JP2008266546A - Novel azo compound and azo dye - Google Patents
Novel azo compound and azo dye Download PDFInfo
- Publication number
- JP2008266546A JP2008266546A JP2007134786A JP2007134786A JP2008266546A JP 2008266546 A JP2008266546 A JP 2008266546A JP 2007134786 A JP2007134786 A JP 2007134786A JP 2007134786 A JP2007134786 A JP 2007134786A JP 2008266546 A JP2008266546 A JP 2008266546A
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- JP
- Japan
- Prior art keywords
- group
- ring
- azo
- general formula
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- -1 azo compound Chemical class 0.000 title claims abstract description 127
- 239000000987 azo dye Substances 0.000 title claims abstract description 16
- 125000001424 substituent group Chemical group 0.000 claims abstract description 51
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 50
- 125000003118 aryl group Chemical group 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims abstract description 19
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims description 49
- 125000000623 heterocyclic group Chemical group 0.000 claims description 27
- 125000001072 heteroaryl group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 13
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 125000001931 aliphatic group Chemical group 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- 150000001721 carbon Chemical group 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000000975 dye Substances 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 125000003277 amino group Chemical group 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- 125000004442 acylamino group Chemical group 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000001769 aryl amino group Chemical group 0.000 description 4
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 3
- 125000005110 aryl thio group Chemical group 0.000 description 3
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- 238000001454 recorded image Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 3
- 125000004149 thio group Chemical group *S* 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 125000005421 aryl sulfonamido group Chemical group 0.000 description 2
- 238000006149 azo coupling reaction Methods 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- GQVCNZBQZKXBMX-UHFFFAOYSA-N butan-2-one;toluene Chemical compound CCC(C)=O.CC1=CC=CC=C1 GQVCNZBQZKXBMX-UHFFFAOYSA-N 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 2
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical group C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical group C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- QEIQICVPDMCDHG-UHFFFAOYSA-N pyrrolo[2,3-d]triazole Chemical compound N1=NC2=CC=NC2=N1 QEIQICVPDMCDHG-UHFFFAOYSA-N 0.000 description 2
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229960000581 salicylamide Drugs 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- KLMVOCFYZRCHEK-UHFFFAOYSA-N (3-nitrophenyl)hydrazine;sulfuric acid Chemical compound OS(O)(=O)=O.NNC1=CC=CC([N+]([O-])=O)=C1 KLMVOCFYZRCHEK-UHFFFAOYSA-N 0.000 description 1
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- SLLFVLKNXABYGI-UHFFFAOYSA-N 1,2,3-benzoxadiazole Chemical group C1=CC=C2ON=NC2=C1 SLLFVLKNXABYGI-UHFFFAOYSA-N 0.000 description 1
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical group C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical group N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 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
- RPEPGIOVXBBUMJ-UHFFFAOYSA-N 2,3-difluorophenol Chemical compound OC1=CC=CC(F)=C1F RPEPGIOVXBBUMJ-UHFFFAOYSA-N 0.000 description 1
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
- INXKVYFOWNAVMU-UHFFFAOYSA-N 2,5-difluorophenol Chemical group OC1=CC(F)=CC=C1F INXKVYFOWNAVMU-UHFFFAOYSA-N 0.000 description 1
- OEICGMPRFOJHKO-UHFFFAOYSA-N 2-(ethoxymethylidene)propanedinitrile Chemical compound CCOC=C(C#N)C#N OEICGMPRFOJHKO-UHFFFAOYSA-N 0.000 description 1
- 125000004174 2-benzimidazolyl group Chemical group [H]N1C(*)=NC2=C([H])C([H])=C([H])C([H])=C12 0.000 description 1
- UXGVMFHEKMGWMA-UHFFFAOYSA-N 2-benzofuran Chemical group C1=CC=CC2=COC=C21 UXGVMFHEKMGWMA-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- MOXDGMSQFFMNHA-UHFFFAOYSA-N 2-hydroxybenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1O MOXDGMSQFFMNHA-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical group O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- QMEQBOSUJUOXMX-UHFFFAOYSA-N 2h-oxadiazine Chemical group N1OC=CC=N1 QMEQBOSUJUOXMX-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical group NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- ATVDXYLNGKFYDC-UHFFFAOYSA-N FC1=C(C=CC=C1)O.C1SC=CS1 Chemical compound FC1=C(C=CC=C1)O.C1SC=CS1 ATVDXYLNGKFYDC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical group C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- JZFICWYCTCCINF-UHFFFAOYSA-N Thiadiazin Chemical group S=C1SC(C)NC(C)N1CCN1C(=S)SC(C)NC1C JZFICWYCTCCINF-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 125000005135 aryl sulfinyl group Chemical group 0.000 description 1
- 125000004657 aryl sulfonyl amino group Chemical group 0.000 description 1
- 125000005279 aryl sulfonyloxy group Chemical group 0.000 description 1
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 1
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
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- 230000000740 bleeding effect Effects 0.000 description 1
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- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
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- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
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- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
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- ACFLGFAYAGXMJV-UHFFFAOYSA-N n-[5-(benzenesulfonamido)-1-hydroxynaphthalen-2-yl]propanamide Chemical compound C=1C=CC2=C(O)C(NC(=O)CC)=CC=C2C=1NS(=O)(=O)C1=CC=CC=C1 ACFLGFAYAGXMJV-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- CQDAMYNQINDRQC-UHFFFAOYSA-N oxatriazole Chemical group C1=NN=NO1 CQDAMYNQINDRQC-UHFFFAOYSA-N 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- GJSGGHOYGKMUPT-UHFFFAOYSA-N phenoxathiine Chemical group C1=CC=C2OC3=CC=CC=C3SC2=C1 GJSGGHOYGKMUPT-UHFFFAOYSA-N 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
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- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 125000004585 polycyclic heterocycle group Chemical group 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
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- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- DWJMBQYORXLGAE-UHFFFAOYSA-N pyridine-2-sulfonamide Chemical group NS(=O)(=O)C1=CC=CC=N1 DWJMBQYORXLGAE-UHFFFAOYSA-N 0.000 description 1
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical group C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- YGNGABUJMXJPIJ-UHFFFAOYSA-N thiatriazole Chemical group C1=NN=NS1 YGNGABUJMXJPIJ-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical group CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
本発明はアゾ化合物及びアゾ色素に関する。さらに詳しくは、本発明は着色剤として好適に使用しうるアゾ化合物及びアゾ色素に関する。 The present invention relates to an azo compound and an azo dye. More specifically, the present invention relates to an azo compound and an azo dye that can be suitably used as a colorant.
アゾ色素は、活性水素を持った化合物やフェノール類またはｐ−ジアルキルアミノベンゼン類等のいわゆるカプラー成分と、アミノアリール化合物またはアミノヘテロ芳香族化合物（いわゆるジアゾ成分）から調製されたジアゾニウム塩とをアゾカップリングさせて形成させた色素で、様々な構造のカプラー成分とアゾ成分とを選択できるため、その色調が多岐に渡り、色素の中でも代表的なものである。
アゾ色素は、またその高い染色性、熱や光及び洗濯に対する堅牢性、及び低い製造コストなど優れた性質を数多く有している為、古くから、多様な製品の着色剤として広く使用されてきた。今日では、染色などの伝統的な着色用途に加え、ディスプレイ用部材などの先端画像関連機器にも応用されており、幅広い範囲で使用されている（非特許文献１参照）。
An azo dye comprises an active hydrogen-containing compound, a so-called coupler component such as phenols or p-dialkylaminobenzenes, and a diazonium salt prepared from an aminoaryl compound or aminoheteroaromatic compound (so-called diazo component). Since the dye formed by ring can select a coupler component and an azo component having various structures, the color tone varies widely and is representative among the dyes.
Azo dyes have long been widely used as a colorant for various products because they have many excellent properties such as high dyeability, fastness to heat, light and washing, and low production costs. . Today, in addition to traditional coloring applications such as dyeing, it is also applied to advanced image-related equipment such as display members and is used in a wide range (see Non-Patent Document 1).
近年、画像記録材料としてカラー画像が主流となり、上述の様に色素の使用用途も多様化してきた。これらのカラー画像記録材料やカラーフィルターでは、フルカラー画像を再現あるいは記録するために、いわゆる加法混色法や減法混色法の３原色の着色剤（染料や顔料）が使用されている。しかし、好ましい色再現域を実現できる吸収特性を有し、且つさまざまな使用条件、環境条件に耐えうる、色相が良く堅牢な着色剤が無いのが現状であり、改善が強く望まれている。
これら各用途で使用する着色剤には、色再現上所望の吸収特性を有すること、使用される環境条件化での堅牢性、モル吸光係数が大きいこと等が要求される。
In recent years, color images have become mainstream as image recording materials, and the use of dyes has also diversified as described above. In these color image recording materials and color filters, three primary colorants (dyes and pigments) of so-called additive color mixing and subtractive color mixing are used to reproduce or record full color images. However, the present situation is that there is no colorant that has an absorption characteristic capable of realizing a preferable color gamut, can withstand various use conditions and environmental conditions, has a good hue, and is robust, and improvement is strongly desired.
The colorant used in each of these uses is required to have desired absorption characteristics for color reproduction, fastness under the environmental conditions used, and a large molar extinction coefficient.
他方、環内にアゾ基を有する新規ヘテロ環化合物については１，１０−ヘテロジ置換ベンゾ［ｃ］シノリン誘導体の合成が報告されているが、環形成反応のメカニズムおよび構造化学的な議論を中心とするものであった（非特許文献２参照）。 On the other hand, the synthesis of 1,10-heterodisubstituted benzo [c] cinoline derivatives has been reported for novel heterocyclic compounds having an azo group in the ring. (See Non-Patent Document 2).
本発明は、鮮明で色濃度が高く、熱及び光などに対する堅牢性に優れ、十分な染着性及び移行性を有する新規なアゾ化合物及びアゾ色素の提供を目的とする。 An object of the present invention is to provide a novel azo compound and an azo dye having a clear and high color density, excellent fastness to heat and light, and sufficient dyeability and migration.
上記の目的は以下の手段により達成された。 The above object has been achieved by the following means.
（１）下記一般式（１）で表されるアゾ化合物。
（２）上記一般式（１）で表される化合物が下記一般式（２）で表されることを特徴とする（１）記載のアゾ化合物。
（３）上記一般式（１）または（２）で表される化合物が下記一般式（３）で表されることを特徴とする（１）または（２）記載のアゾ化合物。
（４）上記一般式（１）または（２）で表される化合物が下記一般式（４）で表されることを特徴とする（１）または（２）記載のアゾ化合物。
（５）前記カプラー成分Ｒが下記一般式（５）で表されることを特徴とする（１）〜（４）のいずれか１項に記載のアゾ化合物。
（６）（１）〜（５）のいずれか１項に記載のアゾ化合物からなるアゾ色素。
(1) An azo compound represented by the following general formula (1).
(2) The azo compound according to (1), wherein the compound represented by the general formula (1) is represented by the following general formula (2).
(3) The azo compound according to (1) or (2), wherein the compound represented by the general formula (1) or (2) is represented by the following general formula (3).
(4) The azo compound according to (1) or (2), wherein the compound represented by the general formula (1) or (2) is represented by the following general formula (4).
(5) The azo compound according to any one of (1) to (4), wherein the coupler component R is represented by the following general formula (5).
(6) An azo dye comprising the azo compound according to any one of (1) to (5).
本発明のアゾ化合物及びアゾ色素は、鮮明で高い色濃度を示し、光や熱等に対して十分な堅牢性を発揮するという優れた効果を奏する。また、本発明のアゾ化合物及びアゾ色素は染料ないし着色剤として好適に用いることができ、十分な染着性及び転写画像形成における十分な転写移行性を有し、高い分光吸収係数を有する。 The azo compound and the azo dye of the present invention exhibit an excellent effect of showing a clear and high color density and exhibiting sufficient fastness to light, heat and the like. The azo compounds and azo dyes of the present invention can be suitably used as dyes or colorants, have sufficient dyeability, sufficient transfer migration in transfer image formation, and have a high spectral absorption coefficient.
以下に本発明について詳細に説明する。
本発明のアゾ化合物は下記一般式（１）で表される。
The azo compound of the present invention is represented by the following general formula (1).
ここでＶ１、Ｖ２、又は後述するＶ３が表す置換基とは、それぞれ芳香環及び複素芳香環のいずれかの水素原子に対して置換可能な基を意味する。このような置換基としては、例えば、脂肪族炭化水素基（好ましくは炭素原子数１〜１５の基、例えばメチル基、エチル基、プロピル基、イソプロピル基、プロパルギル基、ビニル基等）、アリール基（好ましくは炭素原子数６〜１６の基、例えばフェニル基、４−ニトロフェニル基、２，４−ジクロロフェニル基等）、ヘテロ環基（好ましくは５〜１０員環の基、例えば２−テトラヒドロフリル基、２−ピリジル基、ピリミジン−２−イル基、１−イミダゾリル基、１−ピラゾリル基、２−ピロリル基、ベンゾチアゾール−２−イル基、ベンゾイミダゾール−２−イル基等）、アシル基（好ましくは炭素原子数１〜１５、例えばアセチル基、２−メチルプロパノイル基、ピバロイル基、ベンゾイル基等）、アシルオキシ基（好ましくは炭素原子数１〜１６の基、例えばアセトキシ基、プロパノイルオキシ基、ベンゾイルオキシ基等）、アシルアミノ基（好ましくは炭素原子数１〜８の基、例えばアセチルアミノ基、プロピオニルアミノ基、２−メチルプロパノイルアミノ基、クロロアセチルアミノ基、ベンズアミド基等）、脂肪族オキシ基（好ましくは炭素原子数１〜１６の基、例えばメトキシ基、エトキシ基、ブトキシ基、２−メトキシエトキシ基等）、アリールオキシ基（好ましくは炭素原子数６〜１７の基、例えばフェノキシ基、４−ニトロフェノキシ基等）、ヘテロ環オキシ基（好ましくは５〜１０員環の基、例えば２−ピリジルオキシ基、２−フリルオキシ基、３−ピラゾイルオキシ基等）、脂肪族オキシカルボニル基（好ましくは炭素原子数１〜１５の基、例えばメトキシカルボニル基、２−プロピルオキシカルボニル基、ブトキシカルボニル基等）、アリールオキシカルボニル基（好ましくは炭素原子数７〜１７の基、例えばフェノキシカルボニル基、４−メトキシフェノキシカルボニル基等）、ヘテロ環オキシカルボニル基（好ましくは５〜１０員環の基、例えば２−ピリジルオキシカルボニル基、２−チエニルオキシカルボニル基等）、カルバモイル基（好ましくは炭素原子数１〜１２の基、例えばカルバモイル基、Ｎ−エチルカルバモイル基、Ｎ，Ｎ−ジメチルカルバモイル基等）、脂肪族スルホニル基（好ましくは炭素原子数１〜１５の基、例えばメタンスルホニル基、ブタンスルホニル基、メトキシエタンスルホニル基等）、アリールスルホニル基（好ましくは炭素原子数６〜１６の基、例えばフェニルスルホニル基、４−ｔ−ブチルフェニルスルホニル基、ｐ−トルエンスルホニル基等）、ヘテロ環スルホニル基（好ましくは５〜１０員環の基、例えば２−テトラヒドロピラニルスルホニル基等）、脂肪族スルホニルオキシ基（好ましくは炭素原子数１〜１５の基、例えばメタンスルホニルオキシ基、エタンスルホニルオキシ基等）、アリールスルホニルオキシ基（好ましくは炭素原子数６〜１６の基、例えばフェニルスルホニルオキシ基等）、ヘテロ環スルホニルオキシ基（好ましくは５〜１０員環の基、例えば２−ピリジルスルホニルオキシ基等）、スルファモイル基（好ましくは炭素原子数０〜１２の基、例えばスルファモイル基、Ｎ，Ｎ−ジメチルスルファモイル基等）、脂肪族スルホンアミド基（好ましくは炭素原子数１〜１５の基、例えばメタンスルホンアミド基、ブタンスルホンアミド基等）、アリールスルホンアミド基（好ましくは炭素原子数６〜１６の基、例えばベンゼンスルホンアミド基、ｐ−トルエンスルホンアミド基等）、ヘテロ環スルホンアミド基（５〜１０員環の基、例えば２−ピリジルスルホニルアミド基等）、アミノ基、脂肪族アミノ基（好ましくは炭素原子数１〜１６の基、例えばメチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、ブチルアミノ基等）、アリールアミノ基（好ましくは炭素原子数６〜１６の基、例えばフェニルアミノ基等）、ヘテロ環アミノ基（５〜１０員環の基、例えば２−ピリジルアミノ基、ピラゾール−４−イルアミノ基、ベンゾイミダゾール−２−イルアミノ基、ベンゾチアゾール−２−イルアミノ基、ベンゾオキサゾール−２−イルアミノ基、２−オキサゾリルアミノ基、１，２，４−トリアゾール−３−イルアミノ基、１，２，４−チアジアゾール−２−イルアミノ基、１，３，４−チアジアゾール−２−イルアミノ基、１，２，４−オキサジアゾール−２−イルアミノ基、１，３，４−オキサジアゾール−２−イルアミノ基等）、脂肪族オキシカルボニルアミノ基（好ましくは炭素原子数２〜１２の基、例えばメトキシカルボニルアミノ基、エトキシカルボニルアミノ基、ｔ−ブトキシカルボニルアミノ基等）、アリールオキシカルボニルアミノ基（好ましくは炭素原子数７〜１７の基、例えばフェノキシカルボニルアミノ基等）、ヘテロ環オキシカルボニルアミノ基（５〜１０員環の基、例えば２−ピリジルオキシカルボニルアミノ基等）：脂肪族スルフィニル基（好ましくは炭素原子数１〜１２の基、例えばメチルスルフィニル基、ブチルスルフィニル基等）、アリールスルフィニル基（好ましくは炭素原子数６〜１６の基、例えばフェニルスルフィニル基等）、脂肪族チオ基（好ましくは炭素原子数１〜１８の基、例えばメチルチオ基、エチルチオ基、２−エトキシエチルチオ基、ブチルチオ基等）、アリールチオ基（好ましくは炭素原子数６〜１８の基、例えばフェニルチオ基等）、脂肪族オキシアミノ基（好ましくは炭素原子数１〜１２の基、例えばメトキシアミノ基、ブトキシアミノ基等）、アリールオキシアミノ基（好ましくは炭素原子数６〜１６の基、例えばフェノキシアミノ基等）、カルバモイルアミノ基（好ましくは炭素原子数０〜１８の基、例えばカルバモイルアミノ基等）、スルファモイルアミノ基（好ましくは炭素原子数０〜１８の基、例えばスルファモイルアミノ基、Ｎ，Ｎ−ジメチルスルファモイルアミノ基等）、スルファモイルカルバモイル基（好ましくは炭素原子数１〜１２の基、例えばＮ−（スルファモイル）カルバモイル基、Ｎ−（Ｎ’，Ｎ’−ジメチルスルファモイル）カルバモイル基等）、カルバモイルスルファモイル基（好ましくは炭素原子数１〜１２の基、例えばＮ−（カルバモイル）スルファモイル基等）、ジ脂肪族オキシホスフィニル基（好ましくは炭素原子数２〜１６の基、例えばジメトキシホスホニル基等）、ジアリールオキシホスフィニル基（好ましくは炭素原子数６〜１６の基、例えばフェノキシホスフィニル基）、ヒドロキシ基；メルカプト基；シアノ基；ハロゲン原子等が含まれる。 Here, the substituent represented by V 1 , V 2 , or V 3 described later means a group that can be substituted with respect to any hydrogen atom of an aromatic ring or a heteroaromatic ring. Examples of such a substituent include an aliphatic hydrocarbon group (preferably a group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a propargyl group, a vinyl group), an aryl group. (Preferably a group having 6 to 16 carbon atoms, such as phenyl group, 4-nitrophenyl group, 2,4-dichlorophenyl group, etc.), heterocyclic group (preferably a 5- to 10-membered ring group such as 2-tetrahydrofuryl) Group, 2-pyridyl group, pyrimidin-2-yl group, 1-imidazolyl group, 1-pyrazolyl group, 2-pyrrolyl group, benzothiazol-2-yl group, benzimidazol-2-yl group, etc.), acyl group ( Preferably having 1 to 15 carbon atoms, such as acetyl, 2-methylpropanoyl, pivaloyl, benzoyl, etc.), acyloxy groups (preferably carbon 1 to 16 groups such as acetoxy group, propanoyloxy group, benzoyloxy group and the like, acylamino group (preferably 1 to 8 carbon atoms such as acetylamino group, propionylamino group, 2-methylpropano group) Noylamino group, chloroacetylamino group, benzamide group, etc.), aliphatic oxy group (preferably a group having 1 to 16 carbon atoms such as methoxy group, ethoxy group, butoxy group, 2-methoxyethoxy group, etc.), aryloxy A group (preferably a group having 6 to 17 carbon atoms, such as a phenoxy group or a 4-nitrophenoxy group), a heterocyclic oxy group (preferably a 5- to 10-membered ring group such as a 2-pyridyloxy group, 2-furyl) Oxy group, 3-pyrazoyloxy group, etc.), aliphatic oxycarbonyl group (preferably a group having 1 to 15 carbon atoms, such as Xycarbonyl group, 2-propyloxycarbonyl group, butoxycarbonyl group, etc.), aryloxycarbonyl group (preferably a group having 7 to 17 carbon atoms such as phenoxycarbonyl group, 4-methoxyphenoxycarbonyl group, etc.), heterocyclic oxy A carbonyl group (preferably a 5- to 10-membered ring group such as 2-pyridyloxycarbonyl group or 2-thienyloxycarbonyl group), a carbamoyl group (preferably a group having 1 to 12 carbon atoms such as carbamoyl group, N- Ethylcarbamoyl group, N, N-dimethylcarbamoyl group, etc.), aliphatic sulfonyl group (preferably a group having 1 to 15 carbon atoms such as methanesulfonyl group, butanesulfonyl group, methoxyethanesulfonyl group, etc.), arylsulfonyl group ( Preferably a group having 6 to 16 carbon atoms, for example Phenylsulfonyl group, 4-t-butylphenylsulfonyl group, p-toluenesulfonyl group, etc.), heterocyclic sulfonyl group (preferably a 5- to 10-membered ring group such as 2-tetrahydropyranylsulfonyl group, etc.), aliphatic sulfonyl An oxy group (preferably a group having 1 to 15 carbon atoms, such as a methanesulfonyloxy group, an ethanesulfonyloxy group), an arylsulfonyloxy group (preferably a group having 6 to 16 carbon atoms, such as a phenylsulfonyloxy group). A heterocyclic sulfonyloxy group (preferably a 5- to 10-membered ring group such as a 2-pyridylsulfonyloxy group), a sulfamoyl group (preferably a group having 0 to 12 carbon atoms such as a sulfamoyl group, N, N-dimethyl) Sulfamoyl group, etc.), aliphatic sulfonamide group (preferably 1 carbon atom) 15 groups such as methanesulfonamide group and butanesulfonamide group), arylsulfonamide groups (preferably groups having 6 to 16 carbon atoms such as benzenesulfonamide group and p-toluenesulfonamide group), heterocyclic ring Sulfonamide group (5- to 10-membered ring group such as 2-pyridylsulfonylamide group), amino group, aliphatic amino group (preferably a group having 1 to 16 carbon atoms such as methylamino group, N, N- A diethylamino group, a butylamino group and the like), an arylamino group (preferably a group having 6 to 16 carbon atoms, such as a phenylamino group), a heterocyclic amino group (a group having 5 to 10 members, such as a 2-pyridylamino group, Pyrazol-4-ylamino group, benzoimidazol-2-ylamino group, benzothiazol-2-ylamino group, benzoo Sazol-2-ylamino group, 2-oxazolylamino group, 1,2,4-triazol-3-ylamino group, 1,2,4-thiadiazol-2-ylamino group, 1,3,4-thiadiazole-2 -Ylamino group, 1,2,4-oxadiazol-2-ylamino group, 1,3,4-oxadiazol-2-ylamino group and the like, aliphatic oxycarbonylamino group (preferably having 2 to 2 carbon atoms) 12 groups such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, etc., an aryloxycarbonylamino group (preferably a group having 7 to 17 carbon atoms such as a phenoxycarbonylamino group), hetero Ring oxycarbonylamino group (5- to 10-membered ring group such as 2-pyridyloxycarbonylamino group): Fatty Group sulfinyl group (preferably a group having 1 to 12 carbon atoms, such as methylsulfinyl group, butylsulfinyl group, etc.), arylsulfinyl group (preferably a group having 6 to 16 carbon atoms, such as phenylsulfinyl group), aliphatic Thio group (preferably a group having 1 to 18 carbon atoms such as methylthio group, ethylthio group, 2-ethoxyethylthio group, butylthio group, etc.), arylthio group (preferably a group having 6 to 18 carbon atoms such as phenylthio group) Etc.), an aliphatic oxyamino group (preferably a group having 1 to 12 carbon atoms, such as methoxyamino group, butoxyamino group, etc.), an aryloxyamino group (preferably a group having 6 to 16 carbon atoms, such as phenoxyamino) Group), a carbamoylamino group (preferably a group having 0 to 18 carbon atoms, such as carbamoyl group). Sulfamoylamino group (preferably a group having 0 to 18 carbon atoms such as sulfamoylamino group, N, N-dimethylsulfamoylamino group, etc.), sulfamoylcarbamoyl group (preferably A group having 1 to 12 carbon atoms, such as an N- (sulfamoyl) carbamoyl group, N- (N ′, N′-dimethylsulfamoyl) carbamoyl group, etc.), a carbamoylsulfamoyl group (preferably having 1 to 1 carbon atoms) 12 groups such as N- (carbamoyl) sulfamoyl group), dialiphatic oxyphosphinyl groups (preferably groups having 2 to 16 carbon atoms such as dimethoxyphosphonyl group), diaryloxyphosphinyl groups ( Preferably a group having 6 to 16 carbon atoms, such as a phenoxyphosphinyl group), a hydroxy group; a mercapto group; a cyano group; a halogen Includes atoms.
Ｖ１、Ｖ２、又はＶ３が表す置換基としては、なかでも、脂肪族基、アリール基、ハロゲン原子、シアノ基、カルバモイル基、スルファモイル基、アルキルスルホニル基、アリールスルホニル基、又はアシルアミノ基が好ましい。脂肪族基の具体例としては、メチル、エチル、又はｔｅｒｔ−ブチル基が好ましく、メチル基又はエチル基がより好ましい。アリール基の具体例としては、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。ハロゲン原子としてはクロロ原子又はフッ素原子が好ましい。カルバモイル基又はスルファモイル基としては無置換のものが特に好ましい。アルキルスルホニル基としては、メチルスルホニル基又はエチルスルホニル基が好ましい。アリールスルホニル基としてはフェニルスルホニル基又はトシルスルホニル基が好ましい。アシルアミノ基としてはアセチルアミノ基又はプロピオニルアミノ基が好ましい。 Examples of the substituent represented by V 1 , V 2 , or V 3 include an aliphatic group, an aryl group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or an acylamino group. preferable. As specific examples of the aliphatic group, a methyl, ethyl, or tert-butyl group is preferable, and a methyl group or an ethyl group is more preferable. As a specific example of the aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. As the halogen atom, a chloro atom or a fluorine atom is preferable. As the carbamoyl group or sulfamoyl group, an unsubstituted group is particularly preferable. As the alkylsulfonyl group, a methylsulfonyl group or an ethylsulfonyl group is preferable. The arylsulfonyl group is preferably a phenylsulfonyl group or a tosylsulfonyl group. The acylamino group is preferably an acetylamino group or a propionylamino group.
上記の置換基Ｖ１、Ｖ２、又はＶ３の中で、水素原子を有するものは、これを取り去り更に上記の基でさらに置換されていてもよい。そのような、さらなる置換基の例としては、−ＣＯＮＨＳＯ２−基（スルホニルカルバモイル基、カルボニルスルファモイル基）、−ＣＯＮＨＣＯ−基（カルボニルカルバモイル基）、−ＳＯ２ＮＨＳＯ２−基（スルフォニルスルファモイル基）、が挙げられる。より具体的には、アルキルカルボニルアミノスルホニル基（例えば、アセチルアミノスルホニル）、アリールカルボニルアミノスルホニル基（例えば、ベンゾイルアミノスルホニル基）、アルキルスルホニルアミノカルボニル基（例えば、メチルスルホニルアミノカルボニル）、アリールスルホニルアミノカルボニル基（例えば、ｐ−メチルフェニルスルホニルアミノカルボニル）が挙げられる。 Among the above substituents V 1 , V 2 , or V 3 , those having a hydrogen atom may be further substituted with the above group after removing this. Examples of such further substituents include —CONHSO 2 — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO 2 NHSO 2 — group (sulfonylsulfuryl group). Moyl group). More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.
Ｚ１によって形成される芳香環（以下、芳香族炭素環ということもある。）としては、ベンゼン環、ナフタレン環、アントラセン、又はフェナントレン、あるいは以下に説明する芳香族複素環が縮環したベンゼン環などが挙げられる。
Ｚ１によって形成される芳香族炭素環としてはベンゼン環、ベンゾチアゾール環、ベンゾイミダゾール環が好ましく、特にベンゼン環が好ましい。
Ｚ１又はＺ２によって形成される複素芳香環（以下、芳香族複素環ということもある。）としては５、６、７、または８員の芳香族ヘテロ環などが挙げられる。
Ｚ１又はＺ２によって形成される芳香族複素環として好ましくは５又は６員の含窒素複素環である。５又は６員の含窒素ヘテロ環としては、如何なる含窒素複素環でもよく、更にベンゼン環や他の複素環が縮環して多環複素環構造をとっていてもよい。
The aromatic ring formed by Z 1 (hereinafter sometimes referred to as an aromatic carbocycle) is a benzene ring, naphthalene ring, anthracene, or phenanthrene, or a benzene ring condensed with an aromatic heterocycle described below. Etc.
As the aromatic carbocycle formed by Z 1 , a benzene ring, a benzothiazole ring and a benzimidazole ring are preferable, and a benzene ring is particularly preferable.
Examples of the heteroaromatic ring formed by Z 1 or Z 2 (hereinafter sometimes referred to as “aromatic heterocycle”) include 5-, 6-, 7- or 8-membered aromatic heterocycles.
The aromatic heterocycle formed by Z 1 or Z 2 is preferably a 5- or 6-membered nitrogen-containing heterocycle. The 5- or 6-membered nitrogen-containing heterocycle may be any nitrogen-containing heterocycle, and a benzene ring or other heterocycle may be condensed to form a polycyclic heterocycle structure.
Ｚ１又はＺ２によって形成される芳香族複素環に含まれるヘテロ原子として好ましくは、窒素原子、硫黄原子、酸素原子、セレン原子、テルル原子、リン原子、ケイ素原子、又はホウ素原子であり、より好ましくは、窒素原子、硫黄原子、酸素原子、又はセレン原子であり、さらに好ましくは、窒素原子、硫黄原子、又は酸素原子であり、特に好ましくは窒素原子又は硫黄原子である。 The hetero atom contained in the aromatic heterocycle formed by Z 1 or Z 2 is preferably a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, or a boron atom, and more A nitrogen atom, a sulfur atom, an oxygen atom, or a selenium atom is preferable, a nitrogen atom, a sulfur atom, or an oxygen atom is more preferable, and a nitrogen atom or a sulfur atom is particularly preferable.
これらの芳香族複素環として好ましいものは具体的には、フラン環、ピロール環、チオフェン環、イミダゾール環、ピラゾール環、チアゾール環、イソチアゾール環、オキサゾール環、イソオキサゾール環、トリアゾール環、テトラゾール環、チアジアゾール環、オキサジアゾール環、ピラン環、ジオキサン環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、チアジアジン環、オキサジアジン環、オキサトリアゾール環、チアトリアゾール環、インドリジン環、及び、これらにベンゾ縮環したベンゾチアゾール環、ベンゾオキサゾール環、ベンゾトリアゾール環、ベンゾチアジアゾール環、ベンゾオキサジアゾール環、ピラノン環、ピリリウム環、トリアジン環、テトラジン環、インドール環、キノリジン環、キノリン環、フタラジン環、キノキサリン環、イソキノリン環、カルバゾール環、フェナントリジン環、フェナントロリン環、アクリジン環、及び、プリン、プテリジン等が挙げられる。なかでも、ピリジン環、ピラゾール環、イソチアゾール環、イミダゾール環、チアゾール環が好ましい。 Specifically preferred as these aromatic heterocycles are furan ring, pyrrole ring, thiophene ring, imidazole ring, pyrazole ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, triazole ring, tetrazole ring, Thiadiazole ring, oxadiazole ring, pyran ring, dioxane ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, thiadiazine ring, oxadiazine ring, oxatriazole ring, thiatriazole ring, indolizine ring, and benzo condensed Ringed benzothiazole ring, benzoxazole ring, benzotriazole ring, benzothiadiazole ring, benzooxadiazole ring, pyranone ring, pyrylium ring, triazine ring, tetrazine ring, indole ring, quinolidine ring, quinoline ring, phthala Down ring, a quinoxaline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, a phenanthroline ring, an acridine ring, and, purine, pteridine and the like. Of these, a pyridine ring, a pyrazole ring, an isothiazole ring, an imidazole ring, and a thiazole ring are preferable.
これらの複素環には、いかなる置換基が置換していても縮環していてもよく、置換基としては前述のＶ１及びＶ２が挙げられる。なお、複素環の別の互変異性構造を書くことができるどのような場合も、化学的に等価である。 These heterocyclic rings may be substituted or condensed with any substituent, and examples of the substituent include the aforementioned V 1 and V 2 . It should be noted that any case where another tautomeric structure of a heterocycle can be written is chemically equivalent.
ｒは置換基Ｖ１の数を表わし、好ましくは０〜３の数であり、より好ましくは１〜３の数であり、１又は２が特に好ましい。ｓは置換基Ｖ２の数を表わし、好ましくは０〜３の数であり、より好ましくは１〜３の数であり、１又は２が特に好ましい。
一般式（１）で表されるアゾ化合物においては、Ｖ１及びＶ２の少なくとも一方を置換基として有していることが好ましく、Ｖ１及びＶ２の両方を置換基として有していることがより好ましい。
r represents the number of substituents V 1 , preferably 0 to 3, more preferably 1 to 3, and 1 or 2 is particularly preferable. s represents the number of substituents V 2 , preferably a number of 0 to 3, more preferably a number of 1 to 3, and 1 or 2 is particularly preferable.
In the azo compound represented by the general formula (1), that it is preferable, have both V 1 and V 2 as the substituent having a least one substituent of V 1 and V 2 Is more preferable.
次に、本発明の一般式（２）、（３）、又は（４）で表される化合物について説明する。
上記一般式（１）で表されるアゾ化合物は下記一般式（２）で表されることが好ましい。
The azo compound represented by the general formula (1) is preferably represented by the following general formula (2).
上記一般式（１）または（２）で表されるアゾ化合物は、さらに下記一般式（３）で表されることが好ましい。
上記一般式（１）または（２）で表されるアゾ化合物は、また、下記一般式（４）で表されることが好ましい。
The azo compound represented by the general formula (1) or (2) is preferably further represented by the following general formula (3).
The azo compound represented by the general formula (1) or (2) is preferably represented by the following general formula (4).
なお、前記一般式（２）、（３）、又は（４）で表されるアゾ化合物においてＺ２、Ｖ１、Ｖ２、及びＶ３の好ましい範囲は、上述した一般式（１）で表されるアゾ化合物について示したものと同義である。 In the azo compound represented by the general formula (2), (3), or (4), preferred ranges of Z 2 , V 1 , V 2 , and V 3 are represented by the general formula (1) described above. It is synonymous with what was shown about the azo compound.
一般式（４）においては、上述のとおり、Ｖ２とＶ３とが結合して環（芳香族、非芳香族の炭化水素環、又は複素環。これらは、さらに組み合わされて多環縮合環を形成することができる。例えばベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環、トリフェニレン環、ナフタセン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環、フェナジン環、が挙げられる。）を形成することもできる。なかでも、ベンゼン環もしくはピリジン環が好ましい。 In the general formula (4), as described above, V 2 and V 3 are combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These are further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring , Carbazole ring, phenanthridine ring, acrylic Down ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed. Of these, a benzene ring or a pyridine ring is preferable.
一般式（１）、（２）、（３）、又は（４）で表されるアゾ化合物は、アミノ基を有するビ（ヘテロ）アリール化合物を分子内アゾカップリングする方法（例えば、Ｖ． Ｂｅｎｉｎ他著、Ｊ．Ｏｒｇ．Ｃｈｅｍ．、２０００年発行の６５巻、６３８８頁の記載に準じて形成する方法）、ビ（ヘテロ）アリール化合物上のアミノ基と含窒素化合物を反応させて形成する方法（例えば、酸の存在下で亜硝酸塩と反応させて形成する方法）などにより合成することができる。前記アミノ基を有するビ（ヘテロ）アリール化合物の合成法のいずれかを採用するかは、置換基Ｖ１及びＶ２の構造を含め、目的の化合物の構造に応じて定めることができる。
前記置換基Ｖ１、Ｖ２、及びＶ３は、どの反応過程で導入してもよいが、前記分子内アゾカップリングを行う前に導入することが好ましい。反応過程の初期または途中で導入する場合は、Ｖ１、Ｖ２、及びＶ３を適宜に保護・脱保護することにより目的の構造を有する化合物を得ることができる。
本発明のアゾ化合物の合成においてジアゾ成分の合成手順については、特開２００６−１４３９０２号公報、同２００６−１６９２３９号公報及びＬｉｅｂｉｇｓ Ａｎｎａｌｅｎ ｄｅｒ Ｃｈｅｍｉｅ；ＧＥ；１９７９；１５３４−１５４６等を参考にすることができる。
The azo compound represented by the general formula (1), (2), (3), or (4) is a method for intramolecular azo coupling of a bi (hetero) aryl compound having an amino group (for example, V. Benin Other methods, J. Org. Chem., Method published in 2000, 65, page 6388), a method in which an amino group on a bi (hetero) aryl compound is reacted with a nitrogen-containing compound. (For example, a method of forming by reacting with nitrite in the presence of an acid). Or to adopt any of the synthetic methods of bi (hetero) aryl compound having an amino group, including the configuration of the substituents V 1 and V 2, can be determined depending on the structure of the compound of interest.
The substituents V 1 , V 2 , and V 3 may be introduced in any reaction process, but are preferably introduced before the intramolecular azo coupling. In the case where the compound is introduced in the initial stage or in the middle of the reaction process, a compound having the target structure can be obtained by appropriately protecting and deprotecting V 1 , V 2 , and V 3 .
Regarding the synthesis procedure of the diazo component in the synthesis of the azo compound of the present invention, refer to JP-A-2006-143902, 2006-169239 and Liebigs Analder der Chemie; GE; 1979; 1534-1546, etc. it can.
Ｒで表されるカプラー成分とは、ジアゾニウム塩と反応し、アゾ染料を得ることの可能なカプラー化合物由来の部分構造を意味する。この概念はアゾ染料の分野で一般に用いられる。
本発明において、カプラー成分Ｒとしては、下記一般式（５）〜（１７）で表される構造のカプラー成分が好ましい。なお、これらはそれぞれ一般に、フェノール系カプラー、ナフトール系カプラー、活性メチレン系カプラー、ピラゾロン系カプラー、ピラゾロアゾール系カプラー、ピロロトリアゾール系カプラーと総称される成分である。一般式（５）〜（１７）において、Ｙは一般式（１）〜（４）で示したアゾ基と結合する結合手を表す。
The coupler component represented by R means a partial structure derived from a coupler compound that can react with a diazonium salt to obtain an azo dye. This concept is commonly used in the field of azo dyes.
In the present invention, the coupler component R is preferably a coupler component having a structure represented by the following general formulas (5) to (17). These components are generally collectively referred to as phenol couplers, naphthol couplers, active methylene couplers, pyrazolone couplers, pyrazoloazole couplers, and pyrrolotriazole couplers. In the general formulas (5) to (17), Y represents a bond that bonds to the azo group represented by the general formulas (1) to (4).
式中、Ｒ６、Ｒ７、Ｒ８、及びＲ９は各々独立して水素原子又は置換基を表し、互いに結合して縮合環を形成してもよい。Ｗは炭素原子又は窒素原子を表し、Ｗが炭素原子のときｎは１であり、Ｗが窒素原子のときｎは０である。 In the formula, R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom or a substituent, and may be bonded to each other to form a condensed ring. W represents a carbon atom or a nitrogen atom, n is 1 when W is a carbon atom, and n is 0 when W is a nitrogen atom.
Ｒ６、Ｒ７、Ｒ８、及びＲ９で表される置換基としては、前述のＶ１、Ｖ２、もしくはＶ３で表される置換基として例示したものが挙げられる。また、Ｒ６、Ｒ７、Ｒ８、Ｒ９が互いに結合して縮合環を形成するとき、Ｒ６とＲ７とが結合して形成される及び／又はＲ８とＲ９とが結合して形成される、芳香環であっても非芳香環であってもよく、炭素環であっても複素環であってもよい５〜７員環（例えばベンゼン環、ピリジン環）が挙げられる。 Examples of the substituent represented by R 6 , R 7 , R 8 , and R 9 include those exemplified as the substituent represented by the aforementioned V 1 , V 2 , or V 3 . Further, when R 6 , R 7 , R 8 , R 9 are bonded to each other to form a condensed ring, R 6 and R 7 are bonded to each other and / or R 8 and R 9 are bonded to each other. And a 5- to 7-membered ring (for example, a benzene ring or a pyridine ring), which may be an aromatic ring or a non-aromatic ring, and may be a carbocyclic ring or a heterocyclic ring.
Ｒ６、Ｒ７、Ｒ８、及びＲ９で表される置換基として、具体的には、水素原子、脂肪族炭化水素基、アリール基、ヘテロ環基、アシルオキシ基、アシルアミノ基、脂肪族オキシ基、アリールオキシ基、ヘテロ環オキシ基、脂肪族スルホンアミド基、アリールスルホンアミド基、ヘテロ環スルホンアミド基、アミノ基、脂肪族アミノ基、アリールアミノ基、ヘテロ環アミノ基、脂肪族オキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、ヘテロ環オキシカルボニルアミノ基、脂肪族チオ基、アリールチオ基、ヒドロキシ基、シアノ基、スルホ基、カルボキシル基、カルバモイルアミノ基、スルファモイルアミノ基、ハロゲン原子が挙げられる。より好ましくは、水素原子、脂肪族炭化水素基、ヘテロ環基、アシルアミノ基、脂肪族オキシ基、アリールオキシ基、脂肪族スルホンアミド基、アリールスルホンアミド基、脂肪族アミノ基、アリールアミノ基、ヘテロ環アミノ基、脂肪族チオ基、アリールチオ基、ハロゲン原子が挙げられる。 Specific examples of the substituent represented by R 6 , R 7 , R 8 , and R 9 include a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, an acyloxy group, an acylamino group, and an aliphatic oxy. Group, aryloxy group, heterocyclic oxy group, aliphatic sulfonamido group, aryl sulfonamido group, heterocyclic sulfonamido group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino Groups, aryloxycarbonylamino groups, heterocyclic oxycarbonylamino groups, aliphatic thio groups, arylthio groups, hydroxy groups, cyano groups, sulfo groups, carboxyl groups, carbamoylamino groups, sulfamoylamino groups, and halogen atoms. . More preferably, a hydrogen atom, aliphatic hydrocarbon group, heterocyclic group, acylamino group, aliphatic oxy group, aryloxy group, aliphatic sulfonamido group, arylsulfonamido group, aliphatic amino group, arylamino group, hetero A cyclic amino group, an aliphatic thio group, an arylthio group, and a halogen atom are exemplified.
このうち、Ｒ６及びＲ８で表される置換基としては、水素原子、ハロゲン原子、シアノ基、−ＣＯＮＲ１８Ｒ１９、−ＳＯ２ＮＲ１８Ｒ１９、−ＮＨＣＯＲ１８、−ＮＨＣＯＮＲ１８Ｒ１９、及び−ＮＨＳＯ２ＮＲ１８Ｒ１９から選ばれる基が好ましい。ここで、Ｒ１８及びＲ１９は水素原子又は置換基を示し、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１０のアリール基、もしくは炭素原子数１〜１０のヘテロ環基が好ましい。 Among these, as the substituent represented by R 6 and R 8 , a hydrogen atom, a halogen atom, a cyano group, —CONR 18 R 19 , —SO 2 NR 18 R 19 , —NHCOR 18 , —NHCONR 18 R 19 , And a group selected from —NHSO 2 NR 18 R 19 is preferred. Here, R 18 and R 19 represent a hydrogen atom or a substituent, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heterocycle having 1 to 10 carbon atoms. Groups are preferred.
また、Ｒ７及びＲ９で表される置換基としては、水素原子、アシルアミノ基、もしくはハロゲン原子が好ましい。 As the substituent represented by R 7 and R 9, a hydrogen atom, an acylamino group or a halogen atom, it is preferred.
カプラー成分Ｒは、下記一般式（６）〜（９）で表される活性メチレン系カプラー成分であることもまた好ましい。
Ｒ１０、Ｒ１１、又はＲ１２が有してもよい置換基としては、前述の置換基Ｖ１、Ｖ２、もしくはＶ３として例示したものが挙げられる。また、一般式（６）〜（９）において、Ｒ１０とＲ１１とが互いに結合して環を形成してもよく、またＲ１０とＲ１２とが互いに結合して環を形成してもよい。 Examples of the substituent that R 10 , R 11 , or R 12 may have include those exemplified as the aforementioned substituents V 1 , V 2 , or V 3 . In the general formulas (6) to (9), R 10 and R 11 may be bonded to each other to form a ring, or R 10 and R 12 may be bonded to each other to form a ring. Good.
カプラー成分Ｒは、下記一般式（１０）で表される５−ピラゾロン系カプラー成分であることもまた好ましい。
カプラー成分Ｒは、下記一般式（１１）で表されるピラゾロアゾール系カプラー成分であることもまた好ましい。
式中、Ｒ１５は水素原子又は置換基を表す。Ｑは窒素原子を２〜４個含む５員のアゾール環を形成するのに必要な非金属原子群を表し、そのようなアゾール環は置換基（縮合環を含む）を有してもよい。 In the formula, R 15 represents a hydrogen atom or a substituent. Q represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and such an azole ring may have a substituent (including a condensed ring).
カプラー成分Ｒは、下記一般式（１２）〜（１５）で表されるピロロトリアゾール系カプラー成分であることもまた好ましい。
式中、Ｒ２０、Ｒ２１、及びＲ２２は水素原子又は置換基を表す。Ｒ２０、Ｒ２１、及びＲ２２の置換基としては、前述の置換基Ｖ１、Ｖ２、もしくはＶ３として例示したものが挙げられる。 Wherein, R 20, R 21, and R 22 represents a hydrogen atom or a substituent. Examples of the substituent for R 20 , R 21 , and R 22 include those exemplified as the aforementioned substituents V 1 , V 2 , or V 3 .
また、そのほかにも、カプラー成分Ｒは、縮環フェノール系カプラー、イミダゾール系カプラー、ピロール系カプラー、３−ヒドロキシピリジン系カプラー（特開平１−３１５７３６号公報等に記載のカプラー）、上記以外の活性メチレン系カプラー活性性メチン系カプラー、５，５−縮環複素環系カプラー、５，６−縮環複素環系カプラー等が挙げられる。 In addition, the coupler component R includes condensed ring phenol couplers, imidazole couplers, pyrrole couplers, 3-hydroxypyridine couplers (couplers described in JP-A-1-315736, etc.), activities other than those described above. Examples include methylene coupler active methine couplers, 5,5-fused heterocyclic couplers, and 5,6-fused heterocyclic couplers.
カプラー成分Ｒとしては、さらに以下の一般式（１６）又は（１７）で表されるカプラー成分であることもまた好ましい。 The coupler component R is also preferably a coupler component represented by the following general formula (16) or (17).
一般式（１６）はフェノール系カプラー、一般式（１７）はナフトール系カプラーと称されるカプラーであり、式中、Ｒ１６は水素原子、ハロゲン原子、−ＣＯＮＲ１８Ｒ１９、−ＳＯ２ＮＲ１８Ｒ１９、−ＮＨＣＯＲ１８、−ＮＨＣＯＮＲ１８Ｒ１９、及び−ＮＨＳＯ２ＮＲ１８Ｒ１９から選ばれる基を表す。ここで、Ｒ１８及びＲ１９は水素原子又は置換基を表す。Ｒ１７は置換基を示し、ｌは０〜２から選ばれる整数、ｍは０〜４から選ばれる整数を表す。ｌ、ｍが２以上のときは、複数のＲ１７は同じでもそれぞれ異なっていてもよい。 The general formula (16) is a phenol coupler, and the general formula (17) is a coupler called a naphthol coupler. In the formula, R 16 is a hydrogen atom, a halogen atom, -CONR 18 R 19 , -SO 2 NR 18. It represents a group selected from R 19 , —NHCOR 18 , —NHCONR 18 R 19 , and —NHSO 2 NR 18 R 19 . Here, R 18 and R 19 represent a hydrogen atom or a substituent. R 17 represents a substituent, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, the plurality of R 17 may be the same or different.
Ｒ１７、Ｒ１８、又はＲ１９で表される置換基としては、前述の置換基Ｖ１、Ｖ２、もしくはＶ３として例示したものが挙げられる。特に、Ｒ１８及びＲ１９としては、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１０のアリール基、又は炭素原子数１〜１０のヘテロ環基が好ましい。また、一般式（１６）においては、水酸基のオルト位若しくはＲ１６のパラ位にＲ１７が位置することが好ましく、一般式（１７）においては、ナフトール環の５位若しくは８位にＲ１７が位置することが好ましい。 Examples of the substituent represented by R 17 , R 18 , or R 19 include those exemplified as the aforementioned substituents V 1 , V 2 , or V 3 . In particular, R 18 and R 19 are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heterocyclic group having 1 to 10 carbon atoms. In the general formula (16), it is preferred that R 17 is located in the ortho or para position of the R 16 hydroxyl groups, in the general formula (17), is R 17 at the 5-position or 8-position of the naphthol ring Preferably it is located.
カプラー成分Ｒとしては、なかでも、フェノール、２−クロロフェノール、２，５−ジクロロもしくはジフロロフェノール、２−カルバモイルフェノール、２−スルファモイルフェノール、１−ナフトール、２−ナフトール、２−プロピオニルアミノフェノール、２−プロピオニルアミノ−１−ナフトール、５−メチルスルホニルアミノ−１−ナフトール、５−フェニルスルホニルアミノ−２−プロピオニルアミノ−１−ナフトールが好ましく、フェノール、２−クロロフェノール、２，５−ジフロロフェノール、２−カルバモイルフェノールが特に好ましい。 Examples of the coupler component R include phenol, 2-chlorophenol, 2,5-dichloro or difluorophenol, 2-carbamoylphenol, 2-sulfamoylphenol, 1-naphthol, 2-naphthol, and 2-propionylamino. Phenol, 2-propionylamino-1-naphthol, 5-methylsulfonylamino-1-naphthol, 5-phenylsulfonylamino-2-propionylamino-1-naphthol are preferred, phenol, 2-chlorophenol, 2,5-dithiol Fluorophenol and 2-carbamoylphenol are particularly preferred.
次に、一般式（１）で表されるアゾ化合物の具体例を示すが、本発明はこれらに限定されるものではない。 Next, although the specific example of the azo compound represented by General formula (1) is shown, this invention is not limited to these.
なお、本発明の化合物が分子内に不斉炭素を複数個有する場合、同一構造に対して複数の立体異性体が存在するが、本発明のアゾ化合物はすべての立体異性体を含み、複数の立体異性のうち１つだけを使用することも、あるいはそのうちの数種を混合物として使用することもできる。 In addition, when the compound of the present invention has a plurality of asymmetric carbons in the molecule, there are a plurality of stereoisomers for the same structure, but the azo compound of the present invention includes all the stereoisomers, Only one of the stereoisomers can be used, or several of them can be used as a mixture.
本発明のアゾ化合物は色素として好適に用いることができ、具体的には、木綿、毛、若しくは合成繊維などの織物繊維、革、紙、プラスチック、または毛皮などの染色用、食品用、染毛剤用、インク用、インクジェットプリント用、レーザープリント用、コピー用、感熱転写方式画像形成用、光記録材料用、有機ＥＬ用発光材料用、レーザー用、有機半導体用、太陽電池用、蛍光プローブ用、非線形光学材料用、固体撮像管他各種フィルター用、及びカラー液晶などのディスプレイ用に使用される色素として用いることができる。
本発明のアゾ色素は、所望の吸収波長領域に吸収極大を有することが好ましく、特に限定されないが、例えば４００〜８００ｎｍに吸収極大を有することが好ましく、５００〜７００ｎｍに吸収極大を有することがより好ましい。また、モル吸光係数εは１００００〜１５００００であることが好ましく、１００００〜１０００００であることがより好ましい。
The azo compound of the present invention can be suitably used as a pigment, and specifically, textile fibers such as cotton, hair, or synthetic fibers, leather, paper, plastic, fur, and the like, foods, hair dyes. For agents, for ink, for inkjet printing, for laser printing, for copying, for thermal transfer type image formation, for optical recording materials, for organic EL light emitting materials, for lasers, for organic semiconductors, for solar cells, for fluorescent probes It can be used as a dye used for non-linear optical materials, solid-state imaging tubes and other various filters, and displays such as color liquid crystals.
The azo dye of the present invention preferably has an absorption maximum in a desired absorption wavelength region, and is not particularly limited. For example, the azo dye preferably has an absorption maximum at 400 to 800 nm, and more preferably has an absorption maximum at 500 to 700 nm. preferable. Further, the molar extinction coefficient ε is preferably 10,000 to 150,000, and more preferably 10,000 to 100,000.
本発明のアゾ化合物もしくはアゾ色素を染料や着色用組成物として用いるとき、その含有量は特に限定されないが、本発明の化合物もしくは色素を０．１〜９０重量％含有させることが好ましい。 When the azo compound or azo dye of the present invention is used as a dye or coloring composition, its content is not particularly limited, but it is preferable to contain 0.1 to 90% by weight of the compound or dye of the present invention.
以下に本発明を実施例に基づきさらに詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
例示化合物Ｄ−１２を以下のスキーム１のとおり合成した。なお、スキーム中、Ａｃはアセチル基を表し、％は重量％を表す。 Exemplified Compound D-12 was synthesized as shown in Scheme 1 below. In the scheme, Ac represents an acetyl group, and% represents% by weight.
（Ａ）化合物Ａの合成
ｍ−ニトロフェニルヒドラジン硫酸塩７５ｇにエタノール２４０ｍｌを加え攪拌下、トリエチルアミン５５ｍｌを添加した。この液を加熱還流し、これにエトキシメチレンマロノニトリル７６ｇのエタノール５０ｍｌ溶液を滴下した。滴下終了後、３時間加熱還流攪拌した。その後、反応液を全量で１５０ｍｌぐらいになるまで減圧濃縮した。濃縮された反応液を水冷し、得られた結晶を濾取、乾燥することで化合物Ａを６３．６ｇ（収率７５％）得た。
(A) Synthesis of Compound A 240 ml of ethanol was added to 75 g of m-nitrophenylhydrazine sulfate, and 55 ml of triethylamine was added with stirring. The solution was heated to reflux, and a solution of 76 g of ethoxymethylenemalononitrile in 50 ml of ethanol was added dropwise thereto. After completion of the dropwise addition, the mixture was heated and refluxed for 3 hours. Thereafter, the reaction solution was concentrated under reduced pressure to a total volume of about 150 ml. The concentrated reaction liquid was cooled with water, and the resulting crystals were collected by filtration and dried to obtain 63.6 g (yield 75%) of Compound A.
（Ｂ）化合物Ｂの合成
鉄粉１０４ｇ、塩化アンモニウム１１．４ｇ、水８５ｇを混合し、外温１００℃で１０分攪拌した。これに２−プロパノ−ル８５０ｍｌを加え、加熱還流攪拌しながら、化合物Ａ８１．８ｇをゆっくりと３０分かけて分割添加した。添加終了後さらに加熱還流を１時間した。反応液をセライトで熱時濾過した後、濾液を減圧濃縮し、これに水を加え、室温で３時間放置した。析出した結晶を濾取し、メタノールでかけ洗いした結晶を乾燥することで化合物Ｂを６０ｇ（収率８４％）得た。
(B) Synthesis of Compound B Iron powder 104 g, ammonium chloride 11.4 g, and water 85 g were mixed and stirred at an external temperature of 100 ° C. for 10 minutes. To this was added 850 ml of 2-propanol, and 81.8 g of Compound A was slowly added in portions over 30 minutes with stirring under heating and reflux. After completion of the addition, the mixture was further heated to reflux for 1 hour. The reaction solution was filtered with celite while hot, then the filtrate was concentrated under reduced pressure, water was added thereto, and the mixture was left at room temperature for 3 hours. The precipitated crystals were collected by filtration, and the crystals washed with methanol were dried to obtain 60 g of Compound B (yield 84%).
（Ｃ）化合物Ｄの合成
化合物Ａ１０ｇをアセトニトリル５０ｍｌに懸濁させ無水酢酸４．５ｍｌを室温にて加え１時間撹拌後、反応液を減圧下濃縮乾涸し、これを酢酸エチル／水で抽出、水洗し、硫酸マグネシウムにて一夜乾燥後、硫酸マグネシウムを濾別し濾液を濃縮乾涸した（化合物Ｃ）。これに８５重量％リン酸１５０ｇを加え０℃以下で撹拌しながらこれに亜硝酸ナトリウム３．１ｇを約６０分かけて分割添加した。０〜５℃で後反応を２時間行い、反応液に氷水５００ｍｌを加え析出した結晶を濾別、アセトニトリルにてかけ洗いした。この結晶をカラムクロマトにて精製し、化合物Ｄを５ｇ得た。
(C) Synthesis of Compound D Compound A (10 g) was suspended in acetonitrile (50 ml), acetic anhydride (4.5 ml) was added at room temperature and stirred for 1 hour. The reaction solution was concentrated to dryness under reduced pressure, extracted with ethyl acetate / water, washed with water. After drying overnight with magnesium sulfate, the magnesium sulfate was filtered off and the filtrate was concentrated to dryness (Compound C). To this was added 150 g of 85% by weight phosphoric acid, and 3.1 g of sodium nitrite was added in portions over about 60 minutes while stirring at 0 ° C. or lower. The post-reaction was performed at 0 to 5 ° C. for 2 hours, 500 ml of ice water was added to the reaction solution, and the precipitated crystals were separated by filtration and washed with acetonitrile. The crystals were purified by column chromatography to obtain 5 g of compound D.
（Ｄ）化合物Ｅの合成
化合物Ｄ５ｇを３５重量％塩酸３０ｍｌとイソプロパノール３０ｍｌ中に懸濁させ６０〜７０℃で３時間加熱撹拌した。反応混合物を減圧濃縮し、残渣に氷水２００ｍｌを加え析出した結晶を濾別、乾燥し化合物Ｅを２．５ｇ得た。
（Ｅ）化合物Ｄ−１２の合成
室温下、化合物Ｅ１ｇを８５重量％リン酸２０ｍｌ中に溶解し、０℃以下で撹拌しながら亜硝酸ナトリウム０．３６ｇを３０分かけて分割添加した。更に０〜５℃で２時間撹拌を続けて化合物Ｆを得た。
化合物Ｇ１．４ｇをメタノール１５０ｍｌに溶解し０℃以下で撹拌しながら、先に合成したジアゾニウム塩（化合物Ｆ）を０℃以下になるように分割添加した。０〜５℃で１時間、２０〜２５℃（室温）で１時間撹拌を続けた。この反応混合物に水２００ｍｌを加え析出した結晶を濾別乾燥し、カラムクロマトにて精製した。収量０．５ｇの化合物Ｄ−１２を得た（収率２０％）。
(D) Synthesis of Compound E 5 g of Compound D was suspended in 30 ml of 35% by weight hydrochloric acid and 30 ml of isopropanol, and heated and stirred at 60 to 70 ° C. for 3 hours. The reaction mixture was concentrated under reduced pressure, 200 ml of ice water was added to the residue, and the precipitated crystals were separated by filtration and dried to obtain 2.5 g of Compound E.
(E) Synthesis of Compound D-12 At room temperature, 1 g of Compound E was dissolved in 20 ml of 85 wt% phosphoric acid, and 0.36 g of sodium nitrite was added in portions over 30 minutes while stirring at 0 ° C. or lower. Further, stirring was continued at 0 to 5 ° C. for 2 hours to obtain Compound F.
While dissolving 1.4 g of Compound G in 150 ml of methanol and stirring at 0 ° C. or lower, the previously synthesized diazonium salt (Compound F) was added in portions so as to be 0 ° C. or lower. Stirring was continued for 1 hour at 0-5 ° C and 1 hour at 20-25 ° C (room temperature). 200 ml of water was added to the reaction mixture, and the precipitated crystals were separated by filtration, dried and purified by column chromatography. A yield of 0.5 g of compound D-12 was obtained (yield 20%).
化合物Ｄ−１２の融点は２５８〜２６０℃であった。また、同化合物についてＤＭＦ（Ｎ，Ｎ’−ジメチルホルムアミド）中で吸収スペクトルを測定したところ、吸収極大λｍａｘ６７７ｎｍ（ε８２，３００）を示し、色素の色相が良好であることを確認した（図−１参照）。 The melting point of Compound D-12 was 258 to 260 ° C. Further, when the absorption spectrum of the same compound was measured in DMF (N, N′-dimethylformamide), it showed an absorption maximum λmax 677 nm (ε82,300), and it was confirmed that the hue of the dye was good (FIG. 1). reference).
上記の化合物Ｄ−１２と同様な合成法で、スキーム−１のカプラー成分を３−エチルイソオキサゾロンに代えて化合物Ｄ−９を、２，５−ジフロロフェノールに代えて化合物Ｄ−２５を、２−クロロフェノールに代えて化合物Ｄ−３６をそれぞれ合成した。合成した各化合物の融点と極大吸収を以下に示す。
Ｄ−９；融点２１０〜２１２℃（分解）、極大吸収；５６４ｎｍ（図−２参照）
Ｄ−２５；融点２３３℃、極大吸収；６２４ｎｍ（図−３参照）
Ｄ−３６；融点２３７〜２３８℃、極大吸収；６５３ｎｍ（図−４参照）
その他、下記表１に記載の化合物を、上記化合物Ｄ−１２の合成スキームと同様にして合成した。但し、スキーム−１のカプラー成分をそれぞれ所定のものに代えて、またジアゾ成分について必要に応じて特開２００６−１４３９０２号公報、同２００６−１６９２３９号公報及びＬｉｅｂｉｇｓ Ａｎｎａｌｅｎ ｄｅｒ Ｃｈｅｍｉｅ；ＧＥ；１９７９；１５３４−１５４６の文献等を参考して合成した。
得られた各化合物について、吸収極大波長（λｍａｘ）及びモル吸光係数（εｍａｘ）を測定し、その結果を各化合物の色相とあわせて下記表１に示した。
In the same synthesis method as the above compound D-12, the coupler component of Scheme-1 is replaced with 3-ethylisoxazolone, compound D-9 is replaced with 2,5-difluorophenol, compound D-25 is replaced with Compound D-36 was synthesized in place of 2-chlorophenol. The melting point and maximum absorption of each synthesized compound are shown below.
D-9; melting point 210 to 212 ° C. (decomposition), maximum absorption; 564 nm (see FIG. 2)
D-25; melting point 233 ° C., maximum absorption; 624 nm (see FIG. 3)
D-36; melting point 237 to 238 ° C., maximum absorption; 653 nm (see FIG. 4)
In addition, the compounds described in Table 1 below were synthesized in the same manner as in the synthesis scheme of Compound D-12. However, the coupler component of Scheme-1 is replaced with a predetermined one, and the diazo component is disclosed in JP-A Nos. 2006-143902 and 2006-169239 and Liebigs Analender der Chemie; GE; 1979; The synthesis was performed with reference to the literature of -1546.
About each obtained compound, the absorption maximum wavelength ((lambda) max ) and the molar absorption coefficient ((epsilon) max ) were measured, and the result was shown in following Table 1 with the hue of each compound.
上記の化合物Ｄ−１２について、以下のようにして、染着性、移行性、及び堅牢性を確認した。 About said compound D-12, the dyeing property, transferability, and fastness were confirmed as follows.
［熱転写色素供与材料（Ｐ−１）の作製］
片面に耐熱滑性層を設けた、厚さ５μｍのポリエチレンテレフタレートフィルムを支持体とし、この支持体の、耐熱滑性層を設けた側と反対の側に、下記組成の色素供与層塗布用組成物（１）を、グラビアコーターを用いて、乾燥後の厚みが０．６μｍになるように塗布して、熱転写色素供与材料（Ｐ−１）（以下、単に色素供与材料ともいう）を得た。
[Preparation of thermal transfer dye donating material (P-1)]
A 5 μm thick polyethylene terephthalate film provided with a heat resistant slipping layer on one side is used as a support, and on the side opposite to the side where the heat resistant slipping layer is provided, a composition for coating a dye-donating layer having the following composition: The product (1) was applied using a gravure coater so that the thickness after drying was 0.6 μm to obtain a thermal transfer dye donating material (P-1) (hereinafter also simply referred to as a dye donating material). .
＜色素供与層塗布用組成物（１）＞
化合物Ｄ−１２ １０ｇ
ポリビニルブチラール（デンカブチラール５０００Ａ：電気化学社製、商品名）１０ｇ
シリコーンオイル（ＫＦ−９６：信越化学社製、商品名） ０．２ｇ
ポリイソシアネート（タケネートＤ１１０Ｎ：武田薬品社製、商品名）０．５ｇ
メチルエチルケトン １００ｍｌ
トルエン ８０ｍｌ
<Dye-donating layer coating composition (1)>
Compound D-12 10 g
Polyvinyl butyral (Denka butyral 5000A: manufactured by Electrochemical Co., Ltd., trade name) 10 g
Silicone oil (KF-96: Shin-Etsu Chemical Co., Ltd., trade name) 0.2g
Polyisocyanate (Takenate D110N: Takeda Pharmaceutical Co., Ltd., trade name) 0.5g
100 ml of methyl ethyl ketone
Toluene 80ml
［熱転写受像材料（１）の作製］
支持体として、厚さ１５０μｍの積層型合成紙を用い、表面に下記組成の受容層塗布用組成物（１）をワイヤーバーコーターを用いて、乾燥時の厚さが５μｍとなるように塗布して、熱転写受像材料（１）（以下、単に受像材料ともいう）を作製した。乾燥はドライヤーで仮乾燥後、８０℃のオーブン中で１時間行った。
[Preparation of thermal transfer image receiving material (1)]
Using a laminated synthetic paper with a thickness of 150 μm as a support and applying a receiving layer coating composition (1) having the following composition on the surface using a wire bar coater, the thickness when dried is 5 μm. Thus, a thermal transfer image receiving material (1) (hereinafter also simply referred to as an image receiving material) was produced. Drying was carried out for 1 hour in an oven at 80 ° C. after temporary drying with a dryer.
＜受容層塗布用組成物（１）＞
色素固定剤；Ａ−９（三共（株）社製、商品名：ＡＥＡ） ２６ｇ
ポリイソシアネート（ＫＰ−９０：大日本インキ化学社製、商品名） ４ｇ
アミノ変性シリコーンオイル（信越シリコーン社製、商品名：ＫＰ−８５７）０．５ｇ
メチルエチルケトン １００ｍｌ
トルエン ５０ｍｌ
シクロヘキサノン １０ｍｌ
<Receptive layer coating composition (1)>
Dye fixing agent; A-9 (manufactured by Sankyo Co., Ltd., trade name: AEA) 26 g
Polyisocyanate (KP-90: Dainippon Ink & Chemicals, trade name) 4g
Amino-modified silicone oil (trade name: KP-857, manufactured by Shin-Etsu Silicone) 0.5g
100 ml of methyl ethyl ketone
Toluene 50ml
10 ml of cyclohexanone
上記のようにして得られた熱転写色素供与材料（Ｄ−１）を用いて色素供与層と熱転写受像材料（１）の受容層とが接するようにして重ね合わせ、熱転写色素供与材料の支持体側から、サーマルヘッドを使用し、サーマルヘッドの出力０．２５Ｗ／ドット、パルス幅０．１〜１０ｍｓｅｃ、ドット密度６ドット／ｍｍの条件で加熱を行い、受像材料の受容層に色素を像状に染着させたところ、転写むらの無い鮮明な画像記録が得られた。 Using the thermal transfer dye-donating material (D-1) obtained as described above, the dye-donating layer and the receiving layer of the thermal transfer image-receiving material (1) are brought into contact with each other, from the support side of the thermal transfer dye-donating material. Using a thermal head, heating is performed under the conditions of a thermal head output of 0.25 W / dot, a pulse width of 0.1 to 10 msec, and a dot density of 6 dots / mm, and the dye is imaged on the receiving layer of the image receiving material. As a result, a clear image record without transfer unevenness was obtained.
このとき得られた記録済みの受像材料の濃度が飽和している部分（Ｄｍａｘ部分）を反射型濃度計（Ｘ Ｒｉｔｅ Ｉｎｃ．社製、ステータスＡフィルター内蔵）を用いて測定し、画像の最大転写濃度を測定した。次に、記録済みの受像材料を７日間、１７，０００ルクスの蛍光灯に照射し、画像の光堅牢性を調べた。反射濃度１．０を示す部分の試験後の反射濃度を測定し、試験前の反射濃度１．０に対する残存率（％）でその安定性を評価した。また、６０℃のオーブンに１週間保存し画像の熱安定性を調べたが、本発明の化合物Ｄ−１２を用いた材料は殆ど濃度低下や変色が観察されず安定であった。 The portion (Dmax portion) where the density of the recorded image receiving material obtained at this time is saturated is measured using a reflection densitometer (manufactured by X Rite Inc., built in status A filter), and the maximum transfer of the image is performed. Concentration was measured. Next, the recorded image receiving material was irradiated on a 17,000 lux fluorescent lamp for 7 days, and the light fastness of the image was examined. The reflection density after the test of the portion showing the reflection density of 1.0 was measured, and the stability was evaluated by the residual ratio (%) with respect to the reflection density of 1.0 before the test. Further, the image was stored in an oven at 60 ° C. for 1 week, and the thermal stability of the image was examined. However, the material using Compound D-12 of the present invention was stable with almost no decrease in density or discoloration.
さらに、記録済の受像材料を６０℃のオーブンに２週間保存した後の画像のにじみの程度を観察した。判断基準は、画像が保存前とほとんど変化していない場合は○、少し滲んでいる場合を△、非常に滲んでぼけている場合を×とした。本発明の化合物Ｄ−１２を用いて形成した画像は保存前とほとんど変化していなかった（○）。 Further, the degree of bleeding of the image after the recorded image receiving material was stored in an oven at 60 ° C. for 2 weeks was observed. Judgment criteria were ◯ when the image was almost unchanged from before storage, Δ when the image was slightly blurred, and × when the image was very blurred. The image formed by using the compound D-12 of the present invention was hardly changed from that before storage (◯).
以上の結果より、本発明のアゾ化合物によれば、転写濃度が高く（十分な染着性及び移行性を有し）、光や熱に対する堅牢性に優れた鮮明な画像が得られ、しかも経時による画像ボケがほとんどないことがわかる。 From the above results, according to the azo compound of the present invention, a clear image having a high transfer density (having sufficient dyeability and transferability) and excellent fastness to light and heat can be obtained. It can be seen that there is almost no image blur due to.
化合物Ｄ−１２に代えて、化合物Ｄ−９、Ｄ−２５、及びＤ−３６をそれぞれ用いた以外上記と同様にして、色素供与層塗布用組成物Ｐ−２〜Ｐ−４を作製し、各々について上記の試験を行った。その結果、化合物Ｄ−９、Ｄ−２５、及びＤ−３６はいずれも化合物Ｄ−１２と同様に良好な染着性、移行性、及び堅牢性を示した。 Dye-donating layer coating compositions P-2 to P-4 were prepared in the same manner as described above except that compounds D-9, D-25, and D-36 were used instead of compound D-12, respectively. Each of the above tests was performed. As a result, all of the compounds D-9, D-25, and D-36 showed good dyeing property, migration property, and fastness as with the compound D-12.
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| JP2008248211A (en) * | 2007-03-30 | 2008-10-16 | Fujifilm Corp | Azo pigment and azo compound |
| JP2009013069A (en) * | 2007-06-29 | 2009-01-22 | Kao Corp | Hair dye composition |
| JP2009013071A (en) * | 2007-06-29 | 2009-01-22 | Kao Corp | Hair dye composition |
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| JP2003342139A (en) * | 2002-05-28 | 2003-12-03 | Kao Corp | Hair dye composition |
| JP2006143902A (en) * | 2004-11-19 | 2006-06-08 | Fuji Photo Film Co Ltd | New azo pigment compound |
| JP2006169239A (en) * | 2004-11-19 | 2006-06-29 | Fuji Photo Film Co Ltd | New azo dye compound |
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| JP2003342139A (en) * | 2002-05-28 | 2003-12-03 | Kao Corp | Hair dye composition |
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| JP2008248211A (en) * | 2007-03-30 | 2008-10-16 | Fujifilm Corp | Azo pigment and azo compound |
| JP2009013069A (en) * | 2007-06-29 | 2009-01-22 | Kao Corp | Hair dye composition |
| JP2009013071A (en) * | 2007-06-29 | 2009-01-22 | Kao Corp | Hair dye composition |
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