JP3972544B2 - Metal chelate dye and optical recording medium using the metal chelate dye - Google Patents
Metal chelate dye and optical recording medium using the metal chelate dye Download PDFInfo
- Publication number
- JP3972544B2 JP3972544B2 JP33975699A JP33975699A JP3972544B2 JP 3972544 B2 JP3972544 B2 JP 3972544B2 JP 33975699 A JP33975699 A JP 33975699A JP 33975699 A JP33975699 A JP 33975699A JP 3972544 B2 JP3972544 B2 JP 3972544B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- ring
- metal chelate
- atom
- chelate dye
- 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.)
- Expired - Fee Related
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 33
- 239000002184 metal Substances 0.000 title claims description 33
- 230000003287 optical effect Effects 0.000 title claims description 28
- 239000013522 chelant Substances 0.000 title claims description 24
- -1 azo compound Chemical class 0.000 claims description 118
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 19
- 125000005842 heteroatom Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052757 nitrogen Chemical group 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000000975 dye Substances 0.000 description 56
- 239000010410 layer Substances 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 125000003545 alkoxy group Chemical group 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011241 protective layer Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 6
- 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 6
- 238000004528 spin coating Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000006606 n-butoxy group Chemical group 0.000 description 4
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 4
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 4
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 125000005920 sec-butoxy group Chemical group 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 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 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 3
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- ADVGKWPZRIDURE-UHFFFAOYSA-N 2'-Hydroxyacetanilide Chemical compound CC(=O)NC1=CC=CC=C1O ADVGKWPZRIDURE-UHFFFAOYSA-N 0.000 description 2
- BNDRWEVUODOUDW-UHFFFAOYSA-N 3-Hydroxy-3-methylbutan-2-one Chemical compound CC(=O)C(C)(C)O BNDRWEVUODOUDW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001555 benzenes Chemical group 0.000 description 2
- 239000011230 binding agent Substances 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
- 239000004202 carbamide Substances 0.000 description 2
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- YIHRGKXNJGKSOT-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutan-1-ol Chemical compound CC(F)(F)C(F)(F)C(O)(F)F YIHRGKXNJGKSOT-UHFFFAOYSA-N 0.000 description 1
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ORIHZIZPTZTNCU-VMPITWQZSA-N 2-[(E)-hydroxyiminomethyl]phenol Chemical compound O\N=C\C1=CC=CC=C1O ORIHZIZPTZTNCU-VMPITWQZSA-N 0.000 description 1
- MLOXIXGLIZLPDP-UHFFFAOYSA-N 2-amino-1h-imidazole-4,5-dicarbonitrile Chemical compound NC1=NC(C#N)=C(C#N)N1 MLOXIXGLIZLPDP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000000999 acridine dye Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- GGBJHURWWWLEQH-UHFFFAOYSA-N butylcyclohexane Chemical compound CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910000313 chalcogen oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000000268 heptanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000001013 indophenol dye Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000006126 n-butyl sulfonyl group Chemical group 0.000 description 1
- 125000002004 n-butylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000006137 n-hexyl sulfonyl group Chemical group 0.000 description 1
- 125000004718 n-hexylthio group Chemical group C(CCCCC)S* 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000006129 n-pentyl sulfonyl group Chemical group 0.000 description 1
- 125000004712 n-pentylthio group Chemical group C(CCCC)S* 0.000 description 1
- 125000004888 n-propyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006124 n-propyl sulfonyl group Chemical group 0.000 description 1
- 125000004706 n-propylthio group Chemical group C(CC)S* 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- XTVMZZBLCLWBPM-UHFFFAOYSA-N tert-butylcyclohexane Chemical compound CC(C)(C)C1CCCCC1 XTVMZZBLCLWBPM-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical compound C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 1
- 125000003652 trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、特定の構造のアゾ系化合物と金属との金属キレート色素及び該色素を用いた光学記録媒体に関するものである。
近年、発振波長の短い半導体レーザーの開発が進められ、従来の７８０ｎｍ、８３０ｎｍよりも短波長のレーザー光を用いた高密度の記録再生可能な光学記録媒体が求められている。従来提案されている光学記録媒体としては、光磁気記録媒体、相変化記録媒体、カルコゲン酸化物光記録媒体、有機色素系光記録媒体、等がある。これらの中で、安価でプロセス上容易であるという点で、有機色素系光学記録媒体は有意性を有するものと考えられている。
現在、有機色素系光学記録媒体としては、反射率の高い金属層を有機色素層の上に積層したタイプのＣＤ−Ｒが、量産化され広く知られているが、今後、これよりもさらに短波長半導体レーザーで記録再生可能な、高密度の有機色素系光学記録媒体が必要になると考えられる。
【０００２】
【発明が解決しようとする課題】
一般に、ＣＤ−Ｒとして使用されている媒体は、例えば６８０ｎｍ、６５０ｎｍ、６３５ｎｍなどの、本来の記録再生波長（７８０ｎｍ）より短い波長で使用すると、反射率が低く記録再生ができないという問題を有している。また、短波長での記録用として現在提案されている媒体であっても、記録時の色素分解による記録部の変形が大きい、変調度があまり得られない、耐光性や耐久性が不十分である、等の問題を有している。
本発明者らは先に特開平３−２６８９９４号公報において、耐光性と耐久性に優れた新規なアゾ系金属キレート色素を使用した光学記録媒体を提案したが、短波長半導体レーザーによる記録再生特性の更なる向上を求めて改良を行った。
【０００３】
【課題を解決するための手段】
また、先に本出願人は、アゾ系金属キレート色素を形成するアゾ系化合物の、カップリング成分のベンゼン環に結合しているアルキルスルホニルアミノ基がフッ素で置換されており、しかもカップリング成分のベンゼン環が特定のアミノ基を有しているアゾ金属キレート色素を使用することにより、耐光性と耐久性に優れ、記録、再生特性が著しく改良された光学記録媒体を提供できる色素を見出し、出願を行った（特開平１１−１６６１２５号公報）。
今般本発明者らは、更にカップリング成分のベンゼン環上のアミノ基がヘテロ原子を介してベンゼン環に結合し、該ベンゼン環に縮合する環を形成することにより、光学記録媒体の記録特性がより向上する傾向が有ることを見出し、本発明に到達した。
【０００４】
すなわち、下記一般式（１）または（２）で示されるアゾ系化合物と金属からなる金属キレート色素、およびこれを使用する光学記録媒体に存する。
【０００５】
【化３】
（式中、環Ｅはそれぞれ結合している炭素原子及び窒素原子と一緒になって形成する複素環を表し、環ＡはＲ1 と結合する窒素原子以外に少なくとも１個のヘテロ原子を含む、置換されてもよい５〜８員環を表す。環Ｂは少なくともＸ1 及び／又はＸ2 で置換されたベンゼン環を表すが、Ｘ1 かＸ2 の少なくともいずれか一方が−ＮＨＳＯ2 Ｙ基を表し、Ｙは少なくとも２つはフッ素原子で置換されている直鎖または分岐のアルキル基を表す。Ｒ1 は水素原子、置換されてもよい直鎖または分岐のアルキル基を表す。）
【０００７】
【発明の実施の形態】
以下本発明につき詳細に説明する。
本発明におけるアゾ系化合物としては、前記一般式（１）および（２）において、環Ｅはそれぞれ結合している炭素原子及び窒素原子と一緒になって形成する複素環であればよく、それらの群であれば特に制限されないが、好ましくは下記のものが挙げられる。
【０００８】
【化４】
（式中、Ｄ1 〜Ｄ42は水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基などの炭素数１から６の直鎖または分岐のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の炭素数３から６の環状アルキル基；メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｓｅｃ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−ヘキシルオキシ基等の炭素数１から６のアルコキシ基；アセチル基、プロピオル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、ピバロイル基、ヘキサノイル基、ヘプタノイル基等の炭素数１〜６のアルキルカルボニル基；ビニル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等の炭素数２〜６の直鎖または分岐のアルケニル基；シクロペンテニル基、シクロヘキセニル基等の炭素数３〜６の環状アルケニル基；フッ素原子、塩素原子、臭素原子等のハロゲン原子；ホルミル基；ヒドロキシル基；カルボキシル基；ヒドロキシメチル基、ヒドロキシエチル基等の炭素数１〜６のヒドロキシアルキル基；メトキシカルボニル基、エトキシカルボニル基、ｎ−プロポキシカルボニル基、イソプロポキシカルボニル基、ｎ−ブトキシカルボニル基、ｔｅｒｔ−ブトキシカルボニル基、ｓｅｃ−ブトキシカルボニル基、ｎ−ペンチルオキシカルボニル基、ｎ−ヘキシルオキシカルボニル基等の炭素数２〜７のアルコキシカルボニル基；ニトロ基；シアノ基；アミノ基；メチルアミノ基、エチルアミノ基、ｎ−プロピルアミノ基、ｎ−ブチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジ−ｎ−プロピルアミノ基、ジ−ｎ−ブチルアミノ基等の炭素数１〜１０のアルキルアミノ基；メトキシカルボニルメチル基、エトキシカルボニルメチル基、ｎ−プロポキシカルボニルメチル基、イソプロポキシカルボニルエチル基等の炭素数３〜７のアルコキシカルボニルアルキル基；メチルチオ基、エチルチオ基、ｎ−プロピルチオ基、ｔｅｒｔ−ブチルチオ基、ｓｅｃ−ブチルチオ基、ｎ−ペンチルチオ基、ｎ−ヘキシルチオ基等の炭素数１〜６のアルキルチオ基；メチルスルホニル基、エチルスルホニル基、ｎ−プロピルスルホニル基、イソプロピルスルホニル基、ｎ−ブチルスルホニル基、ｔｅｒｔ−ブチルスルホニル基、ｓｅｃ−ブチルスルホニル基、ｎ−ペンチルスルホニル基、ｎ−ヘキシルスルホニル基等の炭素数１〜６のアルキルスルホニル基；置換基を有していてもよい炭素数６〜１６のアリール基；置換基を有していてもよい炭素数７〜１７のアリールカルボニル基；−ＣＤ43＝Ｃ（ＣＮ）Ｄ44（Ｄ43は水素原子またはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基などの炭素数１から６のアルキル基を表わし、Ｄ44はシアノ基またはメトキシカルボニル基、エトキシカルボニル基、ｎ−プロポキシカルボニル基、イソプロポキシカルボニル基、ｎ−ブトキシカルボニル基、ｔｅｒｔ−ブトキシカルボニル基、ｓｅｃ−ブトキシカルボニル基、ｎ−ペンチルカルボニル基、ｎ−ヘキシルオキシカルボニル基等の炭素数２〜７のアルコキシ基を表わす。）；
【００１０】
【化５】
Ｄ45〜Ｄ47はそれぞれ独立して水素原子、ニトロ基、フッ素原子、塩素原子、臭素原子等のハロゲン原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基などの炭素数１から６の直鎖または分岐のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の炭素数３から６の環状のアルキル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｓｅｃ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−ヘキシルオキシ基等の炭素数１から６のアルコキシ基を表わす。）；
【００１２】
【化６】
Ｄ48〜Ｄ50はそれぞれ独立して水素原子、ニトロ基、フッ素原子、塩素原子、臭素原子等のハロゲン原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基などの炭素数１から６の直鎖または分岐のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の炭素数３から６の環状のアルキル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｓｅｃ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−ヘキシルオキシ基等の炭素数１から６のアルコキシ基を表わし、Ｌは−ＳＣＨ2 −、−ＳＯ2 −を表わす。）；トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロ−ｎ−プロピル基、ヘプタフルオロイソプロピル基、パーフルオロ−ｎ−ブチル基、パーフルオロ−ｓｅｃ−ブチル基、パーフルオロ−ｎ−ペンチル基、パーフルオロ−ｎ−ヘキシル基等の炭素数１〜６のハロゲン化アルキル基；トリフルオロメトキシ基、ペンタフルオロエトキシ基、トリフルオロエトキシ基、ペンタフルオロエトキシ基、パーフルオロ−ｎ−ブトキシ基、パーフルオロ−ｔｅｒｔ−ブトキシ基、パーフルオロ−ｓｅｃ−ブトキシ基、パーフルオロ−ｎ−ペンチルオキシ基、パーフルオロ−ｎ−ヘキシルオキシ基等炭素数１から６のハロゲン化アルコキシ基；トリフルオロメチルチオ基、トリフルオロエチルチオ基、ペンタフルオロエチルチオ基、ヘプタフルオロ−ｎ−プロピルチオ基、ヘプタフルオロイソプロピルチオ基、パーフルオロ−ｎ−ブチルチオ基、パーフルオロ−ｔ−ブチルチオ基、パーフルオロ−ｓｅｃ−ブチルチオ基、パーフルオロ−ｎ−ペンチルチオ基、パーフルオロ−ｎ−ヘキシルチオ基等炭素数１から６のハロゲン化アルキルチオ基等を表わす。）
【００１４】
環Ｅに対する置換基Ｄ1 〜Ｄ42として挙げたもののうち好ましい基は、環Ｅの構造によって多少異なるが、水素、無置換のアルキル基、ハロゲン化アルキル基、アルキルチオ基、無置換のアルコキシ基、ハロゲン化アルコキシ基、アルケニル基、アルデヒド基、カルボキシル基、アルキルカルボニル基、アルコキシカルボニル基、シアノ基、ニトロ基またはハロゲン原子である。
【００１５】
また、前記一般式（１）および（２）における環Ａは、Ｒ1 と結合する窒素原子以外に少なくとも１個のヘテロ原子を含む、置換されてもよい５〜８員環を表し、それらの群であれば特に制限されない。ヘテロ原子としては通常、酸素原子、硫黄原子、窒素原子である。
【００１６】
【化７】
構造としては下記のものが挙げられる。
【００１８】
【化８】
【化９】
【化１０】
【化１１】
環Ａにおける、Ｒ1 に結合する窒素原子以外のヘテロ原子の位置に特に制限はないが、好ましくは環Ｂに直接結合する位置にあるもの、すなわち下記部分構造式（３）
【００２３】
【化１２】
（式中、Ｚはヘテロ原子を表し、環ＡおよびＲ1 は一般式（１）におけると同義）で表されるものが好ましい。またヘテロ原子の種類は、酸素原子または−ＮＲ2 −（但しＲ2 は水素原子、または置換されていてもよい直鎖もしくは分岐のアルキル基を表す）が特に好ましい。
環Ａは５〜８員環であるが、より好ましくは５員環または６員環を表し、さらに好ましくは環を構成する原子として合計２個のヘテロ原子を含む５員環または６員環を表す。
【００２５】
Ｒ1 、Ｒ2 、Ｒ2 ′は各々独立に、水素原子または置換されてもよい直鎖もしくは分岐のアルキル基を表す。直鎖または分岐のアルキル基として、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基。ｎ−ブチル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−デシル基、ｎ−ドデシル基、ｎ−オクタデシル基等の炭素数１〜２０の直鎖または分岐のアルキル基、好ましくは炭素数１〜１０の直鎖または分岐のアルキル基、より好ましくは炭素数１〜６の直鎖または分岐のアルキル基を表わす。
【００２６】
かかる炭素数１〜２０の直鎖または分岐のアルキル基はメトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｓｅｃ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−ヘキシルオキシ基、ｎ−ヘプチルオキシ基、ｎ−オクチルオキシ基、ｎ−デシルオキシ基等の炭素数１〜１０のアルコキシ基；メトキシメトキシ基、エトキシメトキシ基、プロポキシメトキシ基、メトキシエトキシ基、エトキシエトキシ基、プロポキシエトキシ基、メトキシプロポキシ基、エトキシプロポキシ基、メトキシブトキシ基、エトキシブトキシ基等の炭素数２〜１２のアルコキシアルコキシ基；メトキシメトキシメトキシ基、メトキシメトキシエトキシ基、メトエキシエトキシメトキシ基、メトキシエトキシエトキシ基、エトキシメトキシメトキシ基、エトキシメトキシエトキシ基、エトキシエトキシメトキシ基、エトキシエトキシエトキシ基等の炭素数３〜１５のアルコキシアルコキシアルコキシ基；アリルオキシ基；フェニル基、トリル基、キシリル基、ナフチル基等の炭素数６〜１２のアリール基；フェノキシ基、トリルオキシ基、キシリルオキシ基、ナフチルオキシ基等の炭素数６〜１２のアリールオキシ基；シアノ基；ニトロ基；ヒドロキシ基；テトラヒドロフリル基；テトラヒドロフリル基；メチルスルホニルアミノ基、エチルスルホニルアミノ基、ｎ−プロピルスルホニルアミノ基、イソプロピルスルホニルアミノ基、ｎ−ブチルスルホニルアミノ基、ｔｅｒｔ−ブチルスルホニルアミノ基、ｓｅｃ−ブチルスルホニルアミノ基、ｎ−ペンチルスルホニル基アミノ、ｎ−ヘキシルスルホニルアミノ基等の炭素数１〜６のアルキルスルホニルアミノ基；フッ素原子、塩素原子、臭素原子等のハロゲン基；メトキシカルボニル基、エトキシカルボニル基、ｎ−プロポキシカルボニル基、イソプロポキシカルボニル基、ｎ−ブトキシカルボニル基、ｔｅｒｔ−ブトキシカルボニル基、ｓｅｃ−ブトキシカルボニル基、ｎ−ペンチルオキシカルボニル基、ｎ−ヘキシルオキシカルボニル基等の炭素数２〜７のアルコキシカルボニル基；メチルカルボニルオキシ基、エチルカルボニルオキシ基、ｎ−プロピルカルボニルオキシ基、イソプロピルカルボニルオキシ基、ｎ−ブチルカルボニルオキシ基、ｔｅｒｔ−ブチルカルボニルオキシ基、ｓｅｃ−ブチルカルボニルオキシ基、ｎ−ペンチルカルボニルオキシ基；ｎ−ヘキシルカルボニルオキシ基等の炭素数２〜７のアルキルカルボニルオキシ基；メトキシカルボニルオキシ基、エトキシカルボニルオキシ基、ｎ−プロポキシカルボニルオキシ基、イソプロポキシカルボニルオキシ基、ｎ−ブトキシカルボニルオキシ基、ｔｅｒｔ−ブトキシカルボニルオキシ基、ｓｅｃ−ブトキシカルボニルオキシ基、ｎ−ペンチルオキシカルボニルオキシ基、ｎ−ヘキシルオキシカルボニルオキシ基等の炭素数２〜７のアルコキシカルボニルオキシ基等で置換されていてもよい。
【００２７】
これらの中で、Ｒ1 、Ｒ2 およびＲ2 ′として特に好ましいのは、いずれも、無置換のアルキル基、ハロゲン原子またはアルケニル基で置換されたアルキル基である。
環Ａは置換されてもよい環、つまりＲ1 、Ｒ2 およびＲ2 ′以外にも置換基を有していてもよい環を表す。その置換基として、特に制限はないが、好ましくは、Ｒ1 として挙げたものがいずれも使用でき、中でも無置換のアルキル基がより好ましい。
環Ｂは少なくともＸ1 及び／又はＸ2 で置換されたベンゼン環を表わすが、Ｘ1 かＸ2 のいずれか１つは−ＮＨＳＯ2 Ｙを表し、Ｙは少なくとも２つのフッ素原子で置換されている直鎖または分岐のアルキル基である。Ｙは具体的にはトリフルオロメチル基、ペンタフルオロエチル基、ペンタフルオロプロピル基、２，２，２−トリフルオロエチル基、３，３，３−トリフルオロプロピル基、２，２，３，３，３−ペンタフルオロプロピル基、等が挙げられ、合計の炭素数が１〜６のアルキル基がより好ましく、吸収スペクトル形状及び耐光性、耐久性の点から−ＣＨ2 ＣＦ3 、−ＣＦ3 が特に好ましい。
【００２８】
環ＢはＸ1 およびＸ2 以外にも置換基を有していてもよく、その置換基として、特に制限はないが、ハロゲン原子、置換されてもよい直鎖または分岐のアルキル基、置換されてもよい直鎖または分岐のアルコキシ基等が挙げられる。置換されてもよい直鎖または分岐アルキル基としては、Ｒ1 として挙げたものがいずれも使用できるが、中でも無置換のアルキル基またはハロゲン化アルキル基が好ましい。
また置換されていてもよい直鎖または分岐のアルコキシ基としても、そのアルキル鎖部分がＲ1 の「置換されてもよい直鎖または分岐のアルキル基」として挙げたものいずれかであるアルコキシ基が使用できるが、中でも好ましいのは、無置換のアルコキシ基及びハロゲン化アルコキシ基である。これらは環Ｂにおいて、Ｘ1 またはＸ2 のいずれか一方のみが−ＮＨＳＯ2 Ｙ基であった場合の他方に相当しても、あるいはＸ1 およびＸ2 以外に環Ｂが有する置換基であっても、どちらでもよい。
【００２９】
一般式（１）または（２）で表されるアゾ系化合物において、特に好ましい例としては下記のものが挙げられる。
【００３０】
【化１３】
【化１４】
【化１５】
【化１６】
【化１７】
【化１８】
【化１９】
【化２０】
【化２１】
【化２２】
【化２３】
【化２４】
【化２５】
【化２６】
【化２７】
【化２８】
【化２９】
【化３０】
【化３１】
【化３２】
【化３３】
また、前記環Ｅの具体例の中でも、より好ましいものは、
【００５２】
【化３４】
（式中、Ｄ1 〜Ｄ33は前出と同様）
である。
一般式（１）または（２）で表される色素に対しては、構造以外の制限は特にないが、今後ますます必要とされる、短波長のレーザー光による記録再生可能な光学記録媒体への利用の点からは、色素単層膜について測定した時に波長６５０ｎｍ以下に吸収極大を有する色素がより好ましく、波長６５０〜５００ｎｍに吸収極大をもつものであれば更に好ましい。
【００５４】
本発明において、アゾ系化合物とキレートを形成する金属としては、錯体形成可能な各種の金属または金属イオンを用いることができるが、吸収スペクトルの形状が良好であるという点から遷移金属、中でもＮｉ、Ｃｏ、またはＣｕが好ましく、また各種溶媒への溶解度や耐光性、耐久性の点から特にＮｉが好ましい。
本発明の金属キレート色素は、例えば一般式（１）で表されるアゾ系化合物を、一般式（４）
【００５５】
【化３５】
で示されるアミノ化合物を公知の方法によりジアゾ化し、一般式（５）
【００５７】
【化３６】
で示されるカップリング成分と反応させることにより合成し、メタノール、テトラヒドロフラン、アセトンなどの有機溶媒中で金属化合物のメタノール溶液や水溶液を加えることにより得られる。一般式（２）で表されるアゾ系化合物の金属キレート色素の場合も同様である。
本発明の光学記録媒体は、少なくとも基板と前記アゾ系化合物の金属キレート色素を含む記録層を有するが、必要に応じて基板上に下引き層、金属反射層、保護層等を設けても良い。
好ましい層構成の一例としては、基板上に記録層、金属反射層および保護層を設けた高反射率の媒体が挙げられる。
【００５９】
以下、この構造の媒体を例に、本発明の光学記録媒体について説明する。
本発明の光学記録媒体における基板の材質としては、基本的には記録光及び再生光の波長で透明であればよい。例えば、ポリカーボネート樹脂、塩化ビニル系樹脂、ポリメタクリル産メチル等のアクリル樹脂、ポリスチレン系樹脂、エポキシ系樹脂、酢酸ビニル樹脂、ポリエステル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリイミド系樹脂等の高分子材料やガラス等の無機材料が利用されるが、高生産性、コスト、耐吸湿性、などの点からポリカーボネート樹脂が好ましい。
【００６０】
これらの基板材料は射出成形法等により円盤状に基板に成形される。必要に応じて、基板表面に案内溝やピットを形成することもある。このような案内溝やピットは、基板の成形時に付与することが好ましいが、基板の上に紫外線硬化樹脂層を用いて付与することもできる。案内溝がスパイラル状の場合、この溝ピッチが０．５〜１．２μｍ程度であることが好ましい。
【００６１】
基板上、または必要に応じ下引き層等を設けた上に、本発明の金属キレート色素を含む記録層を形成する。
記録層の成膜方法としては、真空蒸着法、スパッタリング法、ドクターブレード法、キャスト法、スピンコート法、浸漬法等一般に行われている薄膜形成法が挙げられるが、量産性、コスト面からスピンコート法が特に好ましい。
スピンコート法による成膜の場合、回転数は５００〜５０００ｒｐｍが好ましく、スピンコートの後、場合によっては、加熱あるいは溶媒蒸気にあてる等の処理を行っても良い。
【００６２】
ドクターブレード法、キャスト法、スピンコート法、浸漬法等の塗布方法により記録層を形成する場合の塗布溶媒としては、基板を侵さない溶媒であればよく、特に限定されない。例えば、ジアセトンアルコール、３−ヒドロキシ−３−メチル−２−ブタノン等のケトンアルコール系溶媒、メチルセロソルブ、エチルセロソルブ等のセロソルブ系溶媒、ｎ−ヘキサン、ｎ−オクタン等の鎖状炭化水素系溶媒、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、ジメチルシクロヘキサン、ｎ−ブチルシクロヘキサン、ｔ−ブチルシクロヘキサン、シクロオクタン等の環状炭化水素系溶媒、テトラフルオロプロパノール、オクタフルオロペンタノール、ヘキサフルオロブタノール等のパーフルオロアルキルアルコール系溶媒、乳酸メチル、乳酸エチル、イソ酪酸メチル等のヒドロキシカルボン酸エステル系溶媒等が挙げられる。
【００６３】
記録層を成膜する際に、必要に応じて、前記の色素に、クエンチャー、紫外線吸収剤、接着剤等の添加剤を混合か、あるいは、そのような効果を有する置換基として導入することも可能である。
記録層の耐光性や耐久性向上のために加える一重項酸素クエンチャーとしては、アセチルアセトナート系、ビスジチオ−α−ジケトン系やビスフェニルジチオール系などのビスジチオール系、チオカテコール系、サリチルアルデヒドオキシム系、チオビスフェノレート系等の金属錯体が好ましい。またアミン系化合物も好適である。
【００６４】
また、記録特性などの改善のために、他の色素を併用してもよい。併用可能な色素としては、本発明の色素と同系統の、アゾ系色素またはアゾ系金属キレート色素であっても、シアニン系色素、スクアリリウム系色素、ナフトキノン系色素、アントラキノン系色素、ポルフィリン系色素、テトラピラポルフィラジン系色素、インドフェノール系色素、ピリリウム系色素、チオピリリウム系色素、アズレニウム系色素、トリフェニルメタン系色素、キサンテン系色素、インダンスレン系色素、インジゴ系色素、チオインジゴ系色素、メロシアニン系色素、ビスピロメテン系色素、チアジン系色素、アクリジン系色素、オキサジン系色素、インドアニリン系色素など、他系統の色素でもよい。
【００６５】
色素の熱分解促進剤としては、例えば、金属系アンチノッキング剤、メタロセン化合物、アセチルアセトナト系金属錯体等の金属化合物が挙げられる。
さらに、必要に応じて、バインダー、レベリング剤、消泡剤等を併用することもできる。好ましいバインダーとしては、ポリビニルアルコール、ポリビニルピロリドン、ニトロセルロース、酢酸セルロース、ケトン系樹脂、アクリル系樹脂、ポリスチレン系樹脂、ウレタン系樹脂、ポリビニルブチラール、ポリカーボネート、ポリオレフィン等が挙げられる。
色素層の膜厚は、特に限定するものではないが、好ましくは５０〜３００ｎｍである。色素層の膜厚を５０ｎｍよりあまり薄くすると、熱拡散が大きいため記録出来ないか、記録信号に歪みが発生する上、信号振幅が小さくなる傾向がある。また、膜厚が３００ｎｍよりあまり厚い場合は反射率が低下し、再生信号特性が悪化するおそれがある。
【００６６】
次に記録層の上に、好ましくは、厚さ５０〜３００ｎｍの反射層を形成する。反射層の材料としては、再生光の波長で反射率の十分高いもの、例えば、Ａｕ、Ａｌ、Ａｇ、Ｃｕ、Ｔｉ、Ｃｒ、Ｎｉ、Ｐｔ、Ｔａ、Ｃｒ及びＰｄの金属を単独あるいは合金にして用いることが可能である。この中でもＡｕ、Ａｌ、Ａｇは反射率が高く反射層の材料として適している。これ以外でも下記のものを含んでいてもよい。例えば、Ｍｇ、Ｓｅ、Ｈｆ、Ｖ、Ｎｂ、Ｒｕ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｃｏ、Ｒｈ、Ｉｒ、Ｃｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｔｅ、Ｐｂ、Ｐｏ、Ｓｎ、Ｂｉなどの金属及び半金属を挙げることができる。中でもＡｇを主成分としているものはコストが安い点、アゾ金属キレート系色素と組み合わせた時に反射率が向上する傾向がある点、更に後に述べる印刷受容層を設ける場合には地色が白く美しいものが得られる点、等から、特に好ましい。ここで主成分とは含有率が５０％以上のものをいう。金属以外の材料で低屈折率薄膜と高屈折率薄膜を交互に積み重ねて多層膜を形成し、反射層として用いることも可能である。
【００６７】
反射層を形成する方法としては、例えば、スパッタ法、イオンプレーティング法、化学蒸着法、真空蒸着法等が挙げられる。また、基板の上や反射層の下に反射率の向上、記録特性の改善、密着性の向上等のために公知の無機系または有機系の中間層、接着層を設けることもできる。
反射層の上に形成する保護層の材料としては、反射層を外力から保護するものであれば特に限定しない。有機物質としては、熱可塑性樹脂、熱硬化性樹脂、電子線硬化性樹脂、ＵＶ硬化性樹脂等を挙げることができる。また、無機物質としては、ＳｉＯ2 、ＳｉＮ4 、ＭｇＦ2 、ＳｎＯ2 等が挙げられる。熱可塑性樹脂、熱硬化性樹脂などは適当な溶剤に溶解して塗布液を塗布し、乾燥することによって形成することができる。ＵＶ硬化性樹脂は、そのままもしくは適当な溶剤に溶解して塗布液を調製した後にこの塗布液を塗布し、ＵＶ光を照射して硬化させることによって形成することができる。ＵＶ硬化性樹脂としては、例えば、ウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレートなどのアクリレート系樹脂を用いることができる。これらの材料は単独であるいは混合して用いてもよいし、１層だけでなく多層膜にして用いてもよい。
【００６８】
保護層の形成の方法としては、記録層と同様にスピンコート法やキャスト法などの塗布法やスパッタ法や化学蒸着法等の方法が用いられるが、この中でもスピンコート法が好ましい。
保護層の膜厚は、一般には０．１〜１００μｍの範囲であるが、本発明においては、３〜３０μｍであり、好ましくは５〜２０μｍがより好ましい。
また、反射層面に基板を貼り合わせる、あるいは反射層面相互を内側とし対向させ光記録媒体２枚を貼り合わせる等の手段を用いてもよい。基板鏡面側に、表面保護やゴミ等の付着防止のために紫外線硬化樹脂、無機系薄膜等を成膜してもよい。
反射層上に受けた保護層の上、又は反射層面に貼りあわせた基板の上等に更に印刷受容層を形成することもできる。
【００６９】
上記のようにして得られた光学記録媒体への記録は、基板の両面または片面に設けた記録層にレーザー光をあてることにより行う。レーザー光の照射された部分には、レーザー光エネルギーの吸収による分解、発熱、溶融等の記録層の熱的変形が起こる。記録された情報の再生は、レーザー光により熱的変形が起きている部分と起きてない部分の反射率の差を読みとることにより行う。
本発明の光記録媒体は、記録・再生に使用する波長のレーザー光に対して、基板側から測定した反射率が２０％以上であることが好ましい。
【００７０】
記録・再生に使用するレーザーに特に限定はないが、例えば、可視領域の広範囲で波長選択のできる色素レーザーや、波長６３３ｎｍのヘリウムネオンレーザー、最近開発されている波長６８０、６５０、６３５ｎｍ付近の高出力半導体レーザー、波長５３２ｎｍの高調波変換ＹＡＧレーザーなどが挙げられるが、軽量性、取り扱いの容易さ、コンパクト性、コスト等の点では半導体レーザーが好適である。本発明では、これらから選択される一波長または複数波長において高密度記録及び再生が可能となる。
【００７１】
【実施例】
以下実施例によりこの発明を具体的に説明するが、かかる実施例はその要旨を超えない限り、本発明を限定するものではない。
尚、ε（分子吸光係数）は、金属一原子に対して二原子のアゾ系化合物が配位したものとして算出した。
実施例１
（ａ）製造例
【００７２】
【化３７】
窒素気流化で、上記構造式(a) で示される2-ヒドロキシアセトアニリド25.5g （湿結晶、0.15mol 相当）をＴＨＦ200ml 、トルエン250ml に溶解し、テトラブチルアンモニウムブロミド4.5g、1,2-ジブチルエタン113g、水酸化ナトリウム24g を加えた。
混合物を24〜25℃で12時間攪拌後、反応混合物を水1l中に注いだ。この混合物をトルエンで抽出、水洗した後、無水硫酸ナトリウムで乾燥し、トルエンを留去して下記構造式(b) で示される茶色オイル17.7g を得た。
【００７４】
【化３８】
水酸化ナトリウム60ｇをメタノール200 ｍｌと水70ｍｌの混合溶液に加え溶解した。次に上記構造式(b) で示される化合物30ｇのメタノール50ｍl溶液を加え、45℃で3 時間攪拌反応させた。
反応終了後、反応液にトルエン250 ｍｌと水１ｌを加え抽出し、得たトルエン層を水洗した後、無水硫酸ナトリウムで乾燥した。次に、無水硫酸ナトリウムをろ去し、ろ液を濃縮して下記構造式(c) で示される濃茶色オイル17.3g を得た。
【００７６】
【化３９】
上記構造式(c) で示される化合物8.0 ｇをＮ−メチル−２−ピロリドンに溶解し、ヨウ化イソプロピル15.24 ｇと炭酸カリウム 8.2 ｇを加えた。混合物を攪拌下加温し、80〜90℃で１時間反応させた。反応終了後、反応液にトルエン100 ｍｌと水300 ｍｌを加え抽出、水洗した後、無水硫酸ナトリウムで乾燥、濃縮して下記構造式(d) で示される濃茶色オイルを9.5g得た。
【００７８】
【化４０】
上記構造式(d) で示される化合物10.0ｇを濃硫酸100 ｇに溶解し冷却した。この混合液に60％硝酸6.5 ｇと濃硫酸25ｇの混合液を10℃以下で加え、15分間攪拌した。次に反応液を氷水240 ｇに加え、15℃以下で50％水酸化ナトリウム163.3 ｇを滴下、晶析させた。晶析した結晶をろ別し、結晶を水で良く洗浄した後、乾燥して下記構造式(e) で示される橙色結晶10.8ｇを得た。
【００８０】
【化４１】
鉄粉24.5g をＤＭＦ−水（２：１）150ml に懸濁させ、攪拌しながら85〜90℃に加熱し, そこに35％塩酸4.0 ｇ、ＤＭＦ−水（２：１）75mlを混合させた溶液を滴下した。続いて上記化合物(e) で示される化合物10.8g のDMF 溶液60mlを内温80〜95℃に保ちながら約15分間で滴下した。滴下後、反応混合物を80〜95℃で20分間攪拌し、その後放冷しながら炭酸水素ナトリウム4.9gを添加して10分攪拌後、ろ過して鉄粉を除去し、そのろ液を氷水400ml に注入しトルエン抽出した。無水硫酸ナトリウムで乾燥後、トルエンを留去し下記構造式(f) で示される褐色液体9.6gを得た。
【００８２】
【化４２】
窒素気流下で上記化合物(f)9.6g のトルエン溶液を攪拌しながら5 ℃以下保ち、トリフルオロメタンスルホン酸無水物18.6g を滴下した。滴下後10〜15℃で30分攪拌した後、一晩放置後、デカンテーションでトルエンを除き、残った固体に水100ml を加え、酢酸エチル100ml で抽出した。
無水硫酸ナトリウムで乾燥後、酢酸エチルを留去して下記構造式(g) で示される濃褐色液体8.8gを得た。
【００８４】
【化４３】
下記構造式(h) で示される2-アミノ-4,5- ジシアノイミダゾール3.42g
【００８６】
【化４４】
を水100ml に懸濁し-5〜10℃で35％塩酸を滴下した。続いて-5〜5 ℃で亜硝酸ナトリウム1.95g の水6.6gの溶液を滴下しジアゾ化した。
前記構造式(g) で示される化合物10.0g 、尿素1.02g 、酢酸ナトリウム10.2g をメタノール90mlに溶解させた溶液に、ジアゾ液を-5〜5 ℃で滴下し、3 時間攪拌後、一晩放置した。析出した結晶をろ別し、乾燥して下記構造式(i) で示される赤褐色結晶11.0g を得た。
【００８８】
【化４５】
上記構造式(i) で示されるアゾ化合物11.0ｇをメタノール220ml に溶解し、炭酸カリウム3.9gを加え、攪拌しながら40〜50℃に加温した。40〜50℃でジメチル硫酸3.55g を滴下し、２時間攪拌後、放冷晶析させた。析出した結晶をろ別し、メタノールで洗浄し、乾燥して下記構造式(j) で示される赤色結晶7.9gを得た。
【００９０】
【化４６】
上記構造式(j) で示されるアゾ化合物7.9gをＴＨＦ240mlに溶解し、室温で酢酸ニッケル四水和物2.4gのメタノール50ml溶液を加えた後、室温で3 時間攪拌し、水240ml を加えた。析出した結晶をろ別し、これを水で洗浄、乾燥してニッケルキレート色素4.2gを得た。この化合物のλmax （クロロホルム中）は597nm （ε＝10.5×104 ）であった。
【００９２】
(b) 記録媒体例
前記のようにして得られたニッケルキレート色素をオクタフルオロペンタノールに溶解し、1.1wt ％にした。これを50℃以下で30分間超音波分散した後、0.2 μｍのフィルターでろ過し、その液を回転数800rpmで0.6mm 厚のポリカーボネート基板にスピンコートした。尚、この基板の溝幅は0.32μm であり、（トラックピッチ0.8 μm ）溝深さは140nm である。次にこの塗布膜を80℃のオーブンで乾燥した後、塗布膜の上にスパッタリング法により膜厚100nm のAg膜を成膜し、反射層を形成した。さらにこの反射層の上に紫外線硬化樹脂を3 μｍスピンコートし、これに紫外線を照射して硬化させて保護層を形成し、記録媒体とした。さらに保護層上にホットメルト接着剤をつけ、まったく同様にして得られた記録媒体同士を接着し、光ディスクとした。ニッケルキレート色素の塗布膜（記録層）のλmax は613.5nm であった。記録層の膜厚はランドと溝部平均で60nmであった。
【００９３】
(c) 光記録法
657nm の半導体レーザー評価機（パルステック社製ＤＤＵ−１０００、ＮＡ＝0.65) で、線速3.5m/s、再生パワー0.7mW で、最短マーク長0.40μm の8 ／16変調信号を入力して（３Ｔtop パルス幅＝1.5 Ｔ；ここでＴは基準クロック周波数で本例では38.2ns. ）記録したところ、記録パワー8.0mW 、Itop反射率（上記評価機での偏光ビームスプリッターを通した、８／１６変調記録部トップ（１４Ｔ）の反射率）45％、変調度68％の良好な記録特性が得られた。
実施例２
(a) 製造例
【００９４】
【化４７】
上記構造式(k) で示される3-アミノ-5- メチル-1,2- イソオキサゾール1.0gを酢酸10mL、プロピオン酸5ml に溶解し、0 〜5 ℃で硫酸1ml を添加し、0 〜5 ℃で43％ニトロシル硫酸3.55g を加えジアゾ化した。
上記構造式(g) で示される化合物4.0g、尿素0.4g、酢酸ナトリウム4.0gをメタノール100ml に溶解させた溶液に、ジアゾ液を-5〜5 ℃で滴下し、3 時間攪拌後、一晩放置した。析出した結晶をろ別し、乾燥して下記構造式(l) で示される赤褐色結晶2.23g を得た。
【００９６】
【化４８】
上記構造式(l) で示されるアゾ化合物2.1gをメタノール20mlに溶解し、室温で酢酸ニッケル四水和物0.72g のメタノール15ml溶液を加えた後、室温で3 時間攪拌し、水20mlを加えた。析出した結晶をろ別し、これを水とメタノールで洗浄、乾燥してニッケルキレート色素2.0gを得た。この色素のλmax （クロロホルム中）は568nm （ε＝5.7 ×104 ）であった。
【００９８】
(b) 記録媒体例
前記のようにして得られたニッケルキレート色素を用いて実施例１と同様の方法で光ディスクを作成した。塗布膜のλmax は586nm であった。記録層の平均膜厚は約80nmであった。
【００９９】
(c) 光記録法
実施例１と同様の方法で記録したところ、記録パワー11mW、Itop反射率51％、変調度68％の良好な記録特性が得られた。
【０１００】
【発明の効果】
本発明の金属キレート色素を使用することにより、比較的短波長での記録に対して感度がよいため高速記録に適し、かつ耐光性に優れた光学記録媒体を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal chelate dye of an azo compound having a specific structure and a metal, and an optical recording medium using the dye.
In recent years, development of a semiconductor laser having a short oscillation wavelength has been promoted, and an optical recording medium capable of high-density recording and reproduction using a laser beam having a shorter wavelength than the conventional 780 nm and 830 nm has been demanded. Conventionally proposed optical recording media include magneto-optical recording media, phase change recording media, chalcogen oxide optical recording media, and organic dye-based optical recording media. Among these, organic dye-based optical recording media are considered to be significant in that they are inexpensive and easy to process.
Currently, as an organic dye-based optical recording medium, a CD-R of a type in which a metal layer having a high reflectance is laminated on an organic dye layer is mass-produced and widely known. It is considered that a high-density organic dye-based optical recording medium capable of recording / reproducing with a wavelength semiconductor laser is required.
[0002]
[Problems to be solved by the invention]
In general, a medium used as a CD-R has a problem that, when used at a wavelength shorter than the original recording / reproducing wavelength (780 nm) such as 680 nm, 650 nm, and 635 nm, the reflectance is low and recording / reproducing cannot be performed. ing. In addition, even with a medium currently proposed for recording at a short wavelength, the deformation of the recording part due to dye decomposition during recording is large, the degree of modulation is not obtained so much, and the light resistance and durability are insufficient. There are some problems.
The present inventors previously proposed an optical recording medium using a novel azo-based metal chelate dye having excellent light resistance and durability in Japanese Patent Application Laid-Open No. 3-268994. Improvements were made in search of further improvements.
[0003]
[Means for Solving the Problems]
In addition, the applicant previously described that the alkylsulfonylamino group bonded to the benzene ring of the coupling component of the azo compound forming the azo metal chelate dye is substituted with fluorine, and the coupling component By using an azo metal chelate dye whose benzene ring has a specific amino group, we found a dye that can provide an optical recording medium with excellent light resistance and durability, and markedly improved recording and reproduction characteristics. (Japanese Patent Laid-Open No. 11-166125).
Recently, the present inventors further improved the recording characteristics of the optical recording medium by forming a ring in which the amino group on the benzene ring of the coupling component is bonded to the benzene ring via a heteroatom and condensed to the benzene ring. The present inventors have found that there is a tendency to further improve and have reached the present invention.
[0004]
That is, the present invention resides in a metal chelate dye comprising an azo compound represented by the following general formula (1) or (2) and a metal, and an optical recording medium using the same.
[0005]
[Chemical 3]
(In the formula, ring E represents a heterocyclic ring formed together with the carbon atom and nitrogen atom to which each is bonded, and ring A represents R 1 Represents a 5- to 8-membered ring which may be substituted, containing at least one heteroatom other than the nitrogen atom bonded to. Ring B is at least X 1 And / or X 2 Represents a benzene ring substituted with 1 Or X 2 At least one of -NHSO 2 Y represents a Y group, and Y represents a linear or branched alkyl group substituted with at least two fluorine atoms. R 1 Represents a hydrogen atom or an optionally substituted linear or branched alkyl group. )
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
As the azo compound in the present invention, in the general formulas (1) and (2), the ring E may be a heterocyclic ring formed together with a carbon atom and a nitrogen atom bonded to each other. Although it will not restrict | limit especially if it is a group, Preferably the following are mentioned.
[0008]
[Formula 4]
(Where D 1 ~ D 42 Is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, etc. Linear or branched alkyl group; C3-C6 cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy Group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, n-hexyloxy group and other alkoxy groups having 1 to 6 carbon atoms; acetyl group, propiol group, butyryl group, isobutyryl group, valeryl group, isovaleryl Group, pivaloyl group, hexanoyl group, heptanoyl group, etc., C1-C6 alkylcarbonyl group; vinyl A linear or branched alkenyl group having 2 to 6 carbon atoms such as a propenyl group, a butenyl group, a pentenyl group or a hexenyl group; a cyclic alkenyl group having 3 to 6 carbon atoms such as a cyclopentenyl group or a cyclohexenyl group; a fluorine atom, Halogen atoms such as chlorine atom and bromine atom; formyl group; hydroxyl group; carboxyl group; hydroxyalkyl group having 1 to 6 carbon atoms such as hydroxymethyl group and hydroxyethyl group; methoxycarbonyl group, ethoxycarbonyl group and n-propoxycarbonyl An alkoxycarbonyl group having 2 to 7 carbon atoms such as a group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group; Nitro group; cyano group; amino ; 1-10 carbon atoms such as methylamino group, ethylamino group, n-propylamino group, n-butylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-n-butylamino group; An alkylamino group of 3 to 7 carbon atoms such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, isopropoxycarbonylethyl group; methylthio group, ethylthio group, n-propylthio group Alkyl thio groups having 1 to 6 carbon atoms such as tert-butylthio group, sec-butylthio group, n-pentylthio group and n-hexylthio group; methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group, n -Butylsulfonyl group, tert-butyl An alkylsulfonyl group having 1 to 6 carbon atoms such as a rusulfonyl group, a sec-butylsulfonyl group, an n-pentylsulfonyl group and an n-hexylsulfonyl group; an aryl group having 6 to 16 carbon atoms which may have a substituent; An optionally substituted arylcarbonyl group having 7 to 17 carbon atoms; 43 = C (CN) D 44 (D 43 Has 1 to 6 carbon atoms such as hydrogen atom or methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, etc. Represents an alkyl group, D 44 Is a cyano group or methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentylcarbonyl group, n-hexyl. An alkoxy group having 2 to 7 carbon atoms such as an oxycarbonyl group is represented. );
[0010]
[Chemical formula 5]
D 45 ~ D 47 Are independently a hydrogen atom, a nitro group, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert- A linear or branched alkyl group having 1 to 6 carbon atoms such as a butyl group, an n-pentyl group or an n-hexyl group; a cyclic group having 3 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group; Alkyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, n-hexyloxy group, etc. Represents an alkoxy group of 6; );
[0012]
[Chemical 6]
D 48 ~ D 50 Are independently a hydrogen atom, a nitro group, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert- A linear or branched alkyl group having 1 to 6 carbon atoms such as a butyl group, an n-pentyl group or an n-hexyl group; a cyclic group having 3 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group; Alkyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, n-hexyloxy group, etc. 6 represents an alkoxy group, and L represents —SCH. 2 -, -SO 2 Represents-. ); Trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, perfluoro-n-butyl group, perfluoro-sec-butyl group, perfluoro-n-pentyl group, perfluoro group C1-C6 halogenated alkyl group such as fluoro-n-hexyl group; trifluoromethoxy group, pentafluoroethoxy group, trifluoroethoxy group, pentafluoroethoxy group, perfluoro-n-butoxy group, perfluoro- tert-butoxy group, perfluoro-sec-butoxy group, perfluoro-n-pentyloxy group, perfluoro-n-hexyloxy group and the like, halogenated alkoxy group having 1 to 6 carbon atoms; trifluoromethylthio group, trifluoroethyl Thio group, pentafluoroethylthio group, hep Fluoro-n-propylthio group, heptafluoroisopropylthio group, perfluoro-n-butylthio group, perfluoro-t-butylthio group, perfluoro-sec-butylthio group, perfluoro-n-pentylthio group, perfluoro-n- Represents a halogenated alkylthio group having 1 to 6 carbon atoms, such as a hexylthio group; )
[0014]
Substituent D for Ring E 1 ~ D 42 Preferred groups among those listed above vary depending on the structure of ring E, but are hydrogen, unsubstituted alkyl group, halogenated alkyl group, alkylthio group, unsubstituted alkoxy group, halogenated alkoxy group, alkenyl group, aldehyde group. , Carboxyl group, alkylcarbonyl group, alkoxycarbonyl group, cyano group, nitro group or halogen atom.
[0015]
The ring A in the general formulas (1) and (2) is R 1 It represents an optionally substituted 5- to 8-membered ring containing at least one heteroatom other than the nitrogen atom bonded to and is not particularly limited as long as it is a group thereof. The hetero atom is usually an oxygen atom, a sulfur atom, or a nitrogen atom.
[0016]
[Chemical 7]
Examples of the structure include the following.
[0018]
[Chemical 8]
[Chemical 9]
[Chemical Formula 10]
Embedded image
R in ring A 1 There is no particular limitation on the position of the hetero atom other than the nitrogen atom bonded to the ring.
[0023]
Embedded image
(Wherein Z represents a heteroatom, and ring A and R 1 Is preferably the same as defined in formula (1). Moreover, the kind of hetero atom is oxygen atom or -NR. 2 -(However, R 2 Represents a hydrogen atom or an optionally substituted linear or branched alkyl group).
Ring A is a 5- to 8-membered ring, more preferably a 5-membered or 6-membered ring, and still more preferably a 5-membered or 6-membered ring containing a total of 2 heteroatoms as atoms constituting the ring. To express.
[0025]
R 1 , R 2 , R 2 Each independently represents a hydrogen atom or an optionally substituted linear or branched alkyl group. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octadecyl group, etc. Represents a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms.
[0026]
Such a linear or branched alkyl group having 1 to 20 carbon atoms is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, a sec-butoxy group, or an n-pentyloxy group. , An n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-decyloxy group, etc., an alkoxy group having 1 to 10 carbon atoms; a methoxymethoxy group, an ethoxymethoxy group, a propoxymethoxy group, a methoxyethoxy group, C2-C12 alkoxyalkoxy groups such as ethoxyethoxy group, propoxyethoxy group, methoxypropoxy group, ethoxypropoxy group, methoxybutoxy group, ethoxybutoxy group; methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group , Methoxyethoxyethoxy Groups, ethoxymethoxymethoxy groups, ethoxymethoxyethoxy groups, ethoxyethoxymethoxy groups, ethoxyethoxyethoxy groups, etc., alkoxyalkoxyalkoxy groups having 3 to 15 carbon atoms; allyloxy groups; phenyl groups, tolyl groups, xylyl groups, naphthyl groups, etc. Aryl group having 6 to 12 carbon atoms; aryloxy group having 6 to 12 carbon atoms such as phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group; cyano group; nitro group; hydroxy group; tetrahydrofuryl group; tetrahydrofuryl group; Methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino group, isopropylsulfonylamino group, n-butylsulfonylamino group, tert-butylsulfonylamino group, sec-butylsulfonylamino group, n-pen Alkylsulfonylamino groups having 1 to 6 carbon atoms such as rusulfonyl group amino and n-hexylsulfonylamino group; halogen groups such as fluorine atom, chlorine atom and bromine atom; methoxycarbonyl group, ethoxycarbonyl group and n-propoxycarbonyl group An alkoxycarbonyl group having 2 to 7 carbon atoms such as isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group; Carbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, tert-butylcarbonyloxy group, sec-butylcarbonyloxy group, n-pentylca Carbonyloxy group having 2 to 7 carbon atoms such as n-hexylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyl Substituted with an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as oxy group, tert-butoxycarbonyloxy group, sec-butoxycarbonyloxy group, n-pentyloxycarbonyloxy group, n-hexyloxycarbonyloxy group, etc. Also good.
[0027]
Among these, R 1 , R 2 And R 2 Particularly preferred as ′ is any alkyl group substituted with an unsubstituted alkyl group, a halogen atom or an alkenyl group.
Ring A is an optionally substituted ring, ie R 1 , R 2 And R 2 It represents a ring which may have a substituent other than ′. The substituent is not particularly limited, but preferably R 1 Any of those mentioned above can be used, and an unsubstituted alkyl group is more preferable.
Ring B is at least X 1 And / or X 2 Represents a benzene ring substituted with 1 Or X 2 Any one of -NHSO 2 Y represents a linear or branched alkyl group substituted with at least two fluorine atoms. Y is specifically a trifluoromethyl group, pentafluoroethyl group, pentafluoropropyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3 , 3-pentafluoropropyl group, and the like, and an alkyl group having 1 to 6 carbon atoms in total is more preferable. From the viewpoint of absorption spectrum shape, light resistance, and durability, —CH 2 CF Three , -CF Three Is particularly preferred.
[0028]
Ring B is X 1 And X 2 In addition to the above, there may be a substituent, and the substituent is not particularly limited, but may be a halogen atom, an optionally substituted linear or branched alkyl group, an optionally substituted linear or branched An alkoxy group etc. are mentioned. Examples of the linear or branched alkyl group that may be substituted include R 1 Any of those mentioned above can be used, and among them, an unsubstituted alkyl group or a halogenated alkyl group is preferable.
Also, as the linear or branched alkoxy group which may be substituted, the alkyl chain portion is R 1 Any of the alkoxy groups listed as the “optionally substituted linear or branched alkyl group” can be used, and an unsubstituted alkoxy group and a halogenated alkoxy group are particularly preferable. These in ring B are X 1 Or X 2 Only one of these is -NHSO 2 Even if it corresponds to the other when it is a Y group, or X 1 And X 2 In addition to these, any of the substituents of ring B may be used.
[0029]
In the azo compound represented by the general formula (1) or (2), the following are particularly preferable examples.
[0030]
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Embedded image
Among the specific examples of the ring E, more preferable are:
[0052]
Embedded image
(Where D 1 ~ D 33 Is the same as above)
It is.
The dye represented by the general formula (1) or (2) is not particularly limited except for the structure, but to an optical recording medium capable of recording and reproducing with a short-wavelength laser beam that will be increasingly required in the future. From the viewpoint of utilization, a dye having an absorption maximum at a wavelength of 650 nm or less when measured for a dye monolayer film is more preferable, and a dye having an absorption maximum at a wavelength of 650 to 500 nm is more preferable.
[0054]
In the present invention, various metals or metal ions capable of forming a complex can be used as the metal that forms a chelate with an azo compound, but transition metals, particularly Ni, Co or Cu is preferable, and Ni is particularly preferable from the viewpoints of solubility in various solvents, light resistance, and durability.
For example, the metal chelate dye of the present invention is obtained by converting an azo compound represented by the general formula (1) into the general formula (4).
[0055]
Embedded image
A diazotized amino compound represented by the general formula (5)
[0057]
Embedded image
It can be obtained by adding a methanol solution or an aqueous solution of a metal compound in an organic solvent such as methanol, tetrahydrofuran, or acetone. The same applies to the metal chelate dye of the azo compound represented by the general formula (2).
The optical recording medium of the present invention has at least a substrate and a recording layer containing a metal chelate dye of the azo compound, but an undercoat layer, a metal reflective layer, a protective layer, etc. may be provided on the substrate as necessary. .
As an example of a preferable layer configuration, a high reflectance medium in which a recording layer, a metal reflection layer, and a protective layer are provided on a substrate can be given.
[0059]
Hereinafter, the optical recording medium of the present invention will be described using the medium having this structure as an example.
The material of the substrate in the optical recording medium of the present invention may be basically transparent at the wavelength of recording light and reproducing light. For example, polymers such as polycarbonate resin, vinyl chloride resin, polymethyl methacrylate acrylic resin, polystyrene resin, epoxy resin, vinyl acetate resin, polyester resin, polyethylene resin, polypropylene resin, polyimide resin, etc. Inorganic materials such as materials and glass are used, but polycarbonate resin is preferable from the viewpoint of high productivity, cost, moisture absorption resistance, and the like.
[0060]
These substrate materials are formed into a disk shape by an injection molding method or the like. If necessary, guide grooves and pits may be formed on the substrate surface. Such guide grooves and pits are preferably provided at the time of forming the substrate, but can also be provided on the substrate using an ultraviolet curable resin layer. When the guide groove has a spiral shape, the groove pitch is preferably about 0.5 to 1.2 μm.
[0061]
A recording layer containing the metal chelate dye of the present invention is formed on a substrate or, if necessary, an undercoat layer or the like.
As a method for forming the recording layer, there are generally used thin film forming methods such as a vacuum deposition method, a sputtering method, a doctor blade method, a casting method, a spin coating method, and an immersion method. A coating method is particularly preferred.
In the case of film formation by a spin coating method, the number of rotations is preferably 500 to 5000 rpm, and after spin coating, depending on the case, treatment such as heating or application to solvent vapor may be performed.
[0062]
The coating solvent for forming the recording layer by a coating method such as a doctor blade method, a casting method, a spin coating method, or a dipping method may be any solvent that does not attack the substrate and is not particularly limited. For example, ketone alcohol solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone, cellosolv solvents such as methyl cellosolve and ethyl cellosolve, and chain hydrocarbon solvents such as n-hexane and n-octane Cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, t-butylcyclohexane, cyclooctane, and perfluoroalkyl alcohols such as tetrafluoropropanol, octafluoropentanol, hexafluorobutanol, etc. And hydroxycarboxylic acid ester solvents such as methyl solvent, methyl lactate, ethyl lactate, and methyl isobutyrate.
[0063]
When forming a recording layer, if necessary, additives such as quenchers, ultraviolet absorbers, adhesives, etc. may be mixed with the above dyes or introduced as substituents having such effects. Is also possible.
Singlet oxygen quenchers added to improve the light resistance and durability of the recording layer include bisdithiols such as acetylacetonate, bisdithio-α-diketone and bisphenyldithiol, thiocatechol, and salicylaldehyde oxime. And metal complexes such as thiobisphenolate are preferred. Amine compounds are also suitable.
[0064]
Further, other dyes may be used in combination for improving the recording characteristics. As the dye that can be used in combination, even if it is an azo dye or an azo metal chelate dye of the same type as the dye of the present invention, a cyanine dye, a squarylium dye, a naphthoquinone dye, an anthraquinone dye, a porphyrin dye, Tetrapyrporphyrazine dyes, indophenol dyes, pyrylium dyes, thiopyrylium dyes, azurenium dyes, triphenylmethane dyes, xanthene dyes, indanthrene dyes, indigo dyes, thioindigo dyes, merocyanine dyes Other dyes such as dyes, bispyromethene dyes, thiazine dyes, acridine dyes, oxazine dyes, indoaniline dyes may be used.
[0065]
Examples of the thermal decomposition accelerator for the dye include metal compounds such as metal anti-knock agents, metallocene compounds, and acetylacetonato metal complexes.
Furthermore, a binder, a leveling agent, an antifoaming agent, etc. can also be used together as needed. Preferable binders include polyvinyl alcohol, polyvinyl pyrrolidone, nitrocellulose, cellulose acetate, ketone resin, acrylic resin, polystyrene resin, urethane resin, polyvinyl butyral, polycarbonate, polyolefin and the like.
The thickness of the dye layer is not particularly limited, but is preferably 50 to 300 nm. If the thickness of the dye layer is less than 50 nm, recording cannot be performed due to large thermal diffusion, or the recording signal tends to be distorted and the signal amplitude tends to be small. On the other hand, when the film thickness is much thicker than 300 nm, the reflectance is lowered, and the reproduction signal characteristics may be deteriorated.
[0066]
Next, a reflective layer having a thickness of 50 to 300 nm is preferably formed on the recording layer. As a material for the reflective layer, a material having a sufficiently high reflectance at the wavelength of the reproduction light, for example, Au, Al, Ag, Cu, Ti, Cr, Ni, Pt, Ta, Cr, and Pd metals may be used alone or in an alloy. It is possible to use. Among these, Au, Al, and Ag have high reflectivity and are suitable as the material for the reflective layer. Other than this, the following may be included. For example, Mg, Se, Hf, V, Nb, Ru, W, Mn, Re, Fe, Co, Rh, Ir, Cu, Zn, Cd, Ga, In, Si, Ge, Te, Pb, Po, Sn, Mention may be made of metals such as Bi and metalloids. Among them, those containing Ag as a main component are inexpensive and have a tendency to improve the reflectance when combined with an azo metal chelate dye. Further, when a print receiving layer described later is provided, the ground color is white and beautiful. Is particularly preferable from the viewpoint of obtaining Here, the main component means one having a content of 50% or more. It is also possible to form a multilayer film by alternately stacking a low refractive index thin film and a high refractive index thin film using a material other than metal, and use it as a reflective layer.
[0067]
Examples of the method for forming the reflective layer include sputtering, ion plating, chemical vapor deposition, and vacuum vapor deposition. In addition, a known inorganic or organic intermediate layer or adhesive layer may be provided on the substrate or under the reflective layer in order to improve reflectivity, improve recording characteristics, and improve adhesion.
The material of the protective layer formed on the reflective layer is not particularly limited as long as it protects the reflective layer from external force. Examples of the organic substance include a thermoplastic resin, a thermosetting resin, an electron beam curable resin, and a UV curable resin. In addition, as an inorganic substance, SiO 2 , SiN Four , MgF 2 , SnO 2 Etc. A thermoplastic resin, a thermosetting resin, or the like can be formed by dissolving in an appropriate solvent, applying a coating solution, and drying. The UV curable resin can be formed by preparing a coating solution as it is or by dissolving it in a suitable solvent, and then applying the coating solution and curing it by irradiating with UV light. As the UV curable resin, for example, acrylate resins such as urethane acrylate, epoxy acrylate, and polyester acrylate can be used. These materials may be used alone or in combination, and may be used not only as a single layer but also as a multilayer film.
[0068]
As a method for forming the protective layer, a coating method such as a spin coating method and a casting method, a sputtering method, a chemical vapor deposition method, and the like are used as in the recording layer. Among these, a spin coating method is preferable.
The thickness of the protective layer is generally in the range of 0.1 to 100 μm, but in the present invention, it is 3 to 30 μm, and more preferably 5 to 20 μm.
Also, a means such as bonding the substrate to the reflection layer surface or bonding two optical recording media with the reflection layer surfaces facing each other inside may be used. An ultraviolet curable resin, an inorganic thin film, or the like may be formed on the mirror surface side of the substrate in order to protect the surface or prevent adhesion of dust and the like.
A print receiving layer can also be formed on the protective layer received on the reflective layer or on the substrate bonded to the reflective layer surface.
[0069]
Recording on the optical recording medium obtained as described above is performed by applying a laser beam to the recording layer provided on both sides or one side of the substrate. In the portion irradiated with the laser beam, thermal deformation of the recording layer such as decomposition, heat generation, melting due to absorption of laser beam energy occurs. The recorded information is reproduced by reading the difference in reflectance between the portion where the thermal deformation is caused by the laser beam and the portion where it is not.
The optical recording medium of the present invention preferably has a reflectance of 20% or more measured from the substrate side with respect to laser light having a wavelength used for recording / reproduction.
[0070]
There is no particular limitation on the laser used for recording / reproducing, but for example, a dye laser capable of selecting a wavelength in a wide range in the visible region, a helium neon laser having a wavelength of 633 nm, and a recently developed high wavelength around 680, 650, and 635 nm. An output semiconductor laser, a harmonic conversion YAG laser having a wavelength of 532 nm, and the like can be mentioned. A semiconductor laser is preferable in terms of lightness, ease of handling, compactness, cost, and the like. In the present invention, high-density recording and reproduction can be performed at one wavelength or a plurality of wavelengths selected from these.
[0071]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples. However, the examples do not limit the present invention as long as the gist thereof is not exceeded.
Note that ε (molecular extinction coefficient) was calculated on the assumption that a diatomic azo compound was coordinated to one metal atom.
Example 1
(A) Production example
[0072]
Embedded image
In a nitrogen stream, 25.5 g of 2-hydroxyacetanilide represented by the above structural formula (a) (wet crystals, equivalent to 0.15 mol) is dissolved in 200 ml of THF and 250 ml of toluene, and 4.5 g of tetrabutylammonium bromide, 1,2-dibutylethane. 113 g and 24 g sodium hydroxide were added.
After stirring the mixture at 24-25 ° C. for 12 hours, the reaction mixture was poured into 1 liter of water. The mixture was extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and toluene was distilled off to obtain 17.7 g of a brown oil represented by the following structural formula (b).
[0074]
Embedded image
Sodium hydroxide (60 g) was dissolved in a mixed solution of methanol (200 ml) and water (70 ml). Next, a solution of 30 g of the compound represented by the structural formula (b) in 50 ml of methanol was added, and the mixture was stirred at 45 ° C. for 3 hours.
After completion of the reaction, the reaction solution was extracted by adding 250 ml of toluene and 1 l of water, and the obtained toluene layer was washed with water and then dried over anhydrous sodium sulfate. Next, anhydrous sodium sulfate was removed by filtration, and the filtrate was concentrated to obtain 17.3 g of a dark brown oil represented by the following structural formula (c).
[0076]
Embedded image
8.0 g of the compound represented by the structural formula (c) was dissolved in N-methyl-2-pyrrolidone, and 15.24 g of isopropyl iodide and 8.2 g of potassium carbonate were added. The mixture was warmed with stirring and reacted at 80-90 ° C. for 1 hour. After completion of the reaction, 100 ml of toluene and 300 ml of water were added to the reaction solution, extracted, washed with water, dried over anhydrous sodium sulfate and concentrated to obtain 9.5 g of a dark brown oil represented by the following structural formula (d).
[0078]
Embedded image
10.0 g of the compound represented by the structural formula (d) was dissolved in 100 g of concentrated sulfuric acid and cooled. To this mixed solution, a mixed solution of 6.5 g of 60% nitric acid and 25 g of concentrated sulfuric acid was added at 10 ° C. or lower and stirred for 15 minutes. Next, the reaction solution was added to 240 g of ice water, and 163.3 g of 50% sodium hydroxide was added dropwise at 15 ° C. or lower for crystallization. The crystallized crystals were separated by filtration, and the crystals were washed well with water and dried to obtain 10.8 g of orange crystals represented by the following structural formula (e).
[0080]
Embedded image
Suspend 24.5 g of iron powder in 150 ml of DMF-water (2: 1) and heat to 85-90 ° C. with stirring. Then mix 4.0 g of 35% hydrochloric acid and 75 ml of DMF-water (2: 1). The solution was added dropwise. Subsequently, 60 ml of a DMF solution of 10.8 g of the compound represented by the compound (e) was added dropwise over about 15 minutes while maintaining the internal temperature at 80 to 95 ° C. After the dropwise addition, the reaction mixture was stirred at 80 to 95 ° C. for 20 minutes, then 4.9 g of sodium hydrogen carbonate was added while cooling, and stirred for 10 minutes, followed by filtration to remove iron powder, and the filtrate was added to 400 ml of ice water. And extracted with toluene. After drying over anhydrous sodium sulfate, toluene was distilled off to obtain 9.6 g of a brown liquid represented by the following structural formula (f).
[0082]
Embedded image
Under a nitrogen stream, a toluene solution of 9.6 g of the above compound (f) was kept at 5 ° C. or lower while stirring, and 18.6 g of trifluoromethanesulfonic anhydride was added dropwise. After the dropwise addition, the mixture was stirred at 10 to 15 ° C. for 30 minutes and then allowed to stand overnight. Toluene was removed by decantation, and 100 ml of water was added to the remaining solid, followed by extraction with 100 ml of ethyl acetate.
After drying over anhydrous sodium sulfate, ethyl acetate was distilled off to obtain 8.8 g of a dark brown liquid represented by the following structural formula (g).
[0084]
Embedded image
3.42 g of 2-amino-4,5-dicyanoimidazole represented by the following structural formula (h)
[0086]
Embedded image
Was suspended in 100 ml of water and 35% hydrochloric acid was added dropwise at -5 to 10 ° C. Subsequently, a solution of 1.95 g of sodium nitrite and 6.6 g of water was added dropwise at -5 to 5 ° C. to diazotize.
To a solution of 10.0 g of the compound represented by the structural formula (g), 1.02 g of urea and 10.2 g of sodium acetate dissolved in 90 ml of methanol, the diazo solution was added dropwise at −5 to 5 ° C., stirred for 3 hours, and then overnight. I left it alone. The precipitated crystals were collected by filtration and dried to obtain 11.0 g of reddish brown crystals represented by the following structural formula (i).
[0088]
Embedded image
11.0 g of the azo compound represented by the structural formula (i) was dissolved in 220 ml of methanol, 3.9 g of potassium carbonate was added, and the mixture was heated to 40 to 50 ° C. with stirring. At 40 to 50 ° C., 3.55 g of dimethyl sulfate was added dropwise, stirred for 2 hours, and then allowed to cool and crystallize. The precipitated crystals were separated by filtration, washed with methanol, and dried to obtain 7.9 g of red crystals represented by the following structural formula (j).
[0090]
Embedded image
7.9 g of the azo compound represented by the structural formula (j) above was dissolved in 240 ml of THF, and after adding a solution of 2.4 g of nickel acetate tetrahydrate in 50 ml of methanol at room temperature, the mixture was stirred at room temperature for 3 hours, and 240 ml of water was added. . The precipitated crystals were separated by filtration, washed with water and dried to obtain 4.2 g of nickel chelate dye. Λmax (in chloroform) of this compound is 597 nm (ε = 10.5 × 10 Four )Met.
[0092]
(b) Examples of recording media
The nickel chelate dye obtained as described above was dissolved in octafluoropentanol to give 1.1 wt%. This was ultrasonically dispersed at 50 ° C. or lower for 30 minutes, filtered through a 0.2 μm filter, and spin-coated on a 0.6 mm thick polycarbonate substrate at a rotation speed of 800 rpm. The groove width of this substrate is 0.32 μm, and the groove depth is 140 nm (track pitch 0.8 μm). Next, this coating film was dried in an oven at 80 ° C., and then an Ag film having a thickness of 100 nm was formed on the coating film by a sputtering method to form a reflective layer. Further, an ultraviolet curable resin was spin-coated with 3 μm on the reflective layer, and the protective layer was formed by irradiating it with ultraviolet rays to form a recording medium. Further, a hot melt adhesive was applied on the protective layer, and the recording media obtained in exactly the same manner were bonded together to obtain an optical disk. The λmax of the nickel chelate dye coating film (recording layer) was 613.5 nm. The film thickness of the recording layer was 60 nm on the average of lands and grooves.
[0093]
(c) Optical recording method
Using a 657nm semiconductor laser evaluation machine (DDU-1000, manufactured by Pulse Tech Co., Ltd., NA = 0.65), input 8/16 modulation signal with a linear velocity of 3.5m / s, reproduction power of 0.7mW, and shortest mark length of 0.40μm ( 3Ttop pulse width = 1.5 T; where T is the reference clock frequency and 38.2 ns in this example), the recording power is 8.0 mW, and the Itop reflectance (through the polarizing beam splitter in the evaluator is 8/16) Good recording characteristics with a modulation recording portion top (14T reflectivity) of 45% and a modulation degree of 68% were obtained.
Example 2
(a) Production example
[0094]
Embedded image
1.0 g of 3-amino-5-methyl-1,2-isoxazole represented by the above structural formula (k) is dissolved in 10 mL of acetic acid and 5 ml of propionic acid, 1 ml of sulfuric acid is added at 0 to 5 ° C., and 0 to 5 Diazotization was carried out by adding 3.55 g of 43% nitrosylsulfuric acid at ℃.
To a solution obtained by dissolving 4.0 g of the compound represented by the above structural formula (g), 0.4 g of urea, and 4.0 g of sodium acetate in 100 ml of methanol, the diazo solution was added dropwise at −5 to 5 ° C., stirred for 3 hours, and then overnight. I left it alone. The precipitated crystals were collected by filtration and dried to obtain 2.23 g of reddish brown crystals represented by the following structural formula (l).
[0096]
Embedded image
Dissolve 2.1 g of the azo compound represented by the above structural formula (l) in 20 ml of methanol, add 0.72 g of nickel acetate tetrahydrate in 15 ml of methanol at room temperature, then stir at room temperature for 3 hours, add 20 ml of water. It was. The precipitated crystals were separated by filtration, washed with water and methanol, and dried to obtain 2.0 g of nickel chelate dye. The λmax (in chloroform) of this dye is 568 nm (ε = 5.7 × 10 Four )Met.
[0098]
(b) Examples of recording media
An optical disk was prepared in the same manner as in Example 1 using the nickel chelate dye obtained as described above. The coating film had a λmax of 586 nm. The average film thickness of the recording layer was about 80 nm.
[0099]
(c) Optical recording method
When recording was performed in the same manner as in Example 1, good recording characteristics with a recording power of 11 mW, an Itop reflectance of 51%, and a modulation degree of 68% were obtained.
[0100]
【The invention's effect】
By using the metal chelate dye of the present invention, it is possible to provide an optical recording medium suitable for high-speed recording and excellent in light resistance because of its high sensitivity to recording at a relatively short wavelength.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33975699A JP3972544B2 (en) | 1999-11-30 | 1999-11-30 | Metal chelate dye and optical recording medium using the metal chelate dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33975699A JP3972544B2 (en) | 1999-11-30 | 1999-11-30 | Metal chelate dye and optical recording medium using the metal chelate dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001152040A JP2001152040A (en) | 2001-06-05 |
| JP3972544B2 true JP3972544B2 (en) | 2007-09-05 |
Family
ID=18330518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33975699A Expired - Fee Related JP3972544B2 (en) | 1999-11-30 | 1999-11-30 | Metal chelate dye and optical recording medium using the metal chelate dye |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3972544B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003276342A (en) | 2002-03-26 | 2003-09-30 | Tdk Corp | Optical recording medium |
| JP4481000B2 (en) * | 2003-12-25 | 2010-06-16 | 三菱化学メディア株式会社 | Azo metal chelate dye and optical recording medium |
| DE102004034866A1 (en) * | 2004-07-19 | 2006-02-16 | Lanxess Deutschland Gmbh | Mixtures of azo metal complexes as light-absorbing compounds in the information layer of optical data media |
-
1999
- 1999-11-30 JP JP33975699A patent/JP3972544B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001152040A (en) | 2001-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3438587B2 (en) | Optical recording medium | |
| JP3641874B2 (en) | Optical recording medium and recording method | |
| JP4818000B2 (en) | Optical recording medium and metal complex compound. | |
| US6284877B1 (en) | Sulfonamide compound and method for its production, metal chelate compound employing the sulfonamide compound, and optical recording medium employing the metal chelate compound | |
| WO1991018057A1 (en) | Metal chelate compound and optical recording medium prepared therefrom | |
| EP1903561A1 (en) | Optical recording medium, optical recording material and metal complex compound | |
| JP4078773B2 (en) | Metal chelate dye and optical recording medium using the dye | |
| JP4178783B2 (en) | Optical recording medium | |
| EP0844243A1 (en) | Sulfonamide compound and method for its production, metal chelate compound employing the sulfonamide compound, and optical recording medium employing the metal chelate compound | |
| JP3680428B2 (en) | Metal chelate compound and optical recording medium using the metal chelate compound | |
| JPH11310728A (en) | Azo metal chelate dye and optical recording medium using this dye | |
| JPH11130970A (en) | Metal-containing azo compound and optical recording medium using the compound | |
| JPH08295811A (en) | Metal chelate compound and optical recording medium using the same | |
| EP0477373B1 (en) | Metal chelate compound and optical recording medium comprising the same | |
| JP2001214084A (en) | Metal chelate dye and optical recording medium using the same | |
| JP3972544B2 (en) | Metal chelate dye and optical recording medium using the metal chelate dye | |
| JP4519795B2 (en) | Optical recording medium and metal complex compound | |
| JP3219037B2 (en) | Metal chelate compound and optical recording medium using the metal chelate compound | |
| JP3933864B2 (en) | Azo metal chelate dye and optical recording medium using the same | |
| JP4523366B2 (en) | Azo metal chelate dye and optical recording medium | |
| JP3876970B2 (en) | Dye for recording layer formation of optical recording medium, optical recording medium using the same, and recording method of optical recording medium | |
| JP4540803B2 (en) | Metal-containing azo compound and optical recording medium using the compound | |
| JP4481000B2 (en) | Azo metal chelate dye and optical recording medium | |
| JP4158553B2 (en) | Optical recording method | |
| JPH0751673B2 (en) | Metal chelate compound and optical recording medium using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070125 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070213 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070329 |
|
| 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: 20070522 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070604 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100622 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100622 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |