JP2006160634A - Oxime ester compound and photopolymerization initiator containing the compound - Google Patents
Oxime ester compound and photopolymerization initiator containing the compound Download PDFInfo
- Publication number
- JP2006160634A JP2006160634A JP2004351551A JP2004351551A JP2006160634A JP 2006160634 A JP2006160634 A JP 2006160634A JP 2004351551 A JP2004351551 A JP 2004351551A JP 2004351551 A JP2004351551 A JP 2004351551A JP 2006160634 A JP2006160634 A JP 2006160634A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- oxime ester
- meth
- acrylate
- ester compound
- 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
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- -1 Oxime ester compound Chemical class 0.000 title claims abstract description 82
- 239000003999 initiator Substances 0.000 title abstract description 24
- 150000001875 compounds Chemical class 0.000 title description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 5
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 3
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 abstract 2
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- 239000010453 quartz Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 11
- 229920006243 acrylic copolymer Polymers 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 150000003855 acyl compounds Chemical class 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 5
- 239000000758 substrate Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 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
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000012545 processing Methods 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
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 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
- 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-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
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical compound CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 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
- 238000011161 development Methods 0.000 description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000001914 filtration 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000007654 immersion Methods 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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 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
- 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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 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
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 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
- 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
- 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
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-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
- 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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 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
- 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
- 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
- KDXOONIQRUZGSY-UHFFFAOYSA-N 4-fluoro-2-methylbenzoic acid Chemical compound CC1=CC(F)=CC=C1C(O)=O KDXOONIQRUZGSY-UHFFFAOYSA-N 0.000 description 1
- KZUXJRQQHJREGH-UHFFFAOYSA-N 4-fluoro-2-methylbenzoyl chloride Chemical compound CC1=CC(F)=CC=C1C(Cl)=O KZUXJRQQHJREGH-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
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- MTSDTUBUDDJHEC-UHFFFAOYSA-N FC1=CC(=C(C(=O)Cl)C=C1)C.FC1=CC(=C(C(=O)Cl)C=C1)C Chemical compound FC1=CC(=C(C(=O)Cl)C=C1)C.FC1=CC(=C(C(=O)Cl)C=C1)C MTSDTUBUDDJHEC-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-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
- KYKQHSMYWLWROM-UHFFFAOYSA-N ac1l4yjn Chemical compound [Hg].[Hg] KYKQHSMYWLWROM-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 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
- 238000005917 acylation reaction Methods 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 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
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- AJCHRUXIDGEWDK-UHFFFAOYSA-N bis(ethenyl) butanedioate Chemical compound C=COC(=O)CCC(=O)OC=C AJCHRUXIDGEWDK-UHFFFAOYSA-N 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
- 238000009529 body temperature measurement Methods 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
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 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
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004803 chlorobenzyl group Chemical group 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004850 cyclobutylmethyl group Chemical group C1(CCC1)C* 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
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 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
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- HTEAGOMAXMOFFS-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C HTEAGOMAXMOFFS-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
- 239000012046 mixed solvent Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical group C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 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
- 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 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
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 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
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 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
- 238000012546 transfer Methods 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
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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 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 containing a polymerization 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。また、分解温度が２４０℃以下であり、現像処理後の熱硬化工程において光重合開始剤が分解することにより感光性組成物の密着性及び耐アルカリ性を低下させていた。そのため、熱分解温度が高く、光照射による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. In addition, the decomposition temperature was 240 ° C. or lower, and the photopolymerization initiator was decomposed in the thermosetting step after the development processing, so that the adhesiveness and alkali resistance of the photosensitive composition were lowered. Therefore, there has been a demand for a photopolymerization initiator that has a high thermal decomposition temperature and that does not volatilize the decomposition product of the initiator due to light irradiation 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−アシルオキシム光重合開始剤も、マスク汚れや耐熱性が不十分で耐アルカリ性を低下させていた。また、特許文献７には、カルバゾリル構造を有するＯ−アシルオキシム化合物が記載されているが、本発明者らが検討の結果、本発明の化合物に類似のシクロアルキルオキシベンゾイルで置換されたカルバゾリル化合物は、シクロアルキルエーテルが２級水素を持つために合成できなかった。 Patent Documents 5 to 7 listed below propose O-acyloxime photoinitiators having higher reactivity. However, these O-acyloxime photopolymerization initiators also have poor alkali resistance due to insufficient mask dirt and heat resistance. Patent Document 7 describes an O-acyloxime compound having a carbazolyl structure. As a result of investigations by the present inventors, a carbazolyl compound substituted with a cycloalkyloxybenzoyl similar to the compound of the present invention. Could not be synthesized because the cycloalkyl ether has secondary hydrogen.
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現像性、密着性、耐アルカリ性、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 problems to be solved are, as described above, photopolymerization excellent in developability, adhesion, alkali resistance, and sensitivity without coloring the obtained polymer or contaminating the polymer or equipment. This means that there has never been an initiator.
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 an oxime ester compound represented by the following general formula (I) and a photopolymerization initiator containing the compound as an active ingredient.
本発明のオキシムエステル化合物は、高感度であり、且つ熱分解温度が高く感光性組成物の密着性、耐アルカリ性を損なうことがなく、更に光照射で発生する分解物がマスクに付着することがない、光重合開始剤として有用なものである。 The oxime ester compound of the present invention is highly sensitive and has a high thermal decomposition temperature without impairing the adhesion and alkali resistance of the photosensitive composition, and further, decomposition products generated by light irradiation may adhere to the mask. It is not useful as a photopolymerization initiator.
以下、本発明の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 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、Ｘ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、Ｘ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 include fluorine, chlorine, bromine, and iodine. Examples of the alkyl group represented by X include methyl, ethyl, propyl, isopropyl, and 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, perfluoroethyl, 2- (Be Zookisazoru 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しうる環としては、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 which R ′ and R ′ can form together include a piperidine ring and a morpholine ring.
Ａで表されるシクロアルキルアルキル基としては、シクロプロピルメチル、２−シクロプロピルエチル、３−シクロプロピルプロピル、シクロブチルメチル、２−シクロブチルエチル、３−シクロブチルプロピル、シクロペンチルメチル、２−シクロペンチルエチル、３−シクロペンチルプロピル、シクロヘキシルメチル、３−シクロヘキシルプロピル、２−クロロ−３−シクロヘキシルプロピル等が挙げられる。 Examples of the cycloalkylalkyl group represented by A include cyclopropylmethyl, 2-cyclopropylethyl, 3-cyclopropylpropyl, cyclobutylmethyl, 2-cyclobutylethyl, 3-cyclobutylpropyl, cyclopentylmethyl, 2-cyclopentyl. Examples include ethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 3-cyclohexylpropyl, 2-chloro-3-cyclohexylpropyl, and the like.
本発明の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、Ｘがアルキル基、特にメチル基であるもの；Ｒ1がアルキル基、特にメチル基であるもの；Ｒ2がアルキル基、特にメチル基であるもの；Ｒ3がアルキル基、特にエチル基であるもの；Ａがシクロアルキルアルキル基、特にシクロヘキシルメチル基であるもの；ｍが１であるものが好ましい。 Among the oxime ester compounds of the present invention, in the above general formula (I), X is an alkyl group, particularly a methyl group; R 1 is an alkyl group, particularly a methyl group; R 2 is an alkyl group, particularly a methyl group Preferred are those wherein R 3 is an alkyl group, especially an ethyl group; A is a cycloalkylalkyl group, especially a cyclohexylmethyl group; and m is 1.
従って、上記一般式（Ｉ）で表される本発明の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．３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 oxime ester compound of the present invention represented by the above general formula (I) include the following compound Nos. 1-No. 3 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オキシムエステル化合物は、一般的に以下の方法により製造することができる。まず、カルバゾール化合物１とカルボン酸クロリド２及びＸの１つがハロゲン原子であるカルボン酸クロリド３を同時又は順次に塩化亜鉛の存在下に反応させてアシル化合物４を得る。次いで、アシル化合物４とアルコール化合物５とをカリウム−ｔ−ブトキシドの存在下に反応させてアシル体６を得る。アルコール化合物は、アシル化反応を行う前にカルボン酸クロリドに付加させてもよい。次いで、アシル体６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オキシム化合物７を得る。次いで、オキシム化合物７と酸無水物８あるいは酸クロライド８’を反応させて上記一般式（Ｉ）で表される本発明のオキシムエステル化合物を得る。例えば、化合物Ｎｏ．１は、下記[化５]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。 The oxime ester compound of the present invention represented by the above general formula (I) can be generally produced by the following method. First, the carbazole compound 1 and the carboxylic acid chloride 3 in which one of the carboxylic acid chlorides 2 and X is a halogen atom are reacted simultaneously or sequentially in the presence of zinc chloride to obtain the acyl compound 4. Subsequently, the acyl compound 4 and the alcohol compound 5 are reacted in the presence of potassium t-butoxide to obtain the acyl compound 6. The alcohol compound may be added to the carboxylic acid chloride before the acylation reaction. Next, the oxime compound 7 is obtained by reacting the acyl compound 6 with hydroxylamine hydrochloride in the presence of DMF. Subsequently, the oxime compound 7 and the acid anhydride 8 or the acid chloride 8 'are reacted to obtain the oxime ester compound of the present invention represented by the above general formula (I). For example, Compound No. 1 can be produced by the method represented by the following reaction formula [Chemical Formula 5].
本発明の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 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。 Next, the photosensitive composition of the present invention will be described.
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ペンタ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート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、本発明の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 Didiol (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris (2-acryloylethyl) isocyanurate, pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate Compounds obtained by esterification of polyhydric alcohols such as α, β-unsaturated carboxylic acids; acrylonitrile, (meth) acrylamide, N-substituted (meth) acrylates; vinyl acetate, isobutyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride , Vinylidene chloride, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate and the like. Among these, the photoinitiator which uses the oxime ester compound of this invention as an active ingredient is suitable for styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, and hydroxyethyl (meth) acrylate.
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、エポキシ樹脂等が挙げられ、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、エポキシ樹脂が好ましい。 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, saturated polyester, and epoxy resin. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin 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、本発明のオキシムエステル化合物の他に、必要に応じて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 oxime ester compound of the present invention, the photo-sensitive composition of the present invention can be used in combination with other photopolymerization initiators as necessary. There may be a significant synergistic effect by using a polymerization initiator in combination.
本発明の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、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、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’−ビイミダゾール等が挙げられる。 As the photopolymerization initiator that can be used in combination with the oxime ester compound of the present invention, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyl, benzyldimethyl ketal 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholy-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone , Diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) Benzoylpropane, 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, 2,2-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1-2′-biimidazole 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物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には、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）を溶解または分散しえる溶媒、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ることができる。 In the photosensitive composition of the present invention, 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) is usually used, for example, acetone. , Methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol can be added.
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 oxime ester compound of this invention, what emits light with a wavelength of 300-450 nm can be used, for example, ultrahigh 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重量部に対して、好ましくは１〜５０重量部、より好ましくは５〜３０重量部である。 In the photosensitive composition of the present invention, the amount of photopolymerization initiator added is not particularly limited, but the oxime ester compound of the present invention is 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond. The amount is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight.
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＞４−フルオロ−２−メチル安息香酸クロリドの製造
下記構造を持つ４−フルオロ−２−メチル安息香酸クロリドを、以下のようにして製造した。
Example 1 Compound no. Production of 1 <Step 1> Production of 4-fluoro-2-methylbenzoic acid chloride 4-fluoro-2-methylbenzoic acid chloride having the following structure was produced as follows.
窒素雰囲気下で４−フルオロ−２−メチル安息香酸２０．０ｇ（０．１３モル）、Ｎ，Ｎ−ジメチルホルムアミド０．１０ｇ（１．３ミリモル）及びトルエン１３４ｇを仕込み、室温にて塩化チオニル２３．２ｇ（０．２０モル）を滴下し、６０〜６５℃に昇温して１時間攪拌した。溶媒を留去し、減圧下、５０℃で乾燥して褐色液体１９．７ｇ（収率８８％、ＧＣ純度９９％）を得た。 Under a nitrogen atmosphere, 20.0 g (0.13 mol) of 4-fluoro-2-methylbenzoic acid, 0.10 g (1.3 mmol) of N, N-dimethylformamide and 134 g of toluene were charged, and thionyl chloride 23 was added at room temperature. 0.2 g (0.20 mol) was added dropwise, and the mixture was heated to 60 to 65 ° C. and stirred for 1 hour. The solvent was distilled off and the residue was dried at 50 ° C. under reduced pressure to obtain 19.7 g of a brown liquid (yield 88%, GC purity 99%).
得られた褐色液体のＩＲ測定の結果は次の通りであり、該褐色液体は目的物であることを確認した。
ＩＲ測定：（ｃｍ-1）
２９８５、２９３１、１７６６、１６０６、１５７９、１４８６、１４５０、１３８４、１２４０、１１８９、１１０５、９６４、８６９、８２３
The results of IR measurement of the obtained brown liquid were as follows, and it was confirmed that the brown liquid was the target product.
IR measurement: (cm −1 )
2985, 2931, 1766, 1606, 1579, 1486, 1450, 1384, 1240, 1189, 1105, 964, 869, 823
＜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.
モノクロロベンゼン３３．１ｇ、Ｎ−エチルカルバゾール２１．５ｇ（０．１１モル）及び塩化亜鉛１．４０ｇ（１０ミリモル）を混合して８０℃まで昇温し、４−フルオロ−２−メチル安息香酸クロリド１７．３ｇ（０．１０モル）を滴下した。８０〜８５℃で１時間攪拌後、室温まで冷却した。ｎ−ヘプタン３３．１ｇ及び水１６．５ｇを加えて油層を分離し、１％水酸化ナトリウム水溶液８．３０ｇを加えて中和し、さらに水４０．０ｇを２回に分けて加えて油層を洗浄した。油層を分離してｎ−ヘプタンを留去し、モノクロロベンゼン溶液５０．０ｇを得た。得られたモノクロロベンゼン溶液にモノクロロベンゼン９０．０ｇを滴下し、塩化アルミニウム４０．０ｇを加えて１０〜１５℃に冷却した。塩化アセチル９．９０ｇ（０．１３モル）を１０〜２０℃で滴下し、室温で１時間攪拌した。反応液を、二塩化エタン２２４ｇ及び氷水１３４ｇを混合したものに２５〜３０℃で滴下した。油層を分離し、５％ＨＣｌ水溶液４０ｇ、水４０ｇ、２％ＮａＯＨ水溶液４０ｇの順に洗浄した。二塩化エタンを留去し、酢酸ｎ−プロピル７４．６ｇから再結晶を行った。ろ過、酢酸ｎ−プロピル／ｎ−ヘプタン混合溶媒による洗浄を経て、淡黄色固体２２．４ｇ（収率６０％、ＨＰＬＣ純度９８％）を得た。 Monochlorobenzene 33.1 g, N-ethylcarbazole 21.5 g (0.11 mol) and zinc chloride 1.40 g (10 mmol) were mixed and the temperature was raised to 80 ° C., and 4-fluoro-2-methylbenzoic acid chloride was added. 17.3 g (0.10 mol) was added dropwise. After stirring at 80 to 85 ° C. for 1 hour, the mixture was cooled to room temperature. The oil layer was separated by adding 33.1 g of n-heptane and 16.5 g of water, neutralized by adding 8.30 g of 1% aqueous sodium hydroxide solution, and further adding 40.0 g of water in two portions to add the oil layer. Washed. The oil layer was separated and n-heptane was distilled off to obtain 50.0 g of a monochlorobenzene solution. To the obtained monochlorobenzene solution, 90.0 g of monochlorobenzene was added dropwise, 40.0 g of aluminum chloride was added, and the mixture was cooled to 10 to 15 ° C. 9.90 g (0.13 mol) of acetyl chloride was added dropwise at 10 to 20 ° C., and the mixture was stirred at room temperature for 1 hour. The reaction solution was added dropwise at 25 to 30 ° C. to a mixture of 224 g of ethane dichloride and 134 g of ice water. The oil layer was separated and washed in the order of 40 g of 5% aqueous HCl, 40 g of water, and 40 g of 2% aqueous NaOH. Ethane dichloride was distilled off and recrystallization was performed from 74.6 g of n-propyl acetate. After filtration and washing with a mixed solvent of n-propyl acetate / n-heptane, 22.4 g (yield 60%, HPLC purity 98%) of a pale yellow solid was obtained.
得られた淡黄色結晶は、融点１７５℃で、1Ｈ−ＮＭＲのケミカルシフト及びＩＲの測定結果は次の通りであり、目的物であるアシル体であることを確認した。
1Ｈ−ＮＭＲ測定：（ｐｐｍ）
８．７０（ｓ：１Ｈ）、８．５２（ｓ：１Ｈ）、８．１７（ｄ：１Ｈ）、８．０９（ｄ：１Ｈ）、７．５０（ｓ：１Ｈ）、７．４８（ｄ：１Ｈ）、７．３９（ｄ：１Ｈ）、７．０５（ｄ：１Ｈ）、７．００（ｄ：１Ｈ）、４．４５（ｄ：２Ｈ）、２．７３（ｓ：３Ｈ）、２．３７（ｓ：３Ｈ）、１．４９（ｔ：３Ｈ）
ＩＲ測定：（ｃｍ-1）
３４４８、３０５４、２０６４、１６６２、１６２５、１５８９、１５６７、１４８４、１３８６、１３０５、１２４５、１１５３、１１２４、１０２２、８０９
The obtained pale yellow crystals had a melting point of 175 ° C., 1 H-NMR chemical shift and IR measurement results were as follows, and were confirmed to be the target acyl.
1 H-NMR measurement: (ppm)
8.70 (s: 1H), 8.52 (s: 1H), 8.17 (d: 1H), 8.09 (d: 1H), 7.50 (s: 1H), 7.48 (d : 1H), 7.39 (d: 1H), 7.05 (d: 1H), 7.00 (d: 1H), 4.45 (d: 2H), 2.73 (s: 3H), 2 .37 (s: 3H), 1.49 (t: 3H)
IR measurement: (cm −1 )
3448, 3054, 2064, 1662, 1625, 1589, 1567, 1484, 1386, 1305, 1245, 1153, 1124, 1022, 809
＜ステップ３＞化合物Ｎｏ．１の製造
窒素気流下、シクロヘキサンメタノール５７．１ｇ（０．５モル）及び１，３−ジメチル−２−イミダゾリジノン６６．０ｇを仕込み、３０〜４０℃でカリウム−ｔ−ブトキシド８．４ｇ（０．０７５モル）を加えて７３〜７５℃まで昇温した。続いてステップ２で得られたアシル体の１８．７ｇ（０．０５モル）を加えて１時間攪拌した。塩酸ヒドロキシルアミン６．３ｇ（０．０９モル）を加えて７３〜７５℃で１時間攪拌後、室温まで冷却した。酢酸ｎ−プロピル４８．２ｇ及び４％水酸化カリウム水溶液２４．１ｇを加えて油層を分離し、水７５ｇを２回に分けて加えて油層を洗浄した。油層を分離して脱水後、６０〜７０℃で無水酢酸６．１ｇ（０．０６モル）を加え、８０〜９０℃で１時間攪拌した。室温まで冷却すると淡黄色固体が析出した。ろ過、酢酸ｎ−プロピル／ｎ−ヘプタンによる洗浄を経て、淡黄色結晶１０ｇ（収率３８％、ＨＰＬＣ純度９９％＜）を得た。該淡黄色結晶について分析を行ったところ、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 3> Compound No. Production of 1 Under a nitrogen stream, 57.1 g (0.5 mol) of cyclohexanemethanol and 66.0 g of 1,3-dimethyl-2-imidazolidinone were charged, and 8.4 g of potassium tert-butoxide was added at 30 to 40 ° C. 0.075 mol) was added and the temperature was raised to 73-75 ° C. Subsequently, 18.7 g (0.05 mol) of the acyl compound obtained in Step 2 was added and stirred for 1 hour. After adding 6.3 g (0.09 mol) of hydroxylamine hydrochloride and stirring at 73 to 75 ° C. for 1 hour, the mixture was cooled to room temperature. 48.2 g of n-propyl acetate and 24.1 g of 4% potassium hydroxide aqueous solution were added to separate the oil layer, and 75 g of water was added in two portions to wash the oil layer. After separating and dehydrating the oil layer, 6.1 g (0.06 mol) of acetic anhydride was added at 60 to 70 ° C., and the mixture was stirred at 80 to 90 ° C. for 1 hour. A pale yellow solid precipitated upon cooling to room temperature. Filtration and washing with n-propyl acetate / n-heptane gave 10 g of pale yellow crystals (38% yield, HPLC purity 99% <). When the pale yellow crystal was analyzed, it was found that the pale yellow crystal was the target compound No. 1. 1 was confirmed. The analysis results are shown below.
（分析結果）
（１）融点：１４８．２℃
（２）1Ｈ−ＮＭＲ測定：（ｐｐｍ）
８．５０（ｄ：１Ｈ）、８．４４（ｄ：１Ｈ）、８．０８（ｄｄ：１Ｈ）、７．９８（ｄｄ：１Ｈ）、７．４７（ｄ：１Ｈ）、７．４５（ｄ：１Ｈ）、７．３７（ｄ：１Ｈ）、６．８６（ｄ：１Ｈ）、６．７８（ｄｄ：１Ｈ）、４．４３（ｑ：２Ｈ）、３．８４（ｄ：２Ｈ）、２．５２（ｓ：３Ｈ）、２．４０（ｓ：３Ｈ）、２．３０（ｓ：３Ｈ）、１．９２‐１．７１（ｍ：６Ｈ）、１．４８（ｔ：３Ｈ）１．３８−１．０４（ｍ：５Ｈ）
（３）ＩＲ測定：（ｃｍ‐1）
２９２７、２８５３、１７５１、１６４９、１６２６、１６０５、１５９０、１５６８、１４８８、１４５０、１３７６、１３０８、１２７５、１２４４、１１４９、１１２９、１０４４、１００９、９８３、９４１、８９４、８１２、７７２
（４）ＵＶスペクトル測定（アセトニトリル：水＝９：１）
λｍａｘ＝２７３、２９９、３４１ｎｍ
（５）分解温度測定（窒素ガス雰囲気下、昇温速度１０℃／分、５％重量減少温度）
２４１．２℃
(result of analysis)
(1) Melting point: 148.2 ° C
(2) 1 H-NMR measurement: (ppm)
8.50 (d: 1H), 8.44 (d: 1H), 8.08 (dd: 1H), 7.98 (dd: 1H), 7.47 (d: 1H), 7.45 (d : 1H), 7.37 (d: 1H), 6.86 (d: 1H), 6.78 (dd: 1H), 4.43 (q: 2H), 3.84 (d: 2H), 2 .52 (s: 3H), 2.40 (s: 3H), 2.30 (s: 3H), 1.92-1.71 (m: 6H), 1.48 (t: 3H) 1.38 -1.04 (m: 5H)
(3) IR measurement: (cm- 1 )
2927, 2853, 1751, 1649, 1626, 1605, 1590, 1568, 1488, 1450, 1376, 1308, 1275, 1244, 1149, 1129, 1044, 1009, 983, 941, 894, 812, 772
(4) UV spectrum measurement (acetonitrile: water = 9: 1)
λmax = 273, 299, 341 nm
(5) Decomposition temperature measurement (temperature increase rate 10 ° C / min, 5% weight loss temperature under nitrogen gas atmosphere)
241.2 ° C
[実施例２]感光性組成物Ｎｏ．１の製造
アクリル系共重合体１４ｇに対し、トリメチロールプロパントリアクリレート ５．９ｇ、実施例１で得られた化合物Ｎｏ．１の２．７ｇ 及びエチルセロソルブ ７９ｇを加えて良く攪拌し、感光性組成物Ｎｏ．１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 2] Photosensitive composition no. Production of Compound No. 1 obtained in Example 1, 5.9 g of trimethylolpropane triacrylate, with respect to 14 g of acrylic copolymer. 2.7 g of No. 1 and 79 g of ethyl cellosolve were added and stirred well. 1 was obtained.
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.
[実施例３]感光性組成物Ｎｏ．２の製造
アクリル系共重合体７．２ｇに対し、トリメチロールプロパントリアクリレート ４．３ｇ、実施例１で得られた化合物Ｎｏ．１の２．０ｇ 及びエチルセロソルブ ８７ｇを加えて良く攪拌し、感光性組成物Ｎｏ．２を得た。
[Example 3] Photosensitive composition no. Production of Compound No. 2 obtained in Example 1, 4.3 g of trimethylolpropane triacrylate with respect to 7.2 g of acrylic copolymer. 1 and 2.0 g of ethyl cellosolve were added and stirred well. 2 was obtained.
[実施例４]感光性組成物Ｎｏ．３の製造
スチレン−アクリル系感光性共重合体１４ｇに対し、ジペンタエリスリトールヘキサアクリレート ６．０ｇ、実施例１で得られた化合物Ｎｏ．１の１．３ｇ 、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 １．３ｇ及びエチルセロソルブ８３ｇを加えて良く攪拌し、感光性組成物Ｎｏ．３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、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 4] Photosensitive composition No. Production of Compound No. 3 obtained in Example 1, 6.0 g of dipentaerythritol hexaacrylate with respect to 14 g of styrene-acrylic photosensitive copolymer. 1.3 g of 1, 2,2-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1-2′-biimidazole 1.3 g and ethyl cellosolve 83 g were added and stirred well. , Photosensitive composition No. 3 was obtained.
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, react at 90 ° C. for 5 hours, and then add 23.5 parts by mass of isocyanate ethyl methacrylate and 0.11 parts by mass of tin octylate to 20 parts by mass of ethyl cellosolve. 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.
[実施例５]感光性組成物Ｎｏ．４の製造
スチレン−アクリル系感光性共重合体１２ｇに対し、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 ８．１ｇ、実施例１で得られた化合物Ｎｏ．１の２．５ｇ、エチルセロソルブ４７ｇ 及びシクロヘキサノン ３０ｇを加えて良く攪拌し、感光性組成物Ｎｏ．４を得た。
[Example 5] Photosensitive composition no. Production of Dipentaerythritol Penta and 8.1 g of Hexaacrylate, Compound No. 1 obtained in Example 1 with respect to 12 g of styrene-acrylic photosensitive copolymer. 1 and 2.5 g of ethyl cellosolve and 30 g of cyclohexanone were added and stirred well. 4 was obtained.
[実施例６]感光性組成物Ｎｏ．５の製造
アクリル系共重合体２０ｇに対し、トリメチロールプロパントリアクリレート ８．７ｇ、実施例１で得られた化合物Ｎｏ．１の２．２ｇ 、ビスフェノールＡ型エポキシ樹脂４．６ｇ及びエチルセロソルブ ６５ｇを加えて良く攪拌し、感光性組成物Ｎｏ．５を得た。
[Example 6] Photosensitive composition no. Production of Compound No. 5 obtained in Example 1, 8.7 g of trimethylolpropane triacrylate with respect to 20 g of acrylic copolymer. No. 1 of 2.2 g, bisphenol A type epoxy resin 4.6 g and ethyl cellosolve 65 g were added and stirred well. 5 was obtained.
[比較例１]感光性組成物Ｎｏ．６の製造
実施例２で用いたアクリル系共重合体１４ｇ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５．９ｇ、比較化合物１（下記[化８]）２．１ｇ及びエチルセロソルブ７８ｇを加えてよく攪拌し、感光性組成物Ｎｏ．６を得た。
[Comparative Example 1] Photosensitive composition No. Preparation of 6 To 14 g of the acrylic copolymer used in Example 2, 5.9 g of dipentaerythritol penta and hexaacrylate, 2.1 g of comparative compound 1 (the following [Chemical Formula 8]) and 78 g of ethyl cellosolve were added. Stir well and photosensitive composition no. 6 was obtained.
[比較例２]感光性組成物Ｎｏ．７の製造
アクリル系共重合体の代わりに実施例４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Ｎｏ．７を得た。
[Comparative Example 2] Photosensitive composition No. Production of Photosensitive Composition No. 7 under the same conditions as in Comparative Example 1 except that the styrene-acrylic photosensitive copolymer used in Example 4 was used instead of the acrylic copolymer. 7 was obtained.
[比較例３]感光性組成物Ｎｏ．８の製造
実施例２で用いたアクリル系共重合体７．２ｇに対して、トリメチロールプロパントリアクリレート４．３ｇ、比較化合物２（下記[化９]）１．５ｇ及びエチルセロソルブ８７ｇを加えて良く攪拌し、感光性組成物Ｎｏ．８を得た。
[Comparative Example 3] Photosensitive composition No. Production of 8 To 7.2 g of the acrylic copolymer used in Example 2, 4.3 g of trimethylolpropane triacrylate, 1.5 g of comparative compound 2 (the following [Chemical Formula 9]) and 87 g of ethyl cellosolve were added. Stir well and photosensitive composition no. 8 was obtained.
[比較例４]感光性組成物Ｎｏ．９の製造
アクリル系共重合体の代わりに、実施例４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Ｎｏ．９を得た。
[Comparative Example 4] Photosensitive composition No. Production of Photosensitive Composition No. 9 under the same conditions as in Comparative Example 3 except that the styrene-acrylic photosensitive copolymer used in Example 4 was used instead of the acrylic copolymer. 9 was obtained.
得られた感光性組成物の評価は以下のようにして行った。すなわち、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Ｎｏ．１〜９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％炭酸ナトリウム溶液に２５℃で３０秒間浸漬して現像し、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。得られたパターンについて、以下の評価を行った。各感光性組成物に用いた光重合開始剤とその分解温度および各種評価結果を表１に示す。 Evaluation of the obtained photosensitive composition was performed as follows. That is, after r-glycidoxypropylmethylethoxysilane was spin-coated on a substrate and spin-dried, the above photosensitive composition No. 1 was prepared. 1 to 9 were 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 by immersing in a 2.5% sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly 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 following evaluation was performed about the obtained pattern. Table 1 shows the photopolymerization initiator used in each photosensitive composition, its decomposition temperature, and various evaluation results.
＜密着性＞
ＪＩＳ Ｄ ０２０２の試験方法に従い、露光現像した後２００℃で３０分間加熱した塗膜に基盤目状にクロスカットを入れ、次いでセロハンテープによってピーリングテストを行い、基盤目の剥離の状態を目視により評価した。全く剥離が認められなかったものを○、剥離が認められたものを×とした。
＜耐アルカリ性＞
現像露光した後、２００℃で３０分間加熱処理を行った。加熱処理後の塗膜をａ）５％ＮａＯＨａｑ．中２４時間、ｂ）４％ＫＯＨａｑ．中５０℃で１０分間、ｃ）１％ＮａＯＨａｑ．中８０℃で５分間の条件で浸漬し、浸漬後の外観を目視により評価した。外観変化もなくレジストの剥離も全くなかったものを○、レジストの浮きが見られたものを△、レジストの剥離が認められたものを×とした。
＜感度＞
露光量を、５０ｍＪ／ｃｍ2で行った以外は、上記の現像性の試験と同様にして露光部の形状がマスクの形状に一致するものを５、マスクの形状に対して面積で５％以下ではあるが欠落が認められるものを４、面積で５〜２０％の欠落があるものを３、面積で２０〜５０％の欠落があるものを２、面積で５０％より欠落が大きいものを１として５段階で評価した。結果を表１に示す。
<Adhesion>
According to the test method of JIS D 0202, a cross-cut is made in a substrate pattern on a coating film that has been exposed and developed and heated at 200 ° C. for 30 minutes, and then a peeling test is performed with a cellophane tape to visually evaluate the peeling state of the substrate eye. did. A sample in which no peeling was observed was marked with ○, and a sample in which peeling was observed was marked with ×.
<Alkali resistance>
After the development exposure, heat treatment was performed at 200 ° C. for 30 minutes. The heat-treated coating film was a) 5% NaOH aq. For 24 hours, b) 4% KOH aq. 10 min at 50 ° C., c) 1% NaOH aq. It was immersed for 5 minutes at a medium temperature of 80 ° C., and the appearance after immersion was visually evaluated. The case where the appearance was not changed and the resist was not peeled off was rated as “◯”, the case where the resist was observed to be lifted, and the case where the resist was observed to be peeled as “X”.
<Sensitivity>
Except for the exposure dose of 50 mJ / cm 2 , 5 in which the shape of the exposed portion matches the shape of the mask in the same manner as in the above developability test, 5% or less in area with respect to the mask shape However, there are 4 cases where omissions are recognized, 3 cases with 5-20% omissions in area, 2 cases with omissions of 20-50% in area, and 1 cases with omissions greater than 50% in area. It was evaluated in five stages. The results are shown in Table 1.
実施例１〜６及び比較例１〜４より明らかなように本発明のオキシムエステル化合物を用いた感光性組成物の密着性は公知のオキシムエステル化合物の場合よりも同等又は優れて、耐アルカリ性では優れている。特に比較例１及び２より密着性、耐アルカリ性に優れており、比較化合物１との基本的な性能差であるか、比較化合物１の耐熱性が低いために２３０℃での熱硬化処理において比較化合物１が分解したために感光性組成物の性能が低下したと考えられる。本発明のオキシムエステル化合物は、分解温度が２４０℃以上と公知のオキシムエステル化合物より９〜５０℃耐熱性に優れ、熱硬化処理温度において安定である。 As is clear from Examples 1 to 6 and Comparative Examples 1 to 4, the adhesion of the photosensitive composition using the oxime ester compound of the present invention is equal to or better than that of the known oxime ester compound, Are better. In particular, it has better adhesion and alkali resistance than Comparative Examples 1 and 2, and is a basic performance difference from Comparative Compound 1 or because of the low heat resistance of Comparative Compound 1, it is compared in thermosetting treatment at 230 ° C. It is considered that the performance of the photosensitive composition was lowered due to the decomposition of Compound 1. The oxime ester compound of the present invention has a decomposition temperature of 240 ° C. or higher, excellent heat resistance of 9 to 50 ° C. than known oxime ester compounds, and is stable at the thermosetting temperature.
［実施例７］露光処理における昇華性評価
化合物Ｎｏ．１の開始剤０．５ｇをプロピレングリコールモノメチルエーテルアセテート１０ｇに溶解し、アクリル系重合体（実施例２に同じ）０．５ｇを加え、混合したものを直径７０ｍｍのシャーレに入れて７０℃で１２時間で乾燥した。シャーレに１００×１００ｍｍの石英板を蓋になるように乗せて１０ｍＪ／ｃｍ2で２時間露光した。石英版への附着物の多少により昇華性を評価した。附着物は認められなかった。露光処理前後の石英板の写真を図１及び図２に示す。
[Example 7] Evaluation of sublimation in exposure process 1 g of the initiator 1 was dissolved in 10 g of propylene glycol monomethyl ether acetate, 0.5 g of an acrylic polymer (same as in Example 2) was added, and the mixture was placed in a petri dish having a diameter of 70 mm at 12 ° C. Dried in time. A 100 × 100 mm quartz plate was placed on the petri dish so as to be a lid and exposed at 10 mJ / cm 2 for 2 hours. The sublimation property was evaluated by the amount of attachments to the quartz plate. There were no attachments. Photographs of the quartz plate before and after the exposure processing are shown in FIGS.
［比較例５］比較化合物における昇華性評価
化合物Ｎｏ．１を比較化合物２にかえた以外は、実施例７と同様にして附着物を評価した。多数の附着物があった。露光処理前後の石英板の写真を図３及び図４に示す。
[Comparative Example 5] Evaluation of sublimation in comparative compound The attachment was evaluated in the same manner as in Example 7 except that 1 was replaced with Comparative Compound 2. There were numerous attachments. 3 and 4 show photographs of the quartz plate before and after the exposure processing.
図１は実施例７に用いた石英板の露光前の写真であり、図２は実施例７に用いた石英板の露光後の写真である。図３は比較例５に用いた石英板の露光前の写真であり、図４は比較例５に用いた石英板の露光後の写真である。図１、図２、図３の石英板には附着物は認められない。図４では無数の結晶状の附着物が認められる。 FIG. 1 is a photograph of the quartz plate used in Example 7 before exposure, and FIG. 2 is a photograph of the quartz plate used in Example 7 after exposure. 3 is a photograph of the quartz plate used in Comparative Example 5 before exposure, and FIG. 4 is a photograph of the quartz plate used in Comparative Example 5 after exposure. No attachments are observed on the quartz plates of FIGS. In FIG. 4, countless crystalline attachments are observed.
実施例７および比較例５から本発明の化合物は露光後の昇華物がなく、マスク汚れがないと推測できる。一方、公知の光開始剤では昇華物が多量にあり、マスク汚れを起こすと推測できる。よって、本発明の光開始剤を用いた硬化性組成物は連続使用可能であるが、従来の光開始剤を用いた場合はマスクなど装置の洗浄が必要になるので、本発明の光開始剤を用いることにより生産性の向上が期待できる。 From Example 7 and Comparative Example 5, it can be inferred that the compound of the present invention has no sublimate after exposure and no mask contamination. On the other hand, it can be inferred that the known photoinitiator has a large amount of sublimation and causes mask contamination. Therefore, the curable composition using the photoinitiator of the present invention can be used continuously. However, when the conventional photoinitiator is used, it is necessary to clean a device such as a mask. The use of can be expected to improve productivity.
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| JP2004351551A JP3798008B2 (en) | 2004-12-03 | 2004-12-03 | Oxime ester compound and photopolymerization initiator containing the compound |
| PCT/JP2005/020416 WO2006059458A1 (en) | 2004-12-03 | 2005-11-08 | Oxime ester compound and photopolymerization initiator comprising the compound |
| KR1020077010359A KR101262141B1 (en) | 2004-12-03 | 2005-11-08 | Oxime ester compound and photopolymerization initiator comprising the compound |
| CN2005800373260A CN101048377B (en) | 2004-12-03 | 2005-11-08 | Oxime ester compound and photopolymerization initiator comprising the compound |
| TW094140725A TW200631942A (en) | 2004-12-03 | 2005-11-18 | The oxime ester compounds and the initiator of the photo-polymerization comprising the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200631942A (en) | 2006-09-16 |
| CN101048377A (en) | 2007-10-03 |
| TWI378920B (en) | 2012-12-11 |
| CN101048377B (en) | 2011-09-14 |
| KR101262141B1 (en) | 2013-05-14 |
| KR20070091110A (en) | 2007-09-07 |
| JP3798008B2 (en) | 2006-07-19 |
| WO2006059458A1 (en) | 2006-06-08 |
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