
- Japan
- Prior art keywords
- dimer
- oxime ester
- compound
- ester compound
- photosensitive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 oxime ester compound Chemical class 0.000 title claims abstract description 93
- 239000000539 dimer Substances 0.000 title claims abstract description 66
- 239000004480 active ingredient Substances 0.000 title claims abstract description 8
- 239000003999 initiator Substances 0.000 title abstract description 30
- 150000001875 compounds Chemical class 0.000 title description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 61
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 11
- 238000004040 coloring Methods 0.000 abstract description 4
- 238000010186 staining Methods 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 239000013078 crystal Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 23
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 20
- 150000002923 oximes Chemical class 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229920006243 acrylic copolymer Polymers 0.000 description 6
- 150000003855 acyl compounds Chemical class 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002211 ultraviolet spectrum Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- GLDDVZPZOFCMTE-WCRCJTMVSA-N C(C1CO1)OCCC[Si@H](OCC)C Chemical compound C(C1CO1)OCCC[Si@H](OCC)C GLDDVZPZOFCMTE-WCRCJTMVSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 4
- YZBBUYKPTHDZHF-KNVGNIICSA-N (3R)-7,2'-dihydroxy-4'-methoxyisoflavanol Chemical compound OC1=CC(OC)=CC=C1[C@H]1C(O)C2=CC=C(O)C=C2OC1 YZBBUYKPTHDZHF-KNVGNIICSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000004662 dithiols Chemical group 0.000 description 3
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- IYPNRTQAOXLCQW-UHFFFAOYSA-N [4-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C=C1 IYPNRTQAOXLCQW-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 125000002704 decyl group Chemical group [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])* 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
- 150000002009 diols Chemical group 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001400 nonyl 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])[H] 0.000 description 2
- 125000002347 octyl 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])[H] 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- PGTWZHXOSWQKCY-UHFFFAOYSA-N 1,8-Octanedithiol Chemical compound SCCCCCCCCS PGTWZHXOSWQKCY-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- GJRCLMJHPWCJEI-UHFFFAOYSA-N 1,9-Nonanedithiol Chemical compound SCCCCCCCCCS GJRCLMJHPWCJEI-UHFFFAOYSA-N 0.000 description 1
- IYDQUNGWLDBKOF-UHFFFAOYSA-N 1-(4-butylphenyl)-2,2,2-trichloroethanone Chemical compound CCCCC1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IYDQUNGWLDBKOF-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
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- 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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- JHGGYGMFCRSWIZ-UHFFFAOYSA-N 2,2-dichloro-1-(4-phenoxyphenyl)ethanone Chemical compound C1=CC(C(=O)C(Cl)Cl)=CC=C1OC1=CC=CC=C1 JHGGYGMFCRSWIZ-UHFFFAOYSA-N 0.000 description 1
- CEOCVKWBUWKBKA-UHFFFAOYSA-N 2,4-dichlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1Cl CEOCVKWBUWKBKA-UHFFFAOYSA-N 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- BINAJQFZOKLDLN-UHFFFAOYSA-N 2,4-diethylpentane-1,5-dithiol Chemical compound C(C)C(CS)CC(CS)CC BINAJQFZOKLDLN-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- 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
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- HNAOSJQCTDLQED-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-dithiol Chemical compound C(CCC)C(CS)(CS)CC HNAOSJQCTDLQED-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-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
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- BGCQOUJDESLVAJ-UHFFFAOYSA-N 2-methyloctane-1,8-dithiol Chemical compound SCC(C)CCCCCCS BGCQOUJDESLVAJ-UHFFFAOYSA-N 0.000 description 1
- KUWWECNCVOSNOQ-UHFFFAOYSA-N 2-methylpentane-2,4-dithiol Chemical compound CC(S)CC(C)(C)S KUWWECNCVOSNOQ-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- TZROMDFHBOFGOZ-UHFFFAOYSA-N 2-methylpropane-1,3-dithiol Chemical compound SCC(C)CS TZROMDFHBOFGOZ-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
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- RCPTXQHBPWHDKY-UHFFFAOYSA-N 3-methylpentane-1,5-dithiol Chemical compound SCCC(C)CCS RCPTXQHBPWHDKY-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 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
- FNWSFSXOLMBKDN-UHFFFAOYSA-N CC(C(C)O)C(C)O.OCC(C)(CO)C Chemical compound CC(C(C)O)C(C)O.OCC(C)(CO)C FNWSFSXOLMBKDN-UHFFFAOYSA-N 0.000 description 1
- FBFUGELENSBUSW-UHFFFAOYSA-N CC(S)C(C)C(C)S Chemical compound CC(S)C(C)C(C)S FBFUGELENSBUSW-UHFFFAOYSA-N 0.000 description 1
- GLWQEGORNVVVOQ-BWHQJLJHSA-N CC[n](c(ccc(C(c(c(Cl)c1)ccc1SCc1ccc(CSc(cc2)cc(Cl)c2C(c(cc2)cc(c3c4)c2[n](CC)c3ccc4/C(/C)=N/OC(C)=O)=O)cc1)O)c1)c1c1c2)c1ccc2/C(/C)=N/OC(C)=O Chemical compound CC[n](c(ccc(C(c(c(Cl)c1)ccc1SCc1ccc(CSc(cc2)cc(Cl)c2C(c(cc2)cc(c3c4)c2[n](CC)c3ccc4/C(/C)=N/OC(C)=O)=O)cc1)O)c1)c1c1c2)c1ccc2/C(/C)=N/OC(C)=O GLWQEGORNVVVOQ-BWHQJLJHSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical compound CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004803 chlorobenzyl group Chemical group 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical compound SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- RVVRZLSZZKMJCB-UHFFFAOYSA-N heptane-1,7-dithiol Chemical compound SCCCCCCCS RVVRZLSZZKMJCB-UHFFFAOYSA-N 0.000 description 1
- LKEYTPDHNRHBGD-UHFFFAOYSA-N heptane-3,5-dithiol Chemical compound CCC(S)CC(S)CC LKEYTPDHNRHBGD-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- QHDRKFYEGYYIIK-UHFFFAOYSA-N isovaleronitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- KMTUBAIXCBHPIZ-UHFFFAOYSA-N pentane-1,5-dithiol Chemical compound SCCCCCS KMTUBAIXCBHPIZ-UHFFFAOYSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- WUVMJSSTEMBGRQ-UHFFFAOYSA-N pentane-2,4-dithiol Chemical compound CC(S)CC(C)S WUVMJSSTEMBGRQ-UHFFFAOYSA-N 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 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
- 150000003440 styrenes Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 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
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
- Indole Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
本発明は、感光性組成物に用いられる光重合開始剤として有用な新規な二量体オキシムエステル化合物、該化合物を有効成分とする光重合開始剤、及びエチレン性不飽和結合を有する重合性化合物に該光重合開始剤を含有させてなる感光性組成物に関する。 The present invention relates to a novel dimer oxime ester compound useful as a photopolymerization initiator for use in a photosensitive composition, a photopolymerization initiator containing the compound as an active ingredient, and a polymerizable compound having an ethylenically unsaturated bond The present invention relates to a photosensitive composition comprising the above photopolymerization initiator.
感光性組成物は、エチレン性不飽和結合を有する重合性化合物に光重合開始剤を加えたものであり、この感光性組成物に４０５ｎｍや３６５ｎｍの光を照射することによって重合硬化させることができるので、光硬化性インキ、感光性印刷版、各種フォトレジスト等に用いられている。短波長の光源に感度を持つ感光性組成物は微細な印刷が可能であるため、特に３６５ｎｍ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。 The photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized and cured by irradiating the photosensitive composition with light of 405 nm or 365 nm. Therefore, it is used for photocurable ink, photosensitive printing plate, various photoresists and the like. Since a photosensitive composition having sensitivity to a short wavelength light source can be finely printed, a photopolymerization initiator having excellent sensitivity particularly to a 365 nm light source is desired.
この感光性組成物に用いられる光重合開始剤として、下記特許文献１には、オキシムエステル誘導体を用いることが提案されている。また、下記特許文献２〜４にもオキシムエステル化合物が記載されている。しかし、これらの公知のオキシムエステル化合物は、光重合開始剤として用いた場合に、露光時の光により発生する分解物がマスクに付着し、その結果、焼付け時のパターン形状不良を引き起こし、収率の低下を招いていた。そのため、得られる重合物を着色したり、光重合開始剤の分解物が揮散して重合物や装置等を汚染したりしない光重合開始剤が望まれていた。 As a photopolymerization initiator used in the photosensitive composition, Patent Document 1 below proposes using an oxime ester derivative. The following Patent Documents 2 to 4 also describe oxime ester compounds. However, when these known oxime ester compounds are used as photopolymerization initiators, decomposition products generated by light during exposure adhere to the mask, resulting in pattern shape defects during printing and yield. Has led to a decline. Therefore, there has been a demand for a photopolymerization initiator that does not color the polymer obtained or decompose the decomposition product of the photopolymerization initiator to contaminate the polymer or apparatus.
また、下記特許文献５〜７には、より高い反応性を有するＯ−アシルオキシム光開始剤が提案されている。しかし、これらのＯ−アシルオキシム光開始剤も、感度の観点で未だ満足のいくものではなく、より感度に優れるものが望まれている。 Patent Documents 5 to 7 listed below propose O-acyloxime photoinitiators having higher reactivity. However, these O-acyloxime photoinitiators are not yet satisfactory from the viewpoint of sensitivity, and those having higher sensitivity are desired.
解決しようとする問題点は、上述したように、得られる重合物を着色したり重合物や装置等を汚染したりすることがなく且つ感度に優れた光重合開始剤がこれまでなかったということである。 The problem to be solved is that, as described above, there has never been a photopolymerization initiator excellent in sensitivity without coloring the obtained polymer or contaminating the polymer or equipment. It is.
本発明の目的は、高感度であり、重合物を着色したり重合物及び装置等を汚染したりするおそれのない、光重合開始剤を提供することにある。 An object of the present invention is to provide a photopolymerization initiator that has high sensitivity and does not cause coloration of a polymer or contaminate a polymer and an apparatus.
本発明は、下記一般式（Ｉ）で表される二量体オキシムエステル化合物及び該化合物を有効成分とする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ものである。 The present invention achieves the above object by providing a dimer oxime ester compound represented by the following general formula (I) and a photopolymerization initiator containing the compound as an active ingredient.
本発明の二量体オキシムエステル化合物は、感光性に優れ、経時による感光層表面への析出がないため、経時安定性に優れており、さらに分解物によるマスク付着物がなく焼付け時のパターン形状不良を起こさないため、光重合開始剤として有用なものである。 The dimer oxime ester compound of the present invention is excellent in photosensitivity, has no deposition on the surface of the photosensitive layer over time, and therefore has excellent stability over time, and further has no mask deposit due to decomposition products, and has a pattern shape upon baking. Since it does not cause defects, it is useful as a photopolymerization initiator.
以下、本発明の二量体オキシムエステル化合物及び該化合物を有効成分とする光重合開始剤について詳細に説明する。 Hereinafter, the dimer oxime ester compound of the present invention and the photopolymerization initiator containing the compound as an active ingredient will be described in detail.
上記一般式（Ｉ）中、Ｘ1及びＸ1’で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、Ｘ1及びＸ1’で表されるアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、アミル、イソアミル、第三アミル、ヘキシル、ヘプチル、オクチル、イソオクチル、２−エチルヘキシル、第三オクチル、ノニル、イソノニル、デシル、イソデシル、ビニル、アリル、ブテニル、エチニル、プロピニル、メトキシエチル、エトキシエチル、プロピロキシエチル、メトキシエトキシエチル、エトキシエトキシエチル、プロピロキシエトキシエチル、メトキシプロピル、モノフルオロメチル、ジフルオロメチル、トリフルオロメチル、トリフルオロエチル、パーフルオロエチル、２−（ベンゾオキサゾール−２’−イル）エテニル等が挙げられる。 In the general formula (I), examples of the halogen atom represented by X 1 and X 1 ′ include fluorine, chlorine, bromine and iodine. Examples of the alkyl group represented by X 1 and X 1 ′ include , Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl , Isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, Trifluoroethyl, perful Roechiru, 2- (benzoxazol-2'-yl) ethenyl and the like.
Ｒ及びＲ’で表されるアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、アミル、イソアミル、第三アミル、ヘキシル、ヘプチル、オクチル、イソオクチル、２−エチルヘキシル、第三オクチル、ノニル、イソノニル、デシル、イソデシル、ビニル、アリル、ブテニル、エチニル、プロピニル、メトキシエチル、エトキシエチル、プロピロキシエチル、メトキシエトキシエチル、エトキシエトキシエチル、プロピロキシエトキシエチル、メトキシプロピル、モノフルオロメチル、ジフルオロメチル、トリフルオロメチル、トリフルオロエチル、パーフルオロエチル、２−（ベンゾオキサゾール−２’−イル）エテニル等が挙げられ、Ｒ及びＲ’で表されるアリール基としては、例えば、フェニル、トリル、キシリル、エチルフェニル、クロロフェニル、ナフチル、アンスリル、フェナンスレニル等が挙げられ、Ｒ及びＲ’で表されるアラルキル基としては、例えば、ベンジル、クロロベンジル、α−メチルベンジル、α、α−ジメチルベンジル、フェニルエチル、フェニルエテニル等が挙げられ、Ｒ及びＲ’で表される複素環基としては、例えば、ピリジル、ピリミジル、フリル、チオフェニル等が挙げられ、また、Ｒ及びＲ’が一緒になって形成する環としては、例えば、ピペリジン環、モルホリン環等が挙げられる。 Examples of the alkyl group represented by R and R ′ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propylethoxyethoxyethyl, Methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like, and aryl groups represented by R and R ′ Examples thereof include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like, and examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl. , Α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like, and examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like, and R Examples of the ring formed by combining R ′ and R ′ include a piperidine ring and a morpholine ring.
また、Ｒ4で表されるジオール残基又はジチオール残基は、特に制限を受けるものではなく、ジオール化合物又はジチオール化合物から導入し得る基であるが、該ジオール化合物としては、エチレングリコール、ジエチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、２−メチル−１，３−プロパンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、１，４−ブタンジオール、ネオペンチルグリコール、３−メチル−２，４−ペンタンジオール、２，４−ペンタンジオール、１，５−ペンタンジオール、３−メチル−１，５−ペンタンジオール、２−メチル−２，４−ペンタンジオール、２，４−ジエチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、１，７−ヘプタンジオール、３，５−ヘプタンジオール、１，８−オクタンジオール、２−メチル−１，８−オクタンジオール、１，９−ノナンジオール、１，１０−デカンジオール、チオジエチレングリコール等の脂肪族ジオール化合物、シクロヘキサンジメタノール、シクロヘキサンジオール、水添ビスフェノールＡ等の脂環式ジオール化合物、ｐ−キシレン−α，α’−ジオール等の芳香族環式ジオール化合物が挙げられ、該ジチオール化合物としては、エチレンジチオール、１，２−プロパンジチオール、１，３−プロパンジチオール、２−メチル−１，３−プロパンジチオール、２−ブチル−２−エチル−１，３−プロパンジチオール、１，４−ブタンジチオール、３−メチル−２，４−ペンタンジチオール、２，４−ペンタンジチオール、１，５−ペンタンジチオール、３−メチル−１，５−ペンタンジチオール、２−メチル−２，４−ペンタンジチオール、２，４−ジエチル−１，５−ペンタンジチオール、１，６−ヘキサンジチオール、１，７−ヘプタンジチオール、３，５−ヘプタンジチオール、１，８−オクタンジチオール、２−メチル−１，８−オクタンジチオール、１，９−ノナンジチオール、１，１０−デカンジチオール等の脂肪族ジチオール、シクロヘキサンジメチレンチオール、シクロヘキサンジチオール等の脂環式ジチオール化合物、ｐ−キシレン−α，α’−ジチオール等の芳香族環式ジチオールが挙げられる。 The diol residue or dithiol residue represented by R 4 is not particularly limited and is a group that can be introduced from a diol compound or dithiol compound. Examples of the diol compound include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2, 4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3, -Aliphatic diol compounds such as heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, thiodiethylene glycol, cyclohexanedimethanol, cyclohexane Examples include diols, alicyclic diol compounds such as hydrogenated bisphenol A, and aromatic cyclic diol compounds such as p-xylene-α, α'-diol. Examples of the dithiol compound include ethylenedithiol and 1,2-propane. Dithiol, 1,3-propanedithiol, 2-methyl-1,3-propanedithiol, 2-butyl-2-ethyl-1,3-propanedithiol, 1,4-butanedithiol, 3-methyl-2,4- Pentanedithiol, 2,4-pentanedithiol, 1,5-pentanedithio 3-methyl-1,5-pentanedithiol, 2-methyl-2,4-pentanedithiol, 2,4-diethyl-1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, Aliphatic dithiols such as 3,5-heptanedithiol, 1,8-octanedithiol, 2-methyl-1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, cyclohexanedimethylenethiol, cyclohexane Examples thereof include alicyclic dithiol compounds such as dithiol, and aromatic cyclic dithiols such as p-xylene-α, α′-dithiol.
本発明の二量体オキシムエステル化合物の中でも、上記一般式（Ｉ）において、Ｘ1及び／又はＸ1’、特にＸ1及びＸ1’が塩素原子であるもの；ｍ及び／又はｎ、特にｍ及びｎが１であるもの；Ｒ1及び／又はＲ1’、特にＲ1及びＲ1’がアルキル基、特にメチル基であるもの；Ｒ2及び／又はＲ2’、特にＲ2及びＲ2’がアルキル基、特にメチル基であるもの；Ｒ3及び／又はＲ3’、特にＲ3及びＲ3’がアルキル基、特にエチル基であるもの；Ｒ4がアルキレン基又はアリーレン基、特にブチレン基又はペンチレン基であるものが好ましい。 Among the dimeric oxime ester compounds of the present invention, those in the general formula (I) wherein X 1 and / or X 1 ′, particularly X 1 and X 1 ′ are chlorine atoms; m and / or n, especially m and n are 1; R 1 and / or R 1 ′, in particular R 1 and R 1 ′ are alkyl groups, in particular methyl groups; R 2 and / or R 2 ′, in particular R 2 and R 2 ′ is an alkyl group, especially a methyl group; R 3 and / or R 3 ′, especially R 3 and R 3 ′ are an alkyl group, especially an ethyl group; R 4 is an alkylene group or an arylene group, especially What is a butylene group or a pentylene group is preferable.
従って、上記一般式（Ｉ）で表される本発明の二量体オキシムエステル化合物の好ましい具体例としては、以下の化合物Ｎｏ．１〜Ｎｏ．４の化合物が挙げられる。ただし、本発明は以下の化合物により何ら制限を受けるものではない。 Accordingly, preferred specific examples of the dimer oxime ester compound of the present invention represented by the above general formula (I) include the following compound Nos. 1-No. 4 compounds. However, the present invention is not limited by the following compounds.
上記一般式（Ｉ）で表される本発明の二量体オキシムエステル化合物は、例えば、下記〔化６〕の反応式で示される方法によって製造することができる。まず、Ｘ2がハロゲン原子であるカルバゾール化合物１とカルボン酸クロライド２とを塩化亜鉛の存在下に反応させてアシル化合物３を得る。次いで、アシル化合物３とジチオール化合物あるいはジオール化合物４とをナトリウムメトキシド及びジメチルホルムアミド（ＤＭＦ）の存在下に反応させて二量体５を得る。次いで、二量体５と塩酸ヒドロキシルアミンとをＤＭＦの存在下に反応させて二量体オキシム化合物６を得る。次いで、二量体オキシム化合物６と酸無水物７あるいは酸クロライド７’とを反応させて上記一般式（Ｉ）で表される本発明の二量体オキシムエステル化合物を得る。 The dimer oxime ester compound of the present invention represented by the general formula (I) can be produced, for example, by a method represented by the following reaction formula [Chemical Formula 6]. First, a carbazole compound 1 in which X 2 is a halogen atom and a carboxylic acid chloride 2 are reacted in the presence of zinc chloride to obtain an acyl compound 3. Next, the dimer 5 is obtained by reacting the acyl compound 3 with the dithiol compound or the diol compound 4 in the presence of sodium methoxide and dimethylformamide (DMF). Next, dimer 5 and hydroxylamine hydrochloride are reacted in the presence of DMF to obtain dimer oxime compound 6. Next, the dimer oxime compound 6 and the acid anhydride 7 or acid chloride 7 ′ are reacted to obtain the dimer oxime ester compound of the present invention represented by the above general formula (I).
本発明の二量体オキシムエステル化合物は、エチレン性不飽和結合を有する重合性化合物の光重合開始剤として有用である。 The dimer oxime ester compound of the present invention is useful as a photopolymerization initiator for a polymerizable compound having an ethylenically unsaturated bond.
次に、本発明の感光性組成物について説明する。
本発明の感光性組成物は、エチレン性不飽和結合を有する重合性化合物に、本発明の二量体オキシムエステル化合物を有効成分とする光重合開始剤を含有させてなるものである。
Next, the photosensitive composition of the present invention will be described.
The photosensitive composition of the present invention comprises a polymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator containing the dimer oxime ester compound of the present invention as an active ingredient.
エチレン性不飽和結合を有する上記重合性化合物としては、従来、感光性組成物に用いられているものを用いることができる。即ち、エチレン性不飽和結合を有する上記重合性化合物としては、例えば、スチレン、α−メチルスチレン、クロロスチレン等のスチレン系化合物；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）アクリレート、イソブチル（メタ）アクリレート、第二ブチル（メタ）アクリレート、第三ブチル（メタ）アクリレート、テトラヒドロフリル（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、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ポリ（エトキシ）エチル（メタ）アクリレート、プロピルオキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ブトキシエトキシエチル（メタ）アクリレート、ポリ（プロピルオキシ）プロピル（メタ）アクリレート、ビニル（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、トリエチレングリコールジ（メタ）アクリレート、ポリ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、ポリプロピレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（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、トリメチロールエタントリ（メタ）アクリレート、トリス（２−アクリロイルエチル）イソシアヌラート、ペンタエリスリトールテトラ（メタ）アクリレート等の多価アルコールをα，β−不飽和カルボン酸でエステル化して得られる化合物；アクリロニトリル、（メタ）アクリルアミド、Ｎ−置換（メタ）アクリレート；酢酸ビニル、イソブチルビニルエーテル、Ｎ−ビニルピロリドン、ビニルクロリド、ビニリデンクロリド、ジビニルベンゼン、ジビニルスクシナート、ジアリルフタラート、トリアリルホスファート、トリアリルイソシアヌラート等が挙げられる。これらの中でも、スチレン、メチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレートに対し、本発明の二量体オキシムエステル化合物を有効成分とする光重合開始剤は好適である。 As the polymerizable compound having an ethylenically unsaturated bond, those conventionally used in photosensitive compositions can be used. That is, examples of the polymerizable compound having an ethylenically unsaturated bond include styrene compounds such as styrene, α-methylstyrene, and chlorostyrene; methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meta ) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate Rate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, propyloxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, poly (propyloxy) propyl (meth) ) Acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexa Polyhydric alcohols such as polydiol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris (2-acryloylethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, α, Compounds obtained by esterification with β-unsaturated carboxylic acid; acrylonitrile, (meth) acrylamide, N-substituted (meth) acrylate; vinyl acetate, isobutyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride, divinylbenzene, divinyl Examples thereof include succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate and the like. Among these, the photoinitiator which uses the dimer oxime ester compound of this invention as an active ingredient with respect to styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, and hydroxyethyl (meth) acrylate is suitable. is there.
また、エチレン性不飽和結合を有する上記重合性化合物とともに、熱可塑性有機重合体を用いることによって、硬化物の特性を改善することもできる。該熱可塑性有機重合体としては、例えば、ポリスチレン、ポリメチルメタクリレート、メチルメタクリレート−エチルアクリレート共重合体、ポリ（メタ）アクリル酸、スチレン−（メタ）アクリル酸共重合体、（メタ）アクリル酸−メチルメタクリレート共重合体、ポリビニルブチラール、セルロースエステル、ポリアクリルアミド、飽和ポリエステル等が挙げられ、これらの中でも、ポリスチレン、（メタ）アクリル酸−メチルメタクリレート共重合体が好ましい。 Moreover, the characteristic of hardened | cured material can also be improved by using a thermoplastic organic polymer with the said polymeric compound which has an ethylenically unsaturated bond. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester. Among these, polystyrene and (meth) acrylic acid-methyl methacrylate copolymer are preferable.
また、本発明の感光性組成物には、光重合開始剤として、本発明の二量体オキシムエステル化合物の他に、必要に応じて、その他の光重合開始剤を併用することも可能であり、その他の光重合開始剤を併用することによって著しい相乗効果を奏する場合もある。 In addition to the dimer oxime ester compound of the present invention, if necessary, other photopolymerization initiators can be used in combination with the photosensitive composition of the present invention as a photopolymerization initiator. In some cases, a significant synergistic effect may be obtained by using other photopolymerization initiators together.
本発明の二量体オキシムエステル化合物と併用できる光重合開始剤としては、従来既知の化合物を用いることが可能であり、例えば、ベンゾフェノン、フェニルビフェニルケトン、１−ヒドロキシ−１−ベンゾイルシクロヘキサン、ベンジルジメチルケタール、１−ベンジル−１−ジメチルアミノ−１−（４'−モルホリノベンゾイル）プロパン、２−モルホリル−２−（４'−メチルメルカプト）ベンゾイルプロパン、チオキサントン、１−クロル−４−プロポキシチオキサントン、イソプロピルチオキサントン、ジエチルチオキサントン、エチルアントラキノン、４−ベンゾイル−４'−メチルジフェニルスルフィド、ベンゾインブチルエーテル、２−ヒドロキシ−２−ベンゾイルプロパン、２−ヒドロキシ−２−（４'−イソプロピル）ベンゾイルプロパン、４−ブチルベンゾイルトリクロロメタン、４−フェノキシベンゾイルジクロロメタン、ベンゾイル蟻酸メチル、１，７−ビス（９'−アクリジニル）ヘプタン、９−ｎ−ブチル−３，６−ビス（２'−モルホリノイソブチロイル）カルバゾール、２−メチル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−フェニル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−ナフチル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン等が挙げられる。 As the photopolymerization initiator that can be used in combination with the dimer oxime ester compound of the present invention, conventionally known compounds can be used, for example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyldimethyl. Ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropyl Thioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) ben Zoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoiso) Butyroyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (Trichloromethyl) -s-triazine and the like.
また、本発明の感光性組成物には、必要に応じて、ｐ−アニソール、ハイドロキノン、ピロカテコール、第三ブチルカテコール、フェノチアジン等の熱重合抑制剤；可塑剤；接着促進剤；充填剤等の慣用の添加剤を加えることができる。 In addition, the photosensitive composition of the present invention includes, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, tert-butylcatechol, and phenothiazine; plasticizers; adhesion promoters; Conventional additives can be added.
本発明の感光性組成物は、通常、必要に応じて前記の各成分（本発明のオキシムエステル化合物及びエチレン性不飽和結合を有する重合性化合物）を溶解又は分散し得る溶媒、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、メチルセロソルブ、エチルセロソルブ、クロロホルム、塩化メチレン、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、イソプロパノールを加えた溶液状組成物として用いられる。 The photosensitive composition of the present invention is usually a solvent capable of dissolving or dispersing each of the above components (the oxime ester compound of the present invention and a polymerizable compound having an ethylenically unsaturated bond), for example, acetone, if necessary. Methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol are used as a solution composition.
本発明の感光性組成物は、ロールコーター、カーテンコーター、各種の印刷、浸漬等の公知の手段で、金属、紙、プラスチック等の支持基体上に適用される。また、一旦フィルム等の支持基体上に施した後、他の支持基体上に転写することもでき、その適用方法に制限はない。 The photosensitive composition of the present invention is applied onto a support substrate such as metal, paper, plastic, etc. by a known means such as a roll coater, curtain coater, various printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.
本発明の感光性組成物は、光硬化性塗料、光硬化性インキ、光硬化性接着剤、印刷版、印刷配線板用フォトレジスト等の各種の用途に使用することができ、その用途に特に制限
はない。
The photosensitive composition of the present invention can be used for various applications such as a photocurable paint, a photocurable ink, a photocurable adhesive, a printing plate, and a photoresist for a printed wiring board. There is no limit.
また、本発明の二量体オキシムエステル化合物を含有する感光性組成物を硬化させる際に用いられる活性光の光源としては、波長３００〜４５０ｎｍの光を発光するものを用いることができ、例えば、超高圧水銀、水銀蒸気アーク、カーボンアーク、キセノンアーク等を用いることができる。 Moreover, as a light source of the active light used when hardening the photosensitive composition containing the dimer oxime ester compound of this invention, what emits light with a wavelength of 300-450 nm can be used, for example, Ultra high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be used.
尚、本発明の感光性組成物において、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、本発明の二量体オキシムエステル化合物は、エチレン性不飽和結合を有する上記重合性化合物１００質量部に対して、好ましくは１〜５０質量部、より好ましくは５〜３０質量部である。 In the photosensitive composition of the present invention, the addition amount of the photopolymerization initiator is not particularly limited, but the dimer oxime ester compound of the present invention is the polymerizable compound having an ethylenically unsaturated bond. Preferably it is 1-50 mass parts with respect to 100 mass parts, More preferably, it is 5-30 mass parts.
以下、実施例等を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.
〔実施例１〕化合物Ｎｏ．１の製造
＜ステップ１＞ベンゾイル体の製造
下記ベンゾイル体を、以下のようにして製造した。
Example 1 Compound No. 1 Production of 1 <Step 1> Production of benzoyl compound The following benzoyl compound was produced as follows.
２，４−ジクロロベンゾイルクロライド２０．９ｇ（０．１モル）、Ｎ−エチルカルバゾール３０ｇ（０．１５モル）、塩化アルミニウム１３．３ｇ（０．１モル）及びクロロホルム１５０ｇを仕込み、−４０℃にて１時間攪拌した。その後、酢酸エチル２００ｇ及び水２００ｇを加えて油層を抽出し、水洗を行なった。さらに、溶媒を留去後、カラムクロマトグラフィーにより精製を行い、アモルファス状物（収量８．７ｇ、収率２４％、純度９０％）を得た。 Charge 20.9 g (0.1 mol) of 2,4-dichlorobenzoyl chloride, 30 g (0.15 mol) of N-ethylcarbazole, 13.3 g (0.1 mol) of aluminum chloride and 150 g of chloroform to -40 ° C. And stirred for 1 hour. Thereafter, 200 g of ethyl acetate and 200 g of water were added to extract the oil layer and washed with water. Furthermore, after distilling off the solvent, purification was performed by column chromatography to obtain an amorphous product (yield 8.7 g, yield 24%, purity 90%).
得られたアモルファス状物の1Ｈ−ＮＭＲのケミカルシフトは次の通りであり、該アモルファス状物は目的物であるベンゾイル体であることを確認した。
８．５２（ｓ：１Ｈ）、８．１０（ｄ：１Ｈ）、８．００（ｄ：１Ｈ）、７．５３（ｓ：１Ｈ）、７．５１（ｔ：１Ｈ）、７．４５（ｄ：２Ｈ）、７．４１（ｄ：２Ｈ）、７．２８（ｔ：１Ｈ）、４．４１（ｃ：３Ｈ）、１．４７（ｔ：３Ｈ）
The chemical shift of 1 H-NMR of the obtained amorphous product was as follows, and it was confirmed that the amorphous product was a target benzoyl body.
8.52 (s: 1H), 8.10 (d: 1H), 8.00 (d: 1H), 7.53 (s: 1H), 7.51 (t: 1H), 7.45 (d : 2H), 7.41 (d: 2H), 7.28 (t: 1H), 4.41 (c: 3H), 1.47 (t: 3H)
＜ステップ２＞アシル体の製造
下記アシル体を、以下のようにして製造した。
<Step 2> Production of acyl body The following acyl body was produced as follows.
ステップ１で得られたベンゾイル体３６．５ｇ（０．１０モル）、塩化亜鉛２７．２ｇ（０．２モル）及びクロロホルム１００ｇを仕込み、８０℃まで昇温した後、無水酢酸２０．４ｇ（０．２モル）を１時間かけて滴下し、さらに２時間攪拌した。その後、酢酸エチル２００ｇと塩酸水を加えて塩化亜鉛を分解し、水洗を行なった。さらに溶媒を留去して酢酸エチル５００ｇから再結晶を行い、白色結晶（収量９．０ｇ、収率２２％、純度９１％）を得た。 36.5 g (0.10 mol) of the benzoyl compound obtained in Step 1, 27.2 g (0.2 mol) of zinc chloride and 100 g of chloroform were charged, and the temperature was raised to 80 ° C., and then 20.4 g (0 .2 mol) was added dropwise over 1 hour and the mixture was further stirred for 2 hours. Thereafter, 200 g of ethyl acetate and aqueous hydrochloric acid were added to decompose zinc chloride, followed by washing with water. Further, the solvent was distilled off and recrystallization was performed from 500 g of ethyl acetate to obtain white crystals (yield 9.0 g, yield 22%, purity 91%).
得られた白色結晶は、融点１７２℃で、1Ｈ−ＮＭＲのケミカルシフトが次の通りであり、目的物であるアシル体であることを確認した。
８．７１（ｓ：１Ｈ）、８．５０（ｓ：１Ｈ）、８．１７（ｄ：１Ｈ）、８．０９（ｄ：１Ｈ）、７．５６（ｓ：１Ｈ）、７．５１（ｄ：１Ｈ）、７．４９（ｄ：１Ｈ）、７．４１（ｄ：２Ｈ）、４．４３（ｃ：３Ｈ）、２．７３（ｓ：３Ｈ）、（１．５０ｔ：３Ｈ）
The obtained white crystals had a melting point of 172 ° C., 1 H-NMR chemical shift as follows, and were confirmed to be the target acyl.
8.71 (s: 1H), 8.50 (s: 1H), 8.17 (d: 1H), 8.09 (d: 1H), 7.56 (s: 1H), 7.51 (d : 1H), 7.49 (d: 1H), 7.41 (d: 2H), 4.43 (c: 3H), 2.73 (s: 3H), (1.50t: 3H)
＜ステップ３＞二量体１の製造
下記二量体１を、以下のようにして製造した。
<Step 3> Production of dimer 1 The following dimer 1 was produced as follows.
ステップ２で得られたアシル体９．０３ｇ（０．０２２モル）及びジメチルホルムアミド（ＤＭＦ）２０ｇを仕込み、さらに１，５−ペンタンジチオール１．３９ｇ（０．０１モル）を仕込み、５０℃まで昇温した。ナトリウムメトキシド４．２４ｇ（０．０２２モル）を徐々に滴下し、６０℃で１時間保持し、続いて６０℃で１時間攪拌した。その後、酢酸エチル２０ｇを加え、油層を水２０ｇにて２回洗浄すると結晶が析出したため、これをろ別し、淡黄色結晶を得た。ろ液を水、続いて飽和食塩水で洗浄し、硫酸ナトリウムで乾燥後、溶媒を留去してさらに淡黄色結晶を得た。得られた淡黄色結晶（二量体１）は、あわせて収量５．４７ｇ、収率６３％、純度８５％であった。 9.03 g (0.022 mol) of the acyl compound obtained in Step 2 and 20 g of dimethylformamide (DMF) were charged, and 1.39 g (0.01 mol) of 1,5-pentanedithiol was further charged, and the temperature was raised to 50 ° C. Warm up. 4.24 g (0.022 mol) of sodium methoxide was gradually added dropwise, maintained at 60 ° C. for 1 hour, and then stirred at 60 ° C. for 1 hour. Thereafter, 20 g of ethyl acetate was added, and the oil layer was washed twice with 20 g of water. As a result, crystals were precipitated, which was filtered off to obtain pale yellow crystals. The filtrate was washed with water and then with saturated brine, dried over sodium sulfate, and then the solvent was distilled off to obtain further pale yellow crystals. The obtained pale yellow crystals (dimer 1) had a combined yield of 5.47 g, a yield of 63%, and a purity of 85%.
＜ステップ４＞二量体オキシム１の製造
下記二量体オキシム１を、以下のようにして製造した。
<Step 4> Production of dimer oxime 1 The following dimer oxime 1 was produced as follows.
ステップ３で得られた二量体１の４．４２ｇ（０．００５モル）、ヒドロキシルアミン塩酸塩１．０４ｇ（０．０１５モル）及びＤＭＦ９ｇを仕込み、６０℃で２時間攪拌した。反応液をメタノール：水＝５：１（体積比）５０ｍｌに滴下した。固体をろ別し、メタノール、水で洗浄後、乾燥して淡黄色結晶として二量体オキシム１（収量４．００ｇ、収率８１％、純度８１％）を得た。 4.42 g (0.005 mol) of the dimer 1 obtained in Step 3, 1.04 g (0.015 mol) of hydroxylamine hydrochloride and 9 g of DMF were charged and stirred at 60 ° C. for 2 hours. The reaction solution was added dropwise to 50 ml of methanol: water = 5: 1 (volume ratio). The solid was filtered off, washed with methanol and water, and dried to obtain dimer oxime 1 (yield 4.00 g, yield 81%, purity 81%) as pale yellow crystals.
＜ステップ５＞化合物Ｎｏ．１の製造
ステップ４で得られた二量体オキシム１の３．６６ｇ（０．００４モル）及びクロロホルム１５ｇを仕込み、６０℃まで昇温した。無水酢酸１．２３ｇ（０．０１２モル）を滴下し、６５℃で３０分攪拌した。クロロホルム５０ｍｌを加え、反応液をメタノール１００ｍｌに滴下すると結晶が析出した。結晶をろ別して、淡黄色結晶（収量０．６３ｇ、収率１８％、純度９２％）を得た。該淡黄色結晶について分析を行なったところ、該淡黄色結晶は目的物である化合物Ｎｏ．１であることが確認された。分析結果を以下に示す。
<Step 5> Compound No. Production of 1 3.66 g (0.004 mol) of dimer oxime 1 obtained in Step 4 and 15 g of chloroform were charged, and the temperature was raised to 60 ° C. Acetic anhydride 1.23g (0.012mol) was dripped, and it stirred at 65 degreeC for 30 minutes. When 50 ml of chloroform was added and the reaction solution was added dropwise to 100 ml of methanol, crystals were precipitated. The crystals were filtered off to obtain pale yellow crystals (yield 0.63 g, yield 18%, purity 92%). When the pale yellow crystals were analyzed, the pale yellow crystals were the target compound No. 1 was confirmed. The analysis results are shown below.
（分析結果）
（１）融点：１６０．６℃
（２）1Ｈ−ＮＭＲ測定：
８．５１（ｄ：２Ｈ）、８．４４（ｄ：２Ｈ）、８．０８（ｄｄ：２Ｈ）、７．９７（ｄｄ：２Ｈ）、７．４６（ｄ：２Ｈ）、７．４４（ｄ：２Ｈ）、７．４１（ｄ：２Ｈ）、７．３８（ｄ：２Ｈ）、７．３１（ｄｄ：２Ｈ）、４．４１（ｑ：４Ｈ）、３．４９（ｂｒ：２Ｈ）、３．０７（ｔ：４Ｈ）、２．５１（ｓ：６Ｈ）、２．２９（ｓ：６Ｈ）、１．８４‐１．７８（ｍ：４Ｈ）、１．４７（ｔ：６Ｈ）
（３）ＩＲ測定：（ｃｍ‐1）
２９３２、１７６６、１６５１、１６２７、１５９２、１４８９、１３３７、１２９７、１２７４、１２４７、１１２８、９３４、８９６、８１５、７５９、７２０
（４）ＵＶスペクトル測定（アセトニトリル：水＝９：１）
λｍａｘ＝２６１、３００、３４１ｎｍ
(result of analysis)
(1) Melting point: 160.6 ° C
(2) 1 H-NMR measurement:
8.51 (d: 2H), 8.44 (d: 2H), 8.08 (dd: 2H), 7.97 (dd: 2H), 7.46 (d: 2H), 7.44 (d : 2H), 7.41 (d: 2H), 7.38 (d: 2H), 7.31 (dd: 2H), 4.41 (q: 4H), 3.49 (br: 2H), 3 .07 (t: 4H), 2.51 (s: 6H), 2.29 (s: 6H), 1.84-1.78 (m: 4H), 1.47 (t: 6H)
(3) IR measurement: (cm- 1 )
2932, 1766, 1651, 1627, 1592, 1489, 1337, 1297, 1274, 1247, 1128, 934, 896, 815, 759, 720
(4) UV spectrum measurement (acetonitrile: water = 9: 1)
λmax = 261, 300, 341 nm
〔実施例２〕化合物Ｎｏ．２の製造
＜ステップ１＞二量体２の製造
下記二量体２を、以下のようにして製造した。
Example 2 Compound No. Production of 2 <Step 1> Production of dimer 2 The following dimer 2 was produced as follows.
実施例１のステップ２で製造したアシル体２．２６ｇ（０．００６モル）及びＤＭＦ５ｇを仕込み、１，４−ブタンジチオール０．３２ｇ（０．００３モル）を加え、５０℃まで昇温した。ナトリウムメトキシド０．３０ｇ（０．００６モル）を加え、５０℃で４時間攪拌すると結晶が徐々に析出した。結晶をろ別し、ＤＭＦ、メタノールで洗浄し、薄赤色結晶として二量体２（収量１．８５ｇ、収率８０％、純度９４％）を得た。 2.26 g (0.006 mol) of the acyl compound produced in Step 2 of Example 1 and 5 g of DMF were charged, 0.32 g (0.003 mol) of 1,4-butanedithiol was added, and the temperature was raised to 50 ° C. When 0.30 g (0.006 mol) of sodium methoxide was added and stirred at 50 ° C. for 4 hours, crystals gradually precipitated. The crystals were filtered off and washed with DMF and methanol to obtain Dimer 2 (yield 1.85 g, yield 80%, purity 94%) as pale red crystals.
＜ステップ２＞二量体オキシム２の製造
下記二量体オキシム２を、以下のようにして製造した。
ステップ１で得られた二量体２の３．４８ｇ（０．００４モル）、塩酸ヒドロキシルアミン０．８３ｇ（０．０１２モル）及びＤＭＦ８ｇを仕込み、６０℃で3時間攪拌した。メタノール８ｍｌ及び水４ｍｌを加えて結晶をろ別し、淡黄色結晶として二量体オキシム２（収量２．５４ｇ、収率５８％、純度７４％）を得た。 3.48 g (0.004 mol) of dimer 2 obtained in Step 1, 0.83 g (0.012 mol) of hydroxylamine hydrochloride and 8 g of DMF were charged and stirred at 60 ° C. for 3 hours. 8 ml of methanol and 4 ml of water were added and the crystals were filtered off to obtain dimer oxime 2 (yield 2.54 g, yield 58%, purity 74%) as pale yellow crystals.
＜ステップ３＞化合物Ｎｏ．２の製造
ステップ２で得られた二量体オキシム２の２．２５ｇ（０．００３モル）及びクロロホルム１０ｇを仕込み、６０℃まで昇温した。さらに無水酢酸０．６１ｇ（０．００３モル）を滴下し、６５℃で３０分攪拌した。メタノール１００ｍｌに反応液を加えると結晶が析出したので、これをろ別し、淡黄色粗結晶（収量１．９１ｇ、粗収率１００％、純度８５％）を得た。得られた粗結晶をクロロホルム１０ｍｌに溶解し、６０℃まで加熱してメタノール１５ｍｌを滴下した。固体をろ別し、白色結晶（収量１．１３ｇ、収率５９％、純度９５％）を得た。得られた白色結晶について分析を行なったところ、該白色結晶は目的物である化合物Ｎｏ．２であると確認された。分析結果を以下に示す。
<Step 3> Compound No. Production of 2 2.25 g (0.003 mol) of dimer oxime 2 obtained in Step 2 and 10 g of chloroform were charged, and the temperature was raised to 60 ° C. Further, 0.61 g (0.003 mol) of acetic anhydride was added dropwise and stirred at 65 ° C. for 30 minutes. When the reaction solution was added to 100 ml of methanol, crystals were precipitated. The crystals were separated by filtration to obtain pale yellow crude crystals (yield 1.91 g, crude yield 100%, purity 85%). The obtained crude crystals were dissolved in 10 ml of chloroform, heated to 60 ° C., and 15 ml of methanol was added dropwise. The solid was filtered off to obtain white crystals (yield 1.13 g, yield 59%, purity 95%). When the obtained white crystals were analyzed, the white crystals were the target compound No. 1. 2 was confirmed. The analysis results are shown below.
（分析結果）
（１）融点：１４９．７℃
（２）1Ｈ−ＮＭＲ測定：
８．５１（ｄ：２Ｈ）、８．４６（ｄ：２Ｈ）、８．０９（ｄｄ：２Ｈ）、７．９７（ｄｄ：２Ｈ）、７．４７（ｄ：２Ｈ）、７．４４（ｄ：２Ｈ）、７．４２（ｄ：２Ｈ）、７．３８（ｄ：２Ｈ）、７．３１（ｄｄ：２Ｈ）、４．４１（ｑ：４Ｈ）、３．１２‐３．０８（ｍ：４Ｈ）、２．５１（ｓ：６Ｈ）、２．２８（ｓ：６Ｈ）、１．９７‐１．９４（ｍ：４Ｈ）、１．４７（ｔ：６Ｈ）
（３）ＩＲ測定：（ｃｍ‐1）
２９３１、１７６０、１６５６、１６２２、１５８５、１４８４、１４３２、１３６８、１３４９、１３３４、１３０８、１２７５、１２４８、１１３１、１１０５、９３６、８９６、８２４、８１３
（４）ＵＶスペクトル測定（アセトニトリル：水＝９：１）
λｍａｘ＝２６１、２９９、３４１ｎｍ
(result of analysis)
(1) Melting point: 149.7 ° C
(2) 1 H-NMR measurement:
8.51 (d: 2H), 8.46 (d: 2H), 8.09 (dd: 2H), 7.97 (dd: 2H), 7.47 (d: 2H), 7.44 (d : 2H), 7.42 (d: 2H), 7.38 (d: 2H), 7.31 (dd: 2H), 4.41 (q: 4H), 3.12-3.08 (m: 4H), 2.51 (s: 6H), 2.28 (s: 6H), 1.97-1.94 (m: 4H), 1.47 (t: 6H)
(3) IR measurement: (cm- 1 )
2931, 1760, 1656, 1622, 1585, 1484, 1432, 1368, 1349, 1334, 1308, 1275, 1248, 1131, 1105, 936, 896, 824, 813
(4) UV spectrum measurement (acetonitrile: water = 9: 1)
λmax = 261, 299, 341 nm
〔実施例３〕化合物Ｎｏ．3の製造
＜ステップ１＞二量体３の製造
下記二量体３を、以下のようにして製造した。
Example 3 Compound no. Production of 3 <Step 1> Production of dimer 3 The following dimer 3 was produced as follows.
実施例１のステップ２で製造したアシル体１０．２ｇ（０．０２５モル）、ｐ−キシレン−α，α’−ジチオール２．０３ｇ（０．０１１モル）及びＤＭＦ２０ｇを仕込み、５０℃まで昇温した後、ナトリウムメトキシド１．３４ｇ（０．０２５モル）を１時間かけて少量ずつ加えた。塩化メチレン２０ｇ及び水２０ｇを加えて抽出を行い、油層を水洗後、硫酸マグネシウムで乾燥し、溶媒を留去してテトラヒドロフラン（ＴＨＦ）／ジエチルエーテル混合溶媒から再結晶を行い、肌色結晶として二量体３（収量１１．７９ｇ、収率５２％、純度９５％）を得た。 Charge 10.2 g (0.025 mol) of the acyl compound produced in Step 2 of Example 1, 2.03 g (0.011 mol) of p-xylene-α, α′-dithiol and 20 g of DMF, and heat up to 50 ° C. After that, 1.34 g (0.025 mol) of sodium methoxide was added little by little over 1 hour. Extraction was carried out by adding 20 g of methylene chloride and 20 g of water, and the oil layer was washed with water and dried over magnesium sulfate. The solvent was distilled off, and recrystallization was performed from a tetrahydrofuran (THF) / diethyl ether mixed solvent. Body 3 (yield 11.79 g, yield 52%, purity 95%) was obtained.
＜ステップ２＞二量体オキシム３の製造
下記二量体オキシム３を、以下のようにして製造した。
<Step 2> Production of dimer oxime 3 The following dimer oxime 3 was produced as follows.
ステップ１で得られた二量体３の４．５９ｇ（０．００５モル）及びＤＭＦ１０ｇを仕込み、６５℃まで昇温した。さらに塩酸ヒドロキシルアミン１．０４ｇ（０．０１５モル）を滴下し、６５℃で３時間攪拌した。室温まで冷却し、酢酸エチル２０ｇ及び水２０ｇを加えて抽出し、飽和炭酸水素ナトリウム水溶液、飽和食塩水で洗浄し、硫酸ナトリウムで乾燥後、溶媒を留去して淡黄色固体として二量体オキシム３（収量５．００ｇ、収率７０％、純度５８％）を得た。 4.59 g (0.005 mol) of the dimer 3 obtained in Step 1 and 10 g of DMF were charged, and the temperature was raised to 65 ° C. Further, 1.04 g (0.015 mol) of hydroxylamine hydrochloride was added dropwise, and the mixture was stirred at 65 ° C. for 3 hours. The mixture was cooled to room temperature, extracted by adding 20 g of ethyl acetate and 20 g of water, washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over sodium sulfate, and then the solvent was distilled off to dimer oxime as a pale yellow solid. 3 (yield 5.00 g, yield 70%, purity 58%) was obtained.
＜ステップ３＞化合物Ｎｏ．３の製造
ステップ２で得られた二量体オキシム３の１．５９ｇ（０．００２モル）及びクロロホルム５ｇを仕込み、５５℃まで昇温した。無水酢酸０．４１ｇ（０．００４モル）を滴下し５５℃で３０分攪拌した。その後、反応液をメタノール１００ｍｌに滴下した。固体をろ別し、黄色結晶（収量１．３６ｇ、収率７８％、純度６４％）を得た。得られた黄色結晶について分析を行なったところ、該黄色結晶は目的物である化合物Ｎｏ．３であることが確認された。分析結果を以下に示す。
<Step 3> Compound No. Preparation of 3 1.59 g (0.002 mol) of dimer oxime 3 obtained in Step 2 and 5 g of chloroform were charged, and the temperature was raised to 55 ° C. Acetic anhydride 0.41 g (0.004 mol) was added dropwise and stirred at 55 ° C. for 30 minutes. Thereafter, the reaction solution was added dropwise to 100 ml of methanol. The solid was filtered off to obtain yellow crystals (yield 1.36 g, yield 78%, purity 64%). When the obtained yellow crystals were analyzed, the yellow crystals were the target compound No. 1. 3 was confirmed. The analysis results are shown below.
（分析結果）
（１）融点：１５０．０℃
（２）1Ｈ−ＮＭＲ測定：
８．４９（ｄ：２Ｈ）、８．４５（ｄ：２Ｈ）、８．０６（ｄｄ：２Ｈ）、７．９７（ｄｄ：２Ｈ）、７．４６（ｄ：２Ｈ）、７．４４（ｄ：２Ｈ）、７．４１‐７．３９（ｍ：４Ｈ）、７．３４（ｄ：４Ｈ）、７．２８（ｄｄ：２Ｈ）、４．４１（ｑ：４Ｈ）、４．２４（ｓ：４Ｈ）、２．５２（ｓ：６Ｈ）、２．２９（ｓ：６Ｈ）、１．４７（ｔ：６Ｈ）
（３）ＩＲ測定：（ｃｍ‐1）
２９７５、１７６１、１６４９、１５８９、１４８８、１４２８、１３７２、１２３７、１２９６、１２０４、１１２８、１０４７、９８３、９３４、９０１、８５９、８１８、７６０、７１８、６６９、６２８
（４）ＵＶスペクトル測定（アセトニトリル：水＝９：１）
λｍａｘ＝２６１、３００、３４４ｎｍ
(result of analysis)
(1) Melting point: 150.0 ° C
(2) 1 H-NMR measurement:
8.49 (d: 2H), 8.45 (d: 2H), 8.06 (dd: 2H), 7.97 (dd: 2H), 7.46 (d: 2H), 7.44 (d : 2H), 7.41-7.39 (m: 4H), 7.34 (d: 4H), 7.28 (dd: 2H), 4.41 (q: 4H), 4.24 (s: 4H), 2.52 (s: 6H), 2.29 (s: 6H), 1.47 (t: 6H)
(3) IR measurement: (cm- 1 )
2975, 1761, 1649, 1589, 1488, 1428, 1372, 1237, 1296, 1204, 1128, 1047, 983, 934, 901, 859, 818, 760, 718, 669, 628
(4) UV spectrum measurement (acetonitrile: water = 9: 1)
λmax = 261, 300, 344 nm
〔実施例４〕二量体オキシムエステル化合物の混合物の製造
＜ステップ１＞二量体４の製造
下記二量体４を、以下のようにして製造した。
Example 4 Production of Mixture of Dimer Oxime Ester Compound <Step 1> Production of Dimer 4 The following dimer 4 was produced as follows.
水素化ナトリウム０．３０ｇ（０．００６モル）に１，３‐ ジメチル‐２‐イミダゾリジノン（ＤＭＩ）１ｇを混合し、これにジエチレングリコール０．２９ｇ（０．００３モル）を徐々に滴下して、水素ガスの発生がおさまるまで攪拌した。続いて、実施例１のステップ２で製造したアシル体３．０８ｇ（０．００８モル）及びＤＭＩ ４ｇを仕込み、これに、先に調製した水素化ナトリウム、ＤＭＩ及びジエチレングリコールを混合したものを１時間かけて徐々に滴下した。１００℃で３時間反応を行い、ジクロロメタン２０ｇ及び水２０ｇを加えて抽出を行った。油層を硫酸マグネシウムで乾燥し、溶媒を留去して、クロロホルム／メタノール混合溶媒を用いて再沈殿を行い、淡黄色結晶として二量体４（収量１．７３ｇ、収率２８％、純度３４％）を得た。 To 0.30 g (0.006 mol) of sodium hydride, 1 g of 1,3-dimethyl-2-imidazolidinone (DMI) was mixed, and 0.29 g (0.003 mol) of diethylene glycol was gradually added dropwise thereto. The mixture was stirred until generation of hydrogen gas was stopped. Subsequently, 3.08 g (0.008 mol) of the acyl compound produced in Step 2 of Example 1 and 4 g of DMI were charged, and the mixture of sodium hydride, DMI and diethylene glycol prepared previously was added for 1 hour. It was dripped gradually over the time. Reaction was performed at 100 ° C. for 3 hours, and extraction was performed by adding 20 g of dichloromethane and 20 g of water. The oil layer was dried over magnesium sulfate, the solvent was distilled off, and reprecipitation was performed using a chloroform / methanol mixed solvent, and dimer 4 (yield 1.73 g, yield 28%, purity 34%) as pale yellow crystals. )
＜ステップ２＞二量体オキシム４の製造
下記二量体オキシム４を、以下のようにして製造した。
<Step 2> Production of dimer oxime 4 The following dimer oxime 4 was produced as follows.
ステップ１で得られた二量体４の１．７１ｇ（０．００２モル）、塩酸ヒドロキシルアミン０．４２ｇ（０．００６モル）及びＤＭＦ４ｇを仕込み、６０℃で３時間攪拌した。反応液をメタノール：水＝４：１（体積比）５０ｍｌに滴下した。固体をろ別し、淡黄色結晶として二量体オキシム４（収量２．５０ｇ、収率２９％、純度３８％）を得た。 1.71 g (0.002 mol) of dimer 4 obtained in Step 1, 0.42 g (0.006 mol) of hydroxylamine hydrochloride and 4 g of DMF were charged and stirred at 60 ° C. for 3 hours. The reaction solution was added dropwise to 50 ml of methanol: water = 4: 1 (volume ratio). The solid was filtered off to obtain dimer oxime 4 (yield 2.50 g, yield 29%, purity 38%) as pale yellow crystals.
＜ステップ３＞二量体オキシムエステル化合物の混合物の製造
下記二量体オキシムエステル化合物の混合物を、以下のようにして製造した。
<Step 3> Production of Dimer Oxime Ester Compound Mixture The following dimer oxime ester compound mixture was produced as follows.
ステップ２で得られた二量体オキシム４の０．１５ｇ（０．０００２モル）及びクロロホルム１ｇを仕込み、５５℃まで昇温した。続いて無水酢酸０．０４２ｇ（０．０００４モル）を滴下し、５５℃で１時間攪拌した。反応液をメタノール１０ｍｌに滴下した。固体をろ別し、黄色結晶（収量０．０６５ｇ、収率３６％、純度８８％）を得た。得られた黄色結晶について分析を行なったところ、該黄色結晶は目的物である二量体オキシムエステル化合物の混合物であることが確認され、得られた二量体オキシムエステル化合物の混合物のうち、ｏ‐ｏ体は１６％、ｏ‐ｐ体は４８％、ｐ‐ｐ体は３６％であった。分析結果を以下に示す。なお、融点、1Ｈ−ＮＭＲ測定、ＩＲ測定については混合物についての分析結果であり、ＵＶスペクトル測定については、三次元ＨＰＬＣ分析において検出器をＵＶとし、ｏ‐ｏ体、ｏ‐ｐ体、ｐ‐ｐ体それぞれの保持時間において検出した分析結果である。 0.15 g (0.0002 mol) of dimer oxime 4 obtained in Step 2 and 1 g of chloroform were charged, and the temperature was raised to 55 ° C. Subsequently, 0.042 g (0.0004 mol) of acetic anhydride was added dropwise, and the mixture was stirred at 55 ° C. for 1 hour. The reaction solution was added dropwise to 10 ml of methanol. The solid was filtered off to obtain yellow crystals (yield 0.065 g, yield 36%, purity 88%). When the obtained yellow crystals were analyzed, it was confirmed that the yellow crystals were a mixture of the dimer oxime ester compound as the target product. Of the obtained mixture of dimer oxime ester compounds, o -O form was 16%, op form was 48%, and pp form was 36%. The analysis results are shown below. In addition, about melting | fusing point, < 1 > H-NMR measurement, and IR measurement, it is the analysis result about a mixture, About UV spectrum measurement, the detector is set to UV in three-dimensional HPLC analysis, oo body, op body, p -It is the analysis result detected in the retention time of each p body.
（分析結果）
（１）融点：１６０．７℃
（２）1Ｈ−ＮＭＲ測定：
８．５３ー８．４２（ｍ：４Ｈ）、８．１２ー７．８９（ｍ：４Ｈ）、７．４７ー６．６０（ｍ：１０Ｈ）、４．４４ー４．３１（ｍ：４Ｈ）、４．１６ー３．０４（２Ｈ，２Ｈ，ｔ，ｔ）[４．１６（ｔ：２Ｈ）、３．６８（ｔ：２Ｈ）、３．６５（ｔ：２Ｈ）、３．５５（ｔ：２Ｈ）、３．４５（ｔ：２Ｈ）、３．０４（ｔ：２Ｈ）]、２．５０ー２．４８（ｍ：６Ｈ）、２．２９ー２．２６（ｍ：６Ｈ）、１．５０ー１．３７（ｍ：６Ｈ）
（３）ＩＲ測定：（ｃｍ‐1）
２９３２、１７６２、１６５４、１６２７、１５９１、１４８６、１３６６、１３３６、１２９８、１２７３、１２４６、１１２９、１０９２、１０４２、９３４、８１２、７６９、７６２、７２７
（４）ＵＶスペクトル測定（アセトニトリル：水＝９：１）
ｏ‐ｏ体：λｍａｘ＝２７１、２９９、３４１ｎｍ
ｏ‐ｐ体：λｍａｘ＝２６５、２９７、３４１ｎｍ
ｐ‐ｐ体：λｍａｘ＝２６３、２９６、３３９ｎｍ
(result of analysis)
(1) Melting point: 160.7 ° C
(2) 1 H-NMR measurement:
8.53-8.42 (m: 4H), 8.12-7.89 (m: 4H), 7.47-6.60 (m: 10H), 4.44-4.31 (m: 4H) ), 4.16-3.04 (2H, 2H, t, t) [4.16 (t: 2H), 3.68 (t: 2H), 3.65 (t: 2H), 3.55 ( t: 2H), 3.45 (t: 2H), 3.04 (t: 2H)], 2.50-2.48 (m: 6H), 2.29-2.26 (m: 6H), 1.50-1.37 (m: 6H)
(3) IR measurement: (cm- 1 )
2932, 1762, 1654, 1627, 1591, 1486, 1366, 1336, 1298, 1273, 1246, 1129, 1092, 1042, 934, 812, 769, 762, 727
(4) UV spectrum measurement (acetonitrile: water = 9: 1)
oo body: λmax = 271, 299, 341 nm
op body: λmax = 265, 297, 341 nm
pp body: λmax = 263, 296, 339 nm
〔実施例５〕感光性組成物の製造
アクリル系共重合体１００ｇに対し、トリメチロールプロパンアクリレート０．４ｇ、実施例１で得られた化合物Ｎｏ．１の０．０２ｇ及び２，２−ビス（２−クロロフェニル）−４，５，４'，５'−テトラフェニル−１−２'−ビイミダゾール０．０２ｇを加えて良く攪拌し、感光性組成物を得た。
尚、上記アクリル系共重合体は、メタクリル酸２０質量部、ヒドロキシエチルメタクリレート１５質量部、メチルメタクリレート１０質量部及びブチルメタクリレート５５質量部をエチルセロソルブ３００質量部に溶解し、窒素雰囲気下でアゾビスイソブチルニトリル０．７５質量部を加えて７０℃で５時間反応させることにより得られたものである。
[Example 5] Production of photosensitive composition To 100 g of acrylic copolymer, 0.4 g of trimethylolpropane acrylate, the compound No. obtained in Example 1 was used. 1 and 0.02 g of 2,2-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1-2′-biimidazole were added and stirred well to prepare a photosensitive composition. I got a thing.
The acrylic copolymer was prepared by dissolving 20 parts by mass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate and 55 parts by mass of butyl methacrylate in 300 parts by mass of ethyl cellosolve, and azobis under nitrogen atmosphere. It was obtained by adding 0.75 part by mass of isobutylnitrile and reacting at 70 ° C. for 5 hours.
次いで、基板上にｒ−グリシドキシプロピルメチルエトキシシランをスピンコートして良くスピン乾燥させた後、上記感光性組成物をスピンコート（１０００ｒ．ｐ．ｍ、４０秒間）し乾燥させた。７０℃で２０分間プリベークを行った後、画素サイズ３０μｍ×１００μｍのマスクを用い、光源として超高圧水銀ランプを用いて露光した。次に、２．５質量％炭酸ナトリウム溶液で現像後、良く水洗し、さらに水洗乾燥後、２３０℃で１時間ベークしてパターンを定着させた。尚、露光量は８０ｍＪ／ｃｍ2であった。 Next, r-glycidoxypropylmethylethoxysilane was spin-coated on the substrate and spin-dried well, and then the photosensitive composition was spin-coated (1000 rpm, 40 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, exposure was performed using a mask having a pixel size of 30 μm × 100 μm and an ultrahigh pressure mercury lamp as a light source. Next, after developing with a 2.5% by mass sodium carbonate solution, it was washed thoroughly with water, further washed with water and dried, and baked at 230 ° C. for 1 hour to fix the pattern. The exposure amount was 80 mJ / cm 2 .
光重合開始剤として本発明の二量体オキシムエステル化合物を含有する上記感光性組成物は、感度に優れ、重合物の着色や重合物及び装置の汚染がなく、得られたパターンは鮮明であった。また、上記感光性組成物をスピンコートした後１０日以上放置しても、光重合開始剤の析出はなかった。 The photosensitive composition containing the dimer oxime ester compound of the present invention as a photopolymerization initiator is excellent in sensitivity, free from coloring of the polymer and contamination of the polymer and the apparatus, and the pattern obtained is clear. It was. Further, even when the photosensitive composition was spin-coated and left standing for 10 days or more, no photopolymerization initiator was deposited.
〔実施例６〕感光性組成物の製造
スチレン−アクリル系感光性共重合体１００ｇに対し、トリメチロールプロパンアクリレート０．４ｇ及び実施例１で得られた化合物Ｎｏ．１の０．０２ｇを加えて良く攪拌し、感光性組成物を得た。
尚、上記スチレン−アクリル系感光性共重合体は、スチレン２６．３質量部、２−ヒドロキシメタクリレート４３．８質量部、メタクリル酸３５質量部及びメタクリル酸エチル７０質量部をエチルセロソルブ１７５質量部に溶解し、窒素雰囲気下でアゾビスイソブチルニトリル０．７５質量部を加え９０℃で５時間反応させ、次いで、イソシアネートエチルメタクリレート２３．５質量部及びオクチル酸錫０．１１質量部をエチルセロソルブ２０質量部で溶解したものを約１０分かけて滴下し、滴下後２時間反応させることにより得られたものである。
[Example 6] Production of photosensitive composition To 100 g of a styrene-acrylic photosensitive copolymer, 0.4 g of trimethylolpropane acrylate and the compound No. obtained in Example 1 were used. 0.02 g of No. 1 was added and stirred well to obtain a photosensitive composition.
The styrene-acrylic photosensitive copolymer is composed of 26.3 parts by mass of styrene, 43.8 parts by mass of 2-hydroxymethacrylate, 35 parts by mass of methacrylic acid, and 70 parts by mass of ethyl methacrylate in 175 parts by mass of ethyl cellosolve. Dissolve, add 0.75 parts by mass of azobisisobutylnitrile in a nitrogen atmosphere and react at 90 ° C. for 5 hours. What was melt | dissolved in a part is dripped over about 10 minutes, and it is obtained by making it react for 2 hours after dripping.
次いで、基板上にｒ−グリシドキシプロピルメチルエトキシシランをスピンコートして良くスピン乾燥させた後、上記感光性組成物をスピンコート（１０００ｒ．ｐ．ｍ、４０秒間）し乾燥させた。７０℃で２０分間プリベークを行った後、画素サイズ３０μｍ×１００μｍのマスクを用い、光源として超高圧水銀ランプを用いて露光した。次に、２．５質量％炭酸ナトリウム溶液で現像後、良く水洗し、さらに水洗乾燥後、２３０℃で１時間ベークしてパターンを定着させた。尚、露光量は８０ｍＪ／ｃｍ2であった。 Next, r-glycidoxypropylmethylethoxysilane was spin-coated on the substrate and spin-dried well, and then the photosensitive composition was spin-coated (1000 rpm, 40 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, exposure was performed using a mask having a pixel size of 30 μm × 100 μm and an ultrahigh pressure mercury lamp as a light source. Next, after developing with a 2.5% by mass sodium carbonate solution, it was washed thoroughly with water, further washed with water and dried, and baked at 230 ° C. for 1 hour to fix the pattern. The exposure amount was 80 mJ / cm 2 .
光重合開始剤として本発明の二量体オキシムエステル化合物を含有する上記感光性組成物は、感度に優れ、重合物の着色や重合物及び装置の汚染がなく、得られたパターンは鮮明であった。また、上記感光性組成物をスピンコートした後１０日以上放置しても、光重合開始剤の析出はなかった。 The photosensitive composition containing the dimer oxime ester compound of the present invention as a photopolymerization initiator is excellent in sensitivity, free from coloring of the polymer and contamination of the polymer and the apparatus, and the pattern obtained is clear. It was. Further, even when the photosensitive composition was spin-coated and left standing for 10 days or more, no photopolymerization initiator was deposited.
〔比較例１〕感光性組成物の製造
実施例５で用いたアクリル系共重合体１００ｇに対して、ジペンタエリスリトールペンタ及びヘキサアクリレート０．４ｇ及び比較化合物１（下記〔化１８〕）１０．０２ｇを加えて良く攪拌し、感光性組成物を得た。
[Comparative Example 1] Production of photosensitive composition To 100 g of the acrylic copolymer used in Example 5, 0.4 g of dipentaerythritol penta and hexaacrylate and comparative compound 1 (the following [Chemical Formula 18]) 10. 02 g was added and stirred well to obtain a photosensitive composition.
次いで、基板上にｒ−グリシドキシプロピルメチルエトキシシランをスピンコートして良くスピン乾燥させた後、上記感光性組成物をスピンコート（１３００ｒ．ｐ．ｍ、５０秒間）し乾燥させた。７０℃で２０分間プリベークを行った後、ポリビニルアルコール５質量％溶液をコートして酸素遮断膜とした。７０℃２０分間の乾燥後、所定のマスクを用い、光源として超高圧水銀ランプを用いて露光後、２．５質量％炭酸ナトリウム溶液で現像して良く水洗した。水洗乾燥後、２３０℃で１時間ベークしてパターンを定着させた。尚、露光量は、８０ｍＪ／ｃｍ2であった。得られたパターンは、実施例５で得られたパターンに較べて不鮮明であった。 Next, r-glycidoxypropylmethylethoxysilane was spin-coated on the substrate and spin-dried well, and then the photosensitive composition was spin-coated (1300 rpm, 50 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, a 5% by mass polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, the film was exposed using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, developed with a 2.5% by mass sodium carbonate solution, and washed with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. The exposure amount was 80 mJ / cm 2 . The obtained pattern was unclear compared with the pattern obtained in Example 5.
〔比較例２〕感光性組成物の製造
アクリル系共重合体の代わりに実施例６で用いたスチレン−アクリル系感光性共重合体を用いた以外は、比較例１と同一の条件で、感光性組成物を得、該感光性組成物を用いてパターンを作成した。
[Comparative Example 2] Production of photosensitive composition Photosensitive composition was prepared under the same conditions as in Comparative Example 1 except that the styrene-acrylic photosensitive copolymer used in Example 6 was used instead of the acrylic copolymer. A photosensitive composition was obtained, and a pattern was prepared using the photosensitive composition.
上記感光性組成物は、比較例１の感光性組成物と同様の特性を有しており、実施例６の感光性組成物に較べて感度が劣っていた。また、この感光性組成物をスピンコートした後に５日以上放置すると、光重合開始剤の析出が起こった。 The photosensitive composition had the same characteristics as the photosensitive composition of Comparative Example 1 and was inferior in sensitivity to the photosensitive composition of Example 6. Moreover, when this photosensitive composition was allowed to stand for 5 days or more after spin coating, precipitation of a photopolymerization initiator occurred.
〔比較例３〕感光性組成物の製造
実施例５で用いたアクリル系共重合体１００ｇに対して、ジペンタエリスリトールペンタ及びヘキサアクリレート０．４ｇ及び比較化合物２（下記〔化１９〕）１０．０２ｇを加えて良く攪拌し、感光性組成物を得た。
[Comparative Example 3] Production of photosensitive composition To 100 g of the acrylic copolymer used in Example 5, 0.4 g of dipentaerythritol penta and hexaacrylate and comparative compound 2 (the following [Chemical Formula 19]) 10. 02 g was added and stirred well to obtain a photosensitive composition.
次いで、基板上にｒ−グリシドキシプロピルメチルエトキシシランをスピンコートして良くスピン乾燥させた後、上記感光性組成物をスピンコート（１３００ｒ．ｐ．ｍ、５０秒間）し乾燥させた。７０℃で２０分間プリベークを行った後、ポリビニルアルコール５質量％溶液をコートして酸素遮断膜とした。７０℃２０分間の乾燥後、所定のマスクを用い、光源として超高圧水銀ランプを用いて露光後、２．５質量％炭酸ナトリウム溶液で現像して良く水洗した。水洗乾燥後、２３０℃で１時間ベークしてパターンを定着させた。尚、露光量は、８０ｍＪ／ｃｍ2であった。得られたパターンは、実施例５で得られたパターンに較べて不鮮明であった。 Next, r-glycidoxypropylmethylethoxysilane was spin-coated on the substrate and spin-dried well, and then the photosensitive composition was spin-coated (1300 rpm, 50 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, a 5% by mass polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, the film was exposed using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, developed with a 2.5% by mass sodium carbonate solution, and washed with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. The exposure amount was 80 mJ / cm 2 . The obtained pattern was unclear compared with the pattern obtained in Example 5.
〔比較例４〕感光性組成物の製造
アクリル系共重合体の代わりに、実施例６で用いたスチレン−アクリル系感光性共重合体を用いた以外は、比較例３と同一の条件で、感光性組成物を得、該感光性組成物を用いてパターンを作成した。
[Comparative Example 4] Production of photosensitive composition Under the same conditions as in Comparative Example 3, except that the styrene-acrylic photosensitive copolymer used in Example 6 was used instead of the acrylic copolymer. A photosensitive composition was obtained, and a pattern was prepared using the photosensitive composition.
上記感光性組成物は比較例３の感光性組成物と同様の特性を有しており、実施例６の感光性組成物に較べて感度が劣っていた。また、上記感光性組成物をスピンコートした後に５日以上放置すると、光重合開始剤の析出が起こった。 The photosensitive composition had the same characteristics as the photosensitive composition of Comparative Example 3, and the sensitivity was inferior to the photosensitive composition of Example 6. In addition, when the photosensitive composition was spin-coated and left for 5 days or longer, a photopolymerization initiator was precipitated.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003330877A JP4565824B2 (en) | 2003-09-24 | 2003-09-24 | Dimer oxime ester compound and photopolymerization initiator containing the compound as an active ingredient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003330877A JP4565824B2 (en) | 2003-09-24 | 2003-09-24 | Dimer oxime ester compound and photopolymerization initiator containing the compound as an active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005097141A true JP2005097141A (en) | 2005-04-14 |
| JP4565824B2 JP4565824B2 (en) | 2010-10-20 |
Family
ID=34459672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003330877A Expired - Lifetime JP4565824B2 (en) | 2003-09-24 | 2003-09-24 | Dimer oxime ester compound and photopolymerization initiator containing the compound as an active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4565824B2 (en) |
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007071497A1 (en) * | 2005-12-20 | 2007-06-28 | Ciba Holding Inc. | Oxime ester photoinitiators |
| JP2008094770A (en) * | 2006-10-13 | 2008-04-24 | Adeka Corp | Oxime ester compound and photopolymerization initiator comprising the same as effective component |
| WO2008139924A1 (en) | 2007-05-09 | 2008-11-20 | Adeka Corporation | Novel epoxy compound, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| WO2008138732A1 (en) * | 2007-05-11 | 2008-11-20 | Basf Se | Oxime ester photoinitiators |
| WO2009017064A1 (en) | 2007-08-01 | 2009-02-05 | Adeka Corporation | Alkali-developable photosensitive resin composition and β-diketone compound |
| JP2009029929A (en) * | 2007-07-26 | 2009-02-12 | Adeka Corp | Polymerizable composition containing polymerizable liquid crystal compound and radical photopolymerization initiator |
| WO2009104468A1 (en) | 2008-02-22 | 2009-08-27 | 株式会社Adeka | Liquid crystal composition containing polymerizable compound, and liquid crystal display element comprising the liquid crystal composition |
| WO2009122868A1 (en) | 2008-04-01 | 2009-10-08 | 株式会社Adeka | Trifunctional (meth)acrylate compound and polymerizable composition containing the compound |
| WO2010032591A1 (en) | 2008-09-18 | 2010-03-25 | 株式会社Adeka | Polymerizable optically active imide compound and polymerizable composition containing the compound |
| EP2192163A1 (en) | 2008-11-27 | 2010-06-02 | Fujifilm Corporation | Ink composition and inkjet recording method |
| JP2010527339A (en) * | 2007-05-11 | 2010-08-12 | ビーエーエスエフ ソシエタス・ヨーロピア | Oxime ester photoinitiator |
| JP2010189280A (en) * | 2009-02-16 | 2010-09-02 | Nippon Kagaku Kogyosho:Kk | Oxime ester compound and photosensitive resin composition comprising the same |
| WO2011007566A1 (en) * | 2009-07-15 | 2011-01-20 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| WO2011062017A1 (en) | 2009-11-18 | 2011-05-26 | 株式会社Adeka | Liquid crystal composition comprising polymerizable compound, and liquid crystal display element using said liquid crystal composition |
| CN102161638A (en) * | 2010-02-05 | 2011-08-24 | Jsr株式会社 | Novel compound and radiation sensitive composition comprising the same |
| WO2011122025A1 (en) * | 2010-03-31 | 2011-10-06 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP2011215362A (en) * | 2010-03-31 | 2011-10-27 | Taiyo Holdings Co Ltd | Photocurable resin composition |
| JP2012198532A (en) * | 2011-03-08 | 2012-10-18 | Daicel Corp | Solvent or solvent composition for production of photoresist |
| JP2013047816A (en) * | 2012-10-01 | 2013-03-07 | Taiyo Holdings Co Ltd | Photosetting resin composition for printed wiring board |
| JP2013047817A (en) * | 2012-10-01 | 2013-03-07 | Taiyo Holdings Co Ltd | Photosetting resin composition for solder resist |
| JP2013047818A (en) * | 2012-10-01 | 2013-03-07 | Taiyo Holdings Co Ltd | Photosetting resin composition |
| WO2014065517A1 (en) * | 2012-10-23 | 2014-05-01 | 동우화인켐 주식회사 | Hardening resin composition and optical film manufactured by using same |
| WO2015068703A1 (en) | 2013-11-05 | 2015-05-14 | 太陽インキ製造株式会社 | Curable composition, cured coating film using same, and printed wiring board |
| EP2995658A2 (en) | 2014-09-09 | 2016-03-16 | Fujifilm Corporation | Polymerizable composition, ink composition for inkjet recording, inkkjet recording method and recorded matter |
| EP3000851A1 (en) | 2014-09-26 | 2016-03-30 | Fujifilm Corporation | Ink composition for inkjet recording, inkjet recording method, and printed matter |
| EP3000854A1 (en) | 2014-09-26 | 2016-03-30 | Fujifilm Corporation | Polymerizable composition, ink composition for ink-jet recording, method of ink-jet recording, and printed article |
| JP2016079158A (en) * | 2014-10-22 | 2016-05-16 | 株式会社Adeka | New polymerization initiator and radical polymerizable composition containing polymerization initiator |
| US20170205710A1 (en) * | 2012-05-09 | 2017-07-20 | Basf Se | Oxime ester photoinitiators |
| JP2017124998A (en) * | 2016-01-15 | 2017-07-20 | 株式会社Adeka | Compound, composition and photopolymerization initiator |
| US9891523B2 (en) | 2014-06-30 | 2018-02-13 | Taiyo Ink Mfg. Co., Ltd. | Photosensitive dry film and process for producing printed wiring board using the same |
| WO2022131346A1 (en) | 2020-12-17 | 2022-06-23 | 株式会社Adeka | Compound and composition |
| US11414382B2 (en) | 2018-03-02 | 2022-08-16 | Nippon Kayaku Kabushiki Kaisha | Compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator |
| WO2023002928A1 (en) | 2021-07-20 | 2023-01-26 | 株式会社Adeka | Film-forming material for semiconductor, member-forming material for semiconductor, process member-forming material for semiconductor, underlayer film-forming material, underlayer film, and semiconductor device |
| US11608316B2 (en) | 2018-03-01 | 2023-03-21 | Nippon Kayaku Kabushiki Kaisha | Compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101457172B1 (en) * | 2013-11-28 | 2014-10-31 | 타코마테크놀러지 주식회사 | Photoininiator and photosensitive composition including the same |
| TWI668210B (en) * | 2013-11-28 | 2019-08-11 | 塔可馬科技股份有限公司 | Photoinitiator and photosensitive composition including the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001092128A (en) * | 1999-09-21 | 2001-04-06 | Toppan Printing Co Ltd | Photosensitive composition for columnar spacer and color filter for liquid crystal display device using same |
| JP2002258473A (en) * | 2001-03-02 | 2002-09-11 | Nippon Kayaku Co Ltd | Color photosensitive composition |
| WO2002100903A1 (en) * | 2001-06-11 | 2002-12-19 | Ciba Specialty Chemicals Holding Inc. | Oxime ester photoinitiators having a combined structure |
| JP2003177532A (en) * | 2001-12-13 | 2003-06-27 | Sumitomo Chem Co Ltd | Photosensitive composition |
| JP2005099258A (en) * | 2003-09-24 | 2005-04-14 | Toppan Printing Co Ltd | Photosensitive composition and photosensitive colored composition |
| JP2005099280A (en) * | 2003-09-24 | 2005-04-14 | Toppan Printing Co Ltd | Color filter and its manufacturing method |
-
2003
- 2003-09-24 JP JP2003330877A patent/JP4565824B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001092128A (en) * | 1999-09-21 | 2001-04-06 | Toppan Printing Co Ltd | Photosensitive composition for columnar spacer and color filter for liquid crystal display device using same |
| JP2002258473A (en) * | 2001-03-02 | 2002-09-11 | Nippon Kayaku Co Ltd | Color photosensitive composition |
| WO2002100903A1 (en) * | 2001-06-11 | 2002-12-19 | Ciba Specialty Chemicals Holding Inc. | Oxime ester photoinitiators having a combined structure |
| JP2003177532A (en) * | 2001-12-13 | 2003-06-27 | Sumitomo Chem Co Ltd | Photosensitive composition |
| JP2005099258A (en) * | 2003-09-24 | 2005-04-14 | Toppan Printing Co Ltd | Photosensitive composition and photosensitive colored composition |
| JP2005099280A (en) * | 2003-09-24 | 2005-04-14 | Toppan Printing Co Ltd | Color filter and its manufacturing method |
| JP4342886B2 (en) * | 2003-09-24 | 2009-10-14 | 凸版印刷株式会社 | Photosensitive composition and photosensitive coloring composition |
Cited By (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009519991A (en) * | 2005-12-20 | 2009-05-21 | チバ ホールディング インコーポレーテッド | Oxime ester photoinitiator |
| WO2007071497A1 (en) * | 2005-12-20 | 2007-06-28 | Ciba Holding Inc. | Oxime ester photoinitiators |
| JP2008094770A (en) * | 2006-10-13 | 2008-04-24 | Adeka Corp | Oxime ester compound and photopolymerization initiator comprising the same as effective component |
| WO2008139924A1 (en) | 2007-05-09 | 2008-11-20 | Adeka Corporation | Novel epoxy compound, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| JP2010527339A (en) * | 2007-05-11 | 2010-08-12 | ビーエーエスエフ ソシエタス・ヨーロピア | Oxime ester photoinitiator |
| WO2008138732A1 (en) * | 2007-05-11 | 2008-11-20 | Basf Se | Oxime ester photoinitiators |
| KR101526619B1 (en) * | 2007-05-11 | 2015-06-05 | 바스프 에스이 | Oxime ester photoinitiators |
| CN101679394A (en) * | 2007-05-11 | 2010-03-24 | 巴斯夫欧洲公司 | oxime ester photoinitiators |
| JP2009029929A (en) * | 2007-07-26 | 2009-02-12 | Adeka Corp | Polymerizable composition containing polymerizable liquid crystal compound and radical photopolymerization initiator |
| WO2009017064A1 (en) | 2007-08-01 | 2009-02-05 | Adeka Corporation | Alkali-developable photosensitive resin composition and β-diketone compound |
| WO2009104468A1 (en) | 2008-02-22 | 2009-08-27 | 株式会社Adeka | Liquid crystal composition containing polymerizable compound, and liquid crystal display element comprising the liquid crystal composition |
| WO2009122868A1 (en) | 2008-04-01 | 2009-10-08 | 株式会社Adeka | Trifunctional (meth)acrylate compound and polymerizable composition containing the compound |
| WO2010032591A1 (en) | 2008-09-18 | 2010-03-25 | 株式会社Adeka | Polymerizable optically active imide compound and polymerizable composition containing the compound |
| EP2192163A1 (en) | 2008-11-27 | 2010-06-02 | Fujifilm Corporation | Ink composition and inkjet recording method |
| JP2010189280A (en) * | 2009-02-16 | 2010-09-02 | Nippon Kagaku Kogyosho:Kk | Oxime ester compound and photosensitive resin composition comprising the same |
| WO2011007566A1 (en) * | 2009-07-15 | 2011-01-20 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP2011022328A (en) * | 2009-07-15 | 2011-02-03 | Taiyo Holdings Co Ltd | Photocurable resin composition |
| US8748502B2 (en) | 2009-07-15 | 2014-06-10 | Taiyo Holdings Co., Ltd. | Photocurable resin composition |
| KR101380065B1 (en) | 2009-07-15 | 2014-04-01 | 다이요 홀딩스 가부시키가이샤 | Photocurable resin composition |
| US20120111620A1 (en) * | 2009-07-15 | 2012-05-10 | Taiyo Holdings Co., Ltd. | Photocurable resin composition |
| WO2011062017A1 (en) | 2009-11-18 | 2011-05-26 | 株式会社Adeka | Liquid crystal composition comprising polymerizable compound, and liquid crystal display element using said liquid crystal composition |
| CN102161638A (en) * | 2010-02-05 | 2011-08-24 | Jsr株式会社 | Novel compound and radiation sensitive composition comprising the same |
| WO2011122025A1 (en) * | 2010-03-31 | 2011-10-06 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP5767630B2 (en) * | 2010-03-31 | 2015-08-19 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JPWO2011122025A1 (en) * | 2010-03-31 | 2013-07-04 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP2011215362A (en) * | 2010-03-31 | 2011-10-27 | Taiyo Holdings Co Ltd | Photocurable resin composition |
| JP2012198532A (en) * | 2011-03-08 | 2012-10-18 | Daicel Corp | Solvent or solvent composition for production of photoresist |
| US11209734B2 (en) | 2012-05-09 | 2021-12-28 | Basf Se | Oxime ester photoinitiators |
| US11204554B2 (en) | 2012-05-09 | 2021-12-21 | Basf Se | Oxime ester photoinitiators |
| US10488756B2 (en) * | 2012-05-09 | 2019-11-26 | Basf Se | Oxime ester photoinitiators |
| US20170205710A1 (en) * | 2012-05-09 | 2017-07-20 | Basf Se | Oxime ester photoinitiators |
| US11209733B2 (en) | 2012-05-09 | 2021-12-28 | Basf Se | Oxime ester photoinitiators |
| JP2013047818A (en) * | 2012-10-01 | 2013-03-07 | Taiyo Holdings Co Ltd | Photosetting resin composition |
| JP2013047816A (en) * | 2012-10-01 | 2013-03-07 | Taiyo Holdings Co Ltd | Photosetting resin composition for printed wiring board |
| JP2013047817A (en) * | 2012-10-01 | 2013-03-07 | Taiyo Holdings Co Ltd | Photosetting resin composition for solder resist |
| WO2014065517A1 (en) * | 2012-10-23 | 2014-05-01 | 동우화인켐 주식회사 | Hardening resin composition and optical film manufactured by using same |
| WO2015068703A1 (en) | 2013-11-05 | 2015-05-14 | 太陽インキ製造株式会社 | Curable composition, cured coating film using same, and printed wiring board |
| US9891523B2 (en) | 2014-06-30 | 2018-02-13 | Taiyo Ink Mfg. Co., Ltd. | Photosensitive dry film and process for producing printed wiring board using the same |
| EP2995658A2 (en) | 2014-09-09 | 2016-03-16 | Fujifilm Corporation | Polymerizable composition, ink composition for inkjet recording, inkkjet recording method and recorded matter |
| EP3000851A1 (en) | 2014-09-26 | 2016-03-30 | Fujifilm Corporation | Ink composition for inkjet recording, inkjet recording method, and printed matter |
| EP3101070A1 (en) | 2014-09-26 | 2016-12-07 | Fujifilm Corporation | Polymerizable composition, ink composition for ink-jet recording, method of ink-jet recording, and printed article |
| EP3000854A1 (en) | 2014-09-26 | 2016-03-30 | Fujifilm Corporation | Polymerizable composition, ink composition for ink-jet recording, method of ink-jet recording, and printed article |
| JP2016079158A (en) * | 2014-10-22 | 2016-05-16 | 株式会社Adeka | New polymerization initiator and radical polymerizable composition containing polymerization initiator |
| JP2017124998A (en) * | 2016-01-15 | 2017-07-20 | 株式会社Adeka | Compound, composition and photopolymerization initiator |
| US11608316B2 (en) | 2018-03-01 | 2023-03-21 | Nippon Kayaku Kabushiki Kaisha | Compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator |
| US11414382B2 (en) | 2018-03-02 | 2022-08-16 | Nippon Kayaku Kabushiki Kaisha | Compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator |
| WO2022131346A1 (en) | 2020-12-17 | 2022-06-23 | 株式会社Adeka | Compound and composition |
| WO2023002928A1 (en) | 2021-07-20 | 2023-01-26 | 株式会社Adeka | Film-forming material for semiconductor, member-forming material for semiconductor, process member-forming material for semiconductor, underlayer film-forming material, underlayer film, and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4565824B2 (en) | 2010-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4565824B2 (en) | Dimer oxime ester compound and photopolymerization initiator containing the compound as an active ingredient | |
| JP3798008B2 (en) | Oxime ester compound and photopolymerization initiator containing the compound | |
| JP6196363B2 (en) | Novel β-oxime ester fluorene compound, photopolymerization initiator containing the same, and photoresist composition | |
| JP2004359639A (en) | Oxime ester compound and photopolymerization initiator containing the same | |
| JP7034175B2 (en) | Polymerizable group-containing fluorene oxime ester-based photoinitiator, production method and its application | |
| JP3992725B2 (en) | Oxime ester compound and photopolymerization initiator containing the compound | |
| TWI406847B (en) | Oxime ester compound to used for photosensitive polymer composition | |
| NL1016815C2 (en) | Oximester photo initiators. | |
| JP6328642B2 (en) | Cyclopentanedione oxime ester and its application | |
| JP2005220097A (en) | Oxime ester compound having thiophene structure and photopolymerization initiator containing the compound | |
| JP2905985B2 (en) | Novel oxygen-containing titanocene and its use | |
| JP2013543875A (en) | High-sensitivity carbazole oxime ester photoinitiator, process for its production and use | |
| CN109564387B (en) | Highly sensitive oxime ester photopolymerization initiator and photopolymerizable composition comprising the same | |
| JP4948112B2 (en) | Oxime ester compound and photopolymerization initiator containing the compound as an active ingredient | |
| JP3962781B2 (en) | Triazine compound containing functional alkylthio group and photopolymerization initiator | |
| JP4352833B2 (en) | Color filter and manufacturing method thereof | |
| KR100377643B1 (en) | Difunctional triazine derivatives and photoinitiators | |
| WO1994001806A1 (en) | Photopolymerizable composition | |
| JPH08269049A (en) | Carbazolyltriazine compound and photopolymerization initiator | |
| JP6095408B2 (en) | Novel photopolymerization initiator and photosensitive resin composition using them | |
| KR20000056234A (en) | Triazine-based photoinitators comprising heteroaromatic groups | |
| KR100359884B1 (en) | Tetrahydroquinolinyl and indolinyl triazine compounds and photopolymerization initiators | |
| KR100378015B1 (en) | Triazine-based photoinitiators comprising functionalized alkylthio groups | |
| JPH09118708A (en) | Photopolymerizable composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060522 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091222 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100204 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A132 Effective date: 20100302 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100325 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100706 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100714 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100803 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100803 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4565824 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130813 Year of fee payment: 3 |
|
| EXPY | Cancellation because of completion of term |