JP6386835B2 - Azo compounds - Google Patents
Azo compounds Download PDFInfo
- Publication number
- JP6386835B2 JP6386835B2 JP2014173471A JP2014173471A JP6386835B2 JP 6386835 B2 JP6386835 B2 JP 6386835B2 JP 2014173471 A JP2014173471 A JP 2014173471A JP 2014173471 A JP2014173471 A JP 2014173471A JP 6386835 B2 JP6386835 B2 JP 6386835B2
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- JP
- Japan
- Prior art keywords
- group
- parts
- dye
- formula
- alkenyl
- 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.)
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- -1 sulfomethyl group Chemical group 0.000 claims description 95
- 125000002947 alkylene group Chemical group 0.000 claims description 51
- 239000001257 hydrogen Substances 0.000 claims description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- 125000003342 alkenyl group Chemical group 0.000 claims description 44
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 43
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 36
- 125000003277 amino group Chemical group 0.000 claims description 30
- 125000006699 (C1-C3) hydroxyalkyl group Chemical group 0.000 claims description 17
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 16
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000003282 alkyl amino group Chemical group 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 11
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 11
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 10
- 125000000732 arylene group Chemical group 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims description 7
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 7
- 125000001174 sulfone group Chemical group 0.000 claims description 7
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 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 claims description 2
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000005265 dialkylamine group Chemical group 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 125000004964 sulfoalkyl group Chemical group 0.000 claims 1
- 239000000975 dye Substances 0.000 description 482
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 420
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 255
- 239000000243 solution Substances 0.000 description 217
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 190
- 150000001875 compounds Chemical class 0.000 description 169
- 238000010521 absorption reaction Methods 0.000 description 130
- 230000015572 biosynthetic process Effects 0.000 description 130
- 238000003786 synthesis reaction Methods 0.000 description 130
- 239000000203 mixture Substances 0.000 description 89
- 235000012970 cakes Nutrition 0.000 description 82
- 239000000049 pigment Substances 0.000 description 73
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 72
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 72
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 70
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 68
- 238000006243 chemical reaction Methods 0.000 description 66
- 239000000047 product Substances 0.000 description 66
- 238000001914 filtration Methods 0.000 description 52
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- 235000021463 dry cake Nutrition 0.000 description 38
- 238000001816 cooling Methods 0.000 description 37
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 35
- 235000010288 sodium nitrite Nutrition 0.000 description 35
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 34
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 description 20
- 235000017550 sodium carbonate Nutrition 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 18
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 18
- 239000000976 ink Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- UGNXZCBVIDOPCO-UHFFFAOYSA-N CCCCN1C(O)=CC(C)=C(C#N)C1=O Chemical compound CCCCN1C(O)=CC(C)=C(C#N)C1=O UGNXZCBVIDOPCO-UHFFFAOYSA-N 0.000 description 16
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 15
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 14
- HYCARMRJXWGSON-UHFFFAOYSA-N CCCN1C(O)=CC(C)=C(C#N)C1=O Chemical compound CCCN1C(O)=CC(C)=C(C#N)C1=O HYCARMRJXWGSON-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 11
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- XWVGXTYHPCKSLV-UHFFFAOYSA-N dibutyltin;dodecanoic acid Chemical compound CCCC[Sn]CCCC.CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O XWVGXTYHPCKSLV-UHFFFAOYSA-N 0.000 description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 5
- XPZDQTNHPYEIQQ-UHFFFAOYSA-N CCCCC(CC)CN1C(O)=CC(C)=C(C#N)C1=O Chemical compound CCCCC(CC)CN1C(O)=CC(C)=C(C#N)C1=O XPZDQTNHPYEIQQ-UHFFFAOYSA-N 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 4
- UXZFDLQNZDPYDE-UHFFFAOYSA-N chembl1540129 Chemical compound CC=1C=C(O)N(CCO)C(=O)C=1C#N UXZFDLQNZDPYDE-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 4
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 4
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 3
- 125000004042 4-aminobutyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])N([H])[H] 0.000 description 3
- VHEKFTULOYIMSU-UHFFFAOYSA-N 4-ethenylbenzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=C(C=C)C=C1 VHEKFTULOYIMSU-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- KFOZNPPBKHYHQD-UHFFFAOYSA-N ethenesulfonyl chloride Chemical compound ClS(=O)(=O)C=C KFOZNPPBKHYHQD-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 3
- 125000002004 n-butylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004888 n-propyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004957 naphthylene group Chemical group 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000001454 recorded image Methods 0.000 description 3
- JDTUPLBMGDDPJS-UHFFFAOYSA-N 2-methoxy-2-phenylethanol Chemical compound COC(CO)C1=CC=CC=C1 JDTUPLBMGDDPJS-UHFFFAOYSA-N 0.000 description 2
- HCDMJFOHIXMBOV-UHFFFAOYSA-N 3-(2,6-difluoro-3,5-dimethoxyphenyl)-1-ethyl-8-(morpholin-4-ylmethyl)-4,7-dihydropyrrolo[4,5]pyrido[1,2-d]pyrimidin-2-one Chemical compound C=1C2=C3N(CC)C(=O)N(C=4C(=C(OC)C=C(OC)C=4F)F)CC3=CN=C2NC=1CN1CCOCC1 HCDMJFOHIXMBOV-UHFFFAOYSA-N 0.000 description 2
- VSQJORHLXHADFP-UHFFFAOYSA-N CC(C)OCCCn1c(O)cc(C)c(C#N)c1=O Chemical compound CC(C)OCCCn1c(O)cc(C)c(C#N)c1=O VSQJORHLXHADFP-UHFFFAOYSA-N 0.000 description 2
- 0 CC(N=N[C@@](C(N1*)O)C(*)=C(*)C1=O)=C* Chemical compound CC(N=N[C@@](C(N1*)O)C(*)=C(*)C1=O)=C* 0.000 description 2
- SPDLJPUVRYZYHP-UHFFFAOYSA-N CCCCCCCCN1C(O)=CC(C)=C(C#N)C1=O Chemical compound CCCCCCCCN1C(O)=CC(C)=C(C#N)C1=O SPDLJPUVRYZYHP-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- ZSUMNJYQUKCOBV-UHFFFAOYSA-N chembl1469934 Chemical compound CCN1C(O)=CC(C)=C(C#N)C1=O ZSUMNJYQUKCOBV-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 2
- YPLIFKZBNCNJJN-UHFFFAOYSA-N n,n-bis(ethylamino)ethanamine Chemical compound CCNN(CC)NCC YPLIFKZBNCNJJN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000006608 n-octyloxy group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- AAHFRWRQQDVWPX-UHFFFAOYSA-N prop-2-ene-1-sulfonyl chloride Chemical compound ClS(=O)(=O)CC=C AAHFRWRQQDVWPX-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical group CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- VCGRFBXVSFAGGA-UHFFFAOYSA-N (1,1-dioxo-1,4-thiazinan-4-yl)-[6-[[3-(4-fluorophenyl)-5-methyl-1,2-oxazol-4-yl]methoxy]pyridin-3-yl]methanone Chemical compound CC=1ON=C(C=2C=CC(F)=CC=2)C=1COC(N=C1)=CC=C1C(=O)N1CCS(=O)(=O)CC1 VCGRFBXVSFAGGA-UHFFFAOYSA-N 0.000 description 1
- ABDDQTDRAHXHOC-QMMMGPOBSA-N 1-[(7s)-5,7-dihydro-4h-thieno[2,3-c]pyran-7-yl]-n-methylmethanamine Chemical compound CNC[C@@H]1OCCC2=C1SC=C2 ABDDQTDRAHXHOC-QMMMGPOBSA-N 0.000 description 1
- LQQCVHOXXXWSIC-UHFFFAOYSA-N 1-butyl-3-hydroxypyridin-2-one Chemical compound CCCCN1C=CC=C(O)C1=O LQQCVHOXXXWSIC-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SDHQGBWMLCBNSM-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]ethyl acetate Chemical compound COCCOCCOCCOC(C)=O SDHQGBWMLCBNSM-UHFFFAOYSA-N 0.000 description 1
- UCMCDBAWQIVKTE-UHFFFAOYSA-N 3-(2-hydroxyethyl)-1h-pyridin-2-one Chemical compound OCCC1=CC=CN=C1O UCMCDBAWQIVKTE-UHFFFAOYSA-N 0.000 description 1
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 1
- KIIPHTJVRJBYFC-UHFFFAOYSA-N 3-hydroxy-1-(2-hydroxyethyl)pyridin-2-one Chemical compound OCCN1C=CC=C(O)C1=O KIIPHTJVRJBYFC-UHFFFAOYSA-N 0.000 description 1
- KIBNFCSPPOYXPP-UHFFFAOYSA-N 3-methyl-1-phenylthieno[2,3-c]pyrazole-5-carboxylic acid Chemical compound C1=2SC(C(O)=O)=CC=2C(C)=NN1C1=CC=CC=C1 KIBNFCSPPOYXPP-UHFFFAOYSA-N 0.000 description 1
- KVCQTKNUUQOELD-UHFFFAOYSA-N 4-amino-n-[1-(3-chloro-2-fluoroanilino)-6-methylisoquinolin-5-yl]thieno[3,2-d]pyrimidine-7-carboxamide Chemical compound N=1C=CC2=C(NC(=O)C=3C4=NC=NC(N)=C4SC=3)C(C)=CC=C2C=1NC1=CC=CC(Cl)=C1F KVCQTKNUUQOELD-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- YGNDWDUEMICDLW-UHFFFAOYSA-N 7-anilino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C=1C=C2C(O)=CC(S(O)(=O)=O)=CC2=CC=1NC1=CC=CC=C1 YGNDWDUEMICDLW-UHFFFAOYSA-N 0.000 description 1
- CYJRNFFLTBEQSQ-UHFFFAOYSA-N 8-(3-methyl-1-benzothiophen-5-yl)-N-(4-methylsulfonylpyridin-3-yl)quinoxalin-6-amine Chemical compound CS(=O)(=O)C1=C(C=NC=C1)NC=1C=C2N=CC=NC2=C(C=1)C=1C=CC2=C(C(=CS2)C)C=1 CYJRNFFLTBEQSQ-UHFFFAOYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- YAZVDZNZROIOKJ-UHFFFAOYSA-N C(#N)C=1C(N(C(=CC=1C(F)(F)F)O)CC(CCCC)CC)=O Chemical compound C(#N)C=1C(N(C(=CC=1C(F)(F)F)O)CC(CCCC)CC)=O YAZVDZNZROIOKJ-UHFFFAOYSA-N 0.000 description 1
- ZJZDYSFNHBWLCR-UHFFFAOYSA-N C(#N)C=1C(N(C(=CC=1C(F)(F)F)O)CCN(CC)CC)=O Chemical compound C(#N)C=1C(N(C(=CC=1C(F)(F)F)O)CCN(CC)CC)=O ZJZDYSFNHBWLCR-UHFFFAOYSA-N 0.000 description 1
- LMENZJQRDGSGJA-UHFFFAOYSA-N C(#N)C=1C(N(C(=CC=1CC)O)CCC)=O Chemical compound C(#N)C=1C(N(C(=CC=1CC)O)CCC)=O LMENZJQRDGSGJA-UHFFFAOYSA-N 0.000 description 1
- WYWAXULEXLBPFM-UHFFFAOYSA-N C(#N)C=1C(N(C(=CC=1CC)O)CCN)=O Chemical compound C(#N)C=1C(N(C(=CC=1CC)O)CCN)=O WYWAXULEXLBPFM-UHFFFAOYSA-N 0.000 description 1
- UYBHIGFCNDGCCH-UHFFFAOYSA-N C(CCCCC)N1C(C(=C(C=C1O)C)C(=O)N)=O Chemical compound C(CCCCC)N1C(C(=C(C=C1O)C)C(=O)N)=O UYBHIGFCNDGCCH-UHFFFAOYSA-N 0.000 description 1
- ZETDSOQUFSTLRH-UHFFFAOYSA-N CC=1C=C(O)N(C)C(=O)C=1S(O)(=O)=O Chemical compound CC=1C=C(O)N(C)C(=O)C=1S(O)(=O)=O ZETDSOQUFSTLRH-UHFFFAOYSA-N 0.000 description 1
- AAMOUTZMWNSBOC-UHFFFAOYSA-N CC=1C=C(O)N(CCN)C(=O)C=1C#N Chemical compound CC=1C=C(O)N(CCN)C(=O)C=1C#N AAMOUTZMWNSBOC-UHFFFAOYSA-N 0.000 description 1
- XQSYHRIMOOOLDE-UHFFFAOYSA-N CC=1C=C(O)N(CCS(O)(=O)=O)C(=O)C=1C#N Chemical compound CC=1C=C(O)N(CCS(O)(=O)=O)C(=O)C=1C#N XQSYHRIMOOOLDE-UHFFFAOYSA-N 0.000 description 1
- YOSLGMSQBMTIBD-ZIADKAODSA-N CCCCC(CC)CN(C(C(C#N)=C1C(F)(F)F)=O)C(O)=C1/N=N\c(cc1)ccc1S(CCO)(=O)=O Chemical compound CCCCC(CC)CN(C(C(C#N)=C1C(F)(F)F)=O)C(O)=C1/N=N\c(cc1)ccc1S(CCO)(=O)=O YOSLGMSQBMTIBD-ZIADKAODSA-N 0.000 description 1
- UVGSMRCYYPTSDD-UHFFFAOYSA-N CCCCC(CC)CN1C(O)=CC(C)=C(C(N)=O)C1=O Chemical compound CCCCC(CC)CN1C(O)=CC(C)=C(C(N)=O)C1=O UVGSMRCYYPTSDD-UHFFFAOYSA-N 0.000 description 1
- QZXZCJPQBTUDQR-UHFFFAOYSA-N CCCCC(CC)CN1C=CC=C(C1=O)O Chemical compound CCCCC(CC)CN1C=CC=C(C1=O)O QZXZCJPQBTUDQR-UHFFFAOYSA-N 0.000 description 1
- NISAUPVCCRMFJZ-UHFFFAOYSA-N CCCCCCN1C(O)=CC(C)=C(C#N)C1=O Chemical compound CCCCCCN1C(O)=CC(C)=C(C#N)C1=O NISAUPVCCRMFJZ-UHFFFAOYSA-N 0.000 description 1
- SHFZYSVDXQGHRR-BBCRLRBNSA-N CCCN(C(C(C#N)=C1C)=O)C(O)=C1Nc(cc1)ccc1S(CCNCCCN1CCN(CCCNCCS(c(cc2)ccc2/N=N\C(C(C)=C(C(N2CCC)=O)C#N)=C2O)(=O)=O)CC1)(=O)=O Chemical compound CCCN(C(C(C#N)=C1C)=O)C(O)=C1Nc(cc1)ccc1S(CCNCCCN1CCN(CCCNCCS(c(cc2)ccc2/N=N\C(C(C)=C(C(N2CCC)=O)C#N)=C2O)(=O)=O)CC1)(=O)=O SHFZYSVDXQGHRR-BBCRLRBNSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AYCPARAPKDAOEN-LJQANCHMSA-N N-[(1S)-2-(dimethylamino)-1-phenylethyl]-6,6-dimethyl-3-[(2-methyl-4-thieno[3,2-d]pyrimidinyl)amino]-1,4-dihydropyrrolo[3,4-c]pyrazole-5-carboxamide Chemical compound C1([C@H](NC(=O)N2C(C=3NN=C(NC=4C=5SC=CC=5N=C(C)N=4)C=3C2)(C)C)CN(C)C)=CC=CC=C1 AYCPARAPKDAOEN-LJQANCHMSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241001136629 Pixus Species 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical group NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- XGVXKJKTISMIOW-ZDUSSCGKSA-N simurosertib Chemical compound N1N=CC(C=2SC=3C(=O)NC(=NC=3C=2)[C@H]2N3CCC(CC3)C2)=C1C XGVXKJKTISMIOW-ZDUSSCGKSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
本発明は、エチルスルホニルフェニルアゾ骨格と重合性不飽和基を有することを特徴とするアゾ化合物に関するものである。本発明のアゾ化合物はインクジェット記録液用色素およびフェルトペンのインク用色素として非常に有用であり、さらにボールペン、万年筆等の筆記具用の記録液用色素にも利用することができる。 The present invention relates to an azo compound having an ethylsulfonylphenylazo skeleton and a polymerizable unsaturated group. The azo compound of the present invention is very useful as a dye for ink jet recording liquids and a dye for inks of felt pens, and can also be used for recording liquid dyes for writing instruments such as ballpoint pens and fountain pens.
近年になってインクジェット記録方式はカラー画像を容易に作成できる手段として広く用いられるようになり、更なる高画質化が求められるようになってきている。 In recent years, the ink jet recording system has been widely used as a means for easily creating a color image, and further higher image quality has been demanded.
この高画質化の実現を可能にするため、色素に求められる性能としては色調再現性が優れていること、光学濃度が高く、色調がシャープであることが求められ、更に太陽光を初めとして種々の光に対しての変退色、耐水性、耐湿性といった画像堅牢性が良好な色素が求められ、かつ溶媒への溶解性が高いこと、ノズルの目詰まりを生じないことが望まれている。
さらに環境変化(気温)が伴う中、インクジェット記録用の色素溶解液として最も重要である長期保存性も良好な色素が求められている。
In order to realize this high image quality, the performance required of the pigment is required to have excellent color tone reproducibility, high optical density and sharp color tone, and various types of sunlight and other Therefore, there is a demand for a dye having good image fastness such as discoloration, water resistance and moisture resistance to light, high solubility in a solvent, and no nozzle clogging.
Furthermore, a dye having good long-term storage stability, which is most important as a dye solution for ink jet recording, has been demanded in the presence of environmental changes (temperature).
またフェルトペンのインク用色素に求められる性能も上記と同様に、色調再現性が優れていること、光学濃度が高く、色調がシャープであること、更に太陽光を初めとして種々の光に対しての変退色、耐水性、耐湿性といった画像堅牢性が良好な色素が求められ、かつ溶媒への溶解性が高いことが望まれている。
先行技術文献として、例えば特許文献１〜９には、アゾ化合物が提案されているが、それらが色素として市場で要求されている諸特性を十分に満足させるまでに至っていない。
In addition, the performance required of the felt pen ink coloring matter is excellent in color tone reproducibility, high in optical density and sharp in color tone, and also with respect to various kinds of light such as sunlight. Therefore, there is a demand for a dye having good image fastness such as discoloration, water resistance and moisture resistance, and high solubility in a solvent.
As prior art documents, for example, Patent Documents 1 to 9 propose azo compounds, but they have not yet fully satisfy various characteristics required in the market as dyes.
従って、本発明は、色調再現性が優れており、光学濃度が高く、色調がシャープで、かつ太陽光を初めとして種々の光に対しての変退色、耐水性、耐湿性といった画像堅牢性が良好なインクジェット記録液用色素およびフェルトペンのインク用色素で、さらに高温または低温における過酷な環境下での色素の析出、変色などがなく長期保存性に非常に優れたインクジェット記録液用色素およびフェルトペンのインク用色素を提供することを目的とする。 Accordingly, the present invention has excellent color tone reproducibility, high optical density, sharp color tone, and image fastness such as discoloration, water resistance, and moisture resistance to various kinds of light including sunlight. Dye for ink jet recording liquid and felt dye for felt pen, and ink dye and felt for ink jet recording liquid with excellent long-term storability without dye precipitation or discoloration in harsh environments at high or low temperatures It is an object to provide a pigment for pen ink.
本発明者等は前記したような特性を可能にするインクジェット記録液用色素およびフェルトペンのインク用色素に使用されるアゾ化合物を提供すべく鋭意検討した結果、本発明を完成するに至った。
即ち、本発明は以下の１．〜４．を特徴とするものである。
The inventors of the present invention have intensively studied to provide an azo compound for use in an ink jet recording liquid dye and a felt pen ink dye that enables the above-described characteristics, and as a result, the present invention has been completed.
That is, the present invention provides the following 1. ~ 4. It is characterized by.
１．式（１）
Ｄ−（Ａ）n （１）
〔Ｄはアゾ色素からなる色素母体を表し、
Ａは下記式（２）
Ｘ1は下記式（３）または下記式（４）
Ｒ7およびＲ8はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表す｝を表す]を表し、
ｎは１〜４の整数を表し、またｎが２〜４の場合はＡのそれぞれは同一でも異なっても良く、かつ式（１）には少なくとも１つの重合性不飽和基が含まれる〕で表されるアゾ化合物。
1. Formula (1)
D- (A) n (1)
[D represents a dye matrix composed of an azo dye;
A is the following formula (2)
X 1 is the following formula (3) or the following formula (4)
R 7 and R 8 each independently represent hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group. Represents
n represents an integer of 1 to 4, and when n is 2 to 4, each A may be the same or different, and the formula (1) contains at least one polymerizable unsaturated group] An azo compound represented.
２．式（６）
Ｒ10はシアノ基、カルバモイル基、スルホン基、またはスルホメチル基を表し、
Ｒ11は水素、Ｃ1〜Ｃ10のアルキル基、Ｃ2〜Ｃ8のアルコキシアルキル基、Ｃ1〜Ｃ4のヒドロキシアルキル基、Ｃ2〜Ｃ4のスルホアルキル基、重合性不飽和基を有する基、または 下記式（７）
Ｒ15およびＲ16はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表し、
Ｒ12およびＲ13はそれぞれ独立して、水素、ハロゲン、Ｃ1〜Ｃ3のアルキル基、またはＣ1〜Ｃ3のアルコキシル基を表し、
Ｘ2は下記式（８）または下記式（９）
Ｒ21およびＲ22はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表す｝を表し、かつ式（６）には少なくとも1つの重合性不飽和基が含まれる〕で表される上記１．のアゾ化合物、
2. Formula (6)
R 10 represents a cyano group, a carbamoyl group, a sulfone group, or a sulfomethyl group,
R 11 represents hydrogen, a C 1 -C 10 alkyl group, a C 2 -C 8 alkoxyalkyl group, a C 1 -C 4 hydroxyalkyl group, a C 2 -C 4 sulfoalkyl group, or a polymerizable unsaturated group. Or a group having the following formula (7)
R 15 and R 16 each independently represents hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group).
R 12 and R 13 each independently represent hydrogen, halogen, a C 1 -C 3 alkyl group, or a C 1 -C 3 alkoxyl group;
X 2 is the following formula (8) or the following formula (9)
R 21 and R 22 each independently represent hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group)} And (6) contains at least one polymerizable unsaturated group]. Azo compounds,
３．式（１１）
Ｒ27およびＲ28はそれぞれ独立して、Ｃ1〜Ｃ4のアルキル基、またはトリフルオロメチル基を表し、
Ｒ29およびＲ30はそれぞれ独立して、シアノ基、またはカルバモイル基を表し、
Ｘ3およびＸ4はそれぞれ独立して、下記式（１２）または下記式（１３）
Ｒ35およびＲ36はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表す｝を表し、
ＹはＣ2〜Ｃ6のアルキレン基、または下記式（１５）
Ｌ1はアリーレン基、複素環基、酸素原子、または下記式（１６）
R 27 and R 28 each independently represent an alkyl group or a trifluoromethyl group, a C 1 -C 4,
R 29 and R 30 each independently represents a cyano group or a carbamoyl group,
X 3 and X 4 each independently represent the following formula (12) or the following formula (13)
R 35 and R 36 each independently represent hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group)}
Y is an alkylene group of C 2 -C 6 or the following formula (15)
L 1 represents an arylene group, a heterocyclic group, an oxygen atom, or the following formula (16)
４．式（１７）
Ｒ44およびＲ45はそれぞれ独立して、Ｃ1〜Ｃ4のアルキル基、またはトリフルオロメチル基を表し、
Ｒ46およびＲ47はそれぞれ独立して、シアノ基、またはカルバモイル基を表し、
Ｒ48およびＲ49はそれぞれ独立して、水素、Ｃ1〜Ｃ10のアルキル基、Ｃ2〜Ｃ8のアルコキシアルキル基、Ｃ1〜Ｃ4のヒドロキシアルキル基、重合性不飽和基を有する基、または 下記式（１８）
Ｒ51およびＲ52はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表し、
Ｚは複素環基、下記式（１９）または下記式（２０）
Ｒ54およびＲ55はそれぞれ独立して、水素、Ｃ1〜Ｃ10のアルキル基、Ｃ1〜Ｃ4のヒドロキシアルキル基、または重合性不飽和基を有する基を表し、
Ｌ2はＣ2〜Ｃ6のアルキレン基、または下記式（２２）
Ｌ3はアリーレン基、複素環基、酸素原子、または下記式（２３）
R 44 and R 45 each independently represents a C 1 -C 4 alkyl group or a trifluoromethyl group;
R 46 and R 47 each independently represent a cyano group or a carbamoyl group,
R 48 and R 49 are each independently hydrogen, a C 1 -C 10 alkyl group, a C 2 -C 8 alkoxyalkyl group, a C 1 -C 4 hydroxyalkyl group, or a group having a polymerizable unsaturated group. Or the following formula (18)
R 51 and R 52 each independently represent hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group).
Z is a heterocyclic group, the following formula (19) or the following formula (20)
R 54 and R 55 each independently represent hydrogen, a C 1 -C 10 alkyl group, a C 1 -C 4 hydroxyalkyl group, or a group having a polymerizable unsaturated group;
L 2 is a C 2 to C 6 alkylene group, or the following formula (22)
L 3 represents an arylene group, a heterocyclic group, an oxygen atom, or the following formula (23)
本発明のアゾ化合物は従来のものと比較して、耐光性、耐水性、耐湿性、保存安定性において優れているおり、高品質な画像が保たれるという優れた効果を奏する。 The azo compound of the present invention is superior in light resistance, water resistance, moisture resistance, and storage stability as compared with conventional ones, and has an excellent effect that a high-quality image is maintained.
以下、本発明について詳細に説明する。
本発明のアゾ化合物において、前記式（１）中のＤは、化合物を構成する原子団中に少なくとも１つはアゾ（−Ｎ＝Ｎ−）結合を有する色素母体で、例えばベンゼンアゾ系、ナフタレンアゾ系、ピリドンアゾ系、ピラゾロンアゾ系、バルビツール酸アゾ系などの色素母体を表す。
Ｄの具体例としては、以下の（Ａ−１）〜（Ａ−８）が挙げられる。
Hereinafter, the present invention will be described in detail.
In the azo compound of the present invention, D in the above formula (1) is a dye matrix having at least one azo (—N═N—) bond in the atomic group constituting the compound. Represents a dye matrix such as a dye, pyridoneazo, pyrazolone azo, and barbituric acid azo.
Specific examples of D include the following (A-1) to (A-8).
（式中、Ｒ9、Ｒ10、Ｒ11、Ｒ27、Ｒ28、Ｒ29およびＲ30は、前記式（６）または式（１１）において定義されたとおりであり、Ｒ60はヒドロキシル基、アミノ基、Ｃ1〜Ｃ4のア
ルキルアミノ基、Ｃ1〜Ｃ4のジアルキルアミノ基、アセチルアミノ基などを表し、Ｒ61およびＲ62はそれぞれ独立して、水素、Ｃ1〜Ｃ3のアルキル基、Ｃ1〜Ｃ3のアルコキシル基、アミノ基、ヒドロキシル基、アセチルアミノ基、ハロゲン基などを表し、Ｒ63はヒドロキシル基、Ｃ1〜Ｃ10のアルキルアミノ基などを表し、Ｒ64はヒドロキシル基、アミノ基、Ｃ1〜Ｃ4のアルキルアミノ基、Ｃ1〜Ｃ4のジアルキルアミノ基、アセチルアミノ基などを表し、Ｒ65は水素、ヒドロキシル基、アミノ基、Ｃ1〜Ｃ4のアルキルアミノ基、Ｃ1〜Ｃ4のジアルキルアミノ基、アセチルアミノ基、フェニルアミノ基、ベンゾイルアミノ基などを表し、Ｒ66はヒドロキシル基、Ｃ1〜Ｃ10のアルキルアミノ基などを表し、Ｒ67およびＲ68はそれぞれ独立して、ヒドロキシル基、アミノ基などを表し、Ｒ69はヒドロキシル基、Ｃ1〜Ｃ10のアルキルアミノ基などを表し、Ｒ70は水素、アミノ基、Ｃ1〜Ｃ3のアルキル基、カルボキシル基などを表し、Ｒ71およびＲ72はそれぞれ独立して、水素、Ｃ1〜Ｃ3のアルキル基、Ｃ1〜Ｃ3のアルコキシル基、ハロゲン基などを表し、Ｒ73はヒドロキシル基、Ｃ1〜Ｃ10のアルキルアミノ基、Ｃ1〜Ｃ10のアルキルアミノエチル基などを表し、Ｒ74は水素、Ｃ1〜Ｃ10のアルキル基などを表し、Ｒ75およびＲ76はそれぞれ独立して、水素、Ｃ1〜Ｃ10のアルキル基などを表す。また式（Ａ−１）、（Ａ−３）〜（Ａ−６）にスルホン基が含まれる場合、そのスルホン基は−ＳＯ3ＨまたはＣ1〜Ｃ8のアルキルアミン塩、Ｃ1〜Ｃ16のジアルキルアミン塩、Ｃ1〜Ｃ24のトリアルキルアミン塩でもよい。）
(Wherein R 9 , R 10 , R 11 , R 27 , R 28 , R 29 and R 30 are as defined in the above formula (6) or formula (11), R 60 is a hydroxyl group, amino group, an alkylamino group of C 1 -C 4, a dialkylamino group of C 1 -C 4, represents an acetyl amino group, R 61 and R 62 each independently represent hydrogen, alkyl of C 1 -C 3 group, an alkoxyl group of C 1 -C 3, an amino group, a hydroxyl group, an acetylamino group, etc. a halogen group, R 63 represents a hydroxyl group and the like, an alkylamino group of C 1 ~C 10, R 64 is a hydroxyl group, an amino group, an alkylamino group of C 1 -C 4, a dialkylamino group of C 1 -C 4, represents an acetyl group, R 65 is hydrogen, hydroxyl group, amino group, alkyl C 1 -C 4 amino group, dialkyl of C 1 -C 4 Amino group, an acetylamino group, phenylamino group, etc. benzoylamino group, R 66 represents a hydroxyl group and the like, an alkylamino group of C 1 ~C 10, R 67 and R 68 are each independently a hydroxyl group R 69 represents a hydroxyl group, a C 1 -C 10 alkylamino group or the like, R 70 represents hydrogen, an amino group, a C 1 -C 3 alkyl group, a carboxyl group, or the like; 71 and R 72 each independently represent hydrogen, a C 1 -C 3 alkyl group, a C 1 -C 3 alkoxyl group, a halogen group, or the like; R 73 is a hydroxyl group, a C 1 -C 10 alkylamino group group, C 1 -C represents an alkyl aminoethyl group 10, R 74 is hydrogen, C 1 -C represents an alkyl group of 10, R 75 and R 76 are each independently hydrogen, C 1 -C 10 alkyl groups etc. When a sulfone group is contained in the formulas (A-1) and (A-3) to (A-6), the sulfone group is —SO 3 H or a C 1 to C 8 alkylamine salt, C 1. dialkylamine salts -C 16, it may be a trialkyl amine salts of C 1 ~C 24.)
また、前記式（１）中に少なくとも1つ含まれる重合性不飽和基は、ラジカル重合しうる不飽和基を意味し、具体的には、アルケニル基などが含まれる。したがって、前記式（１）中に含まれる重合性不飽和基を有する基は、上記不飽和基を有する基をいい、例えば−Ｃ（＝Ｏ）−（Ｃ2〜Ｃ6）アルケニル基、−ＳＯ2−アリーレン−（Ｃ2〜Ｃ4）アルケニル基、−Ｃ（＝Ｏ）ＮＨ−（Ｃ1〜Ｃ4）アルキレン−ＯＣ（＝Ｏ）−（Ｃ2〜Ｃ6）アルケニル基、−（Ｃ1〜Ｃ4）アルキレン−ＯＣ（＝Ｏ）−（Ｃ2〜Ｃ6）アルケニル基、−（Ｃ1〜Ｃ6）アルキレン（ＯＨ）−ＯＣ（＝Ｏ）−（Ｃ2〜Ｃ6）アルケニル基および−ＳＯ2−（Ｃ2〜Ｃ6）アルケニル基、ならびにヒドロキシル基、第一級アミノ基、第二級アミノ基を含む基であって、前記基のヒドロキシル基またはアミノ基の水素原子が、前述のアルケニル基を含む基により置換された基などが挙げられる。ここで、前記のヒドロキシル基やアミノ基を含む基の具体例としては、−（Ｃ1〜Ｃ4）アルキレン−ＯＨ、−（Ｃ1〜Ｃ4）アルキレン−ＮＨ2などが挙げられ、また、前記におけるアリーレンとしては、５〜１５個の炭素原子を含む芳香族単環式または二環式、例えば、フェニレン、ナフチレンなどが挙げられる。重合性不飽和基を有する基の具体例は、以下の（Ｂ−１）〜（Ｂ−１２）、およびヒドロキシル基またはアミノ基の水素原子が（Ｂ−１）〜（Ｂ−１２）により置換された、−（Ｃ1〜Ｃ4）アルキレン−ＯＨ、−（Ｃ1〜Ｃ4）アルキレン−ＮＨ2などである。 The at least one polymerizable unsaturated group contained in the formula (1) means an unsaturated group capable of radical polymerization, and specifically includes an alkenyl group. Therefore, the group having a polymerizable unsaturated group contained in the formula (1) refers to a group having the unsaturated group, for example, —C (═O) — (C 2 -C 6 ) alkenyl group, — SO 2 -arylene- (C 2 -C 4 ) alkenyl group, —C (═O) NH— (C 1 -C 4 ) alkylene-OC (═O) — (C 2 -C 6 ) alkenyl group, — ( C 1 -C 4) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 6) alkylene (OH) -OC (= O) - (C 2 ~C 6) An alkenyl group and a —SO 2 — (C 2 -C 6 ) alkenyl group, and a group containing a hydroxyl group, a primary amino group, and a secondary amino group, wherein the hydroxyl group or the hydrogen atom of the amino group Is a group substituted with a group containing the aforementioned alkenyl group. Here, specific examples of the group containing a hydroxyl group or an amino group include-(C 1 -C 4 ) alkylene-OH,-(C 1 -C 4 ) alkylene-NH 2, etc. Examples of the arylene include aromatic monocyclic or bicyclic compounds containing 5 to 15 carbon atoms such as phenylene and naphthylene. Specific examples of the group having a polymerizable unsaturated group include the following (B-1) to (B-12), and the hydrogen atom of the hydroxyl group or amino group is substituted by (B-1) to (B-12). is, - (C 1 ~C 4) alkylene -OH, - (C 1 ~C 4 ) and the like alkylene -NH 2.
また前記式（２）中のＲ1およびＲ2はそれぞれ独立して、例えば水素原子、塩素原子、メチル基、エチル基、メトキシ基、またはエトキシ基などであり、Ｘ1としては例えば前記式（Ｂ−１）〜（Ｂ−１２）、またはヒドロキシル基またはアミノ基の水素原子が（Ｂ−１）〜（Ｂ−１２）により置換された、−（Ｃ1〜Ｃ4）アルキレン−ＯＨ、−（Ｃ1〜Ｃ4）アルキレン−ＮＨ2などにより置換された基、もしくはヒドロキシル基、アミノ基、２−ヒドロキシエチルオキシ基、２−ヒドロキシプロピルオキシ基、エチルオキシ基、ｎ−ブチルオキシ基、ｎ−ヘキシルオキシ基、ｎ−オクチルオキシ基、２−エチルヘキシルオキシ基、ｎ−プロピルアミノ基、ｎ−ブチルアミノ基、ｎ−ヘキシルアミノ基、ｎ−オクチルアミノ基、２−エチルヘキシルアミノ基、ジエチルアミノ基、ジブチルアミノ基、ジ（２−エチルヘキシル）アミノ基、２−ヒドロキシエチルアミノ基、ジ（２−ヒドロキシエチル）アミノ基、３−（２−ヒドロキシエチルアミノ）プロピルアミノ基、２−アミノエチルアミノ基、４−アミノブチルアミノ基、６−アミノヘキシルアミノ基、ジ（３−アミノプロピル）アミノ基、ジエチルアミノエチルアミノ基、ジメチルアミノプロピルアミノ基、ジエチルアミノプロピルアミノ基またはＮ−メチル−Ｎ−（アミノエチル）アミノ基などが挙げられる。 R 1 and R 2 in the formula (2) are each independently, for example, a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and X 1 is, for example, the above formula ( B-1) to (B-12), or — (C 1 to C 4 ) alkylene-OH, wherein a hydrogen atom of a hydroxyl group or an amino group is substituted by (B-1) to (B-12), — A group substituted by (C 1 -C 4 ) alkylene-NH 2 or the like, or a hydroxyl group, amino group, 2-hydroxyethyloxy group, 2-hydroxypropyloxy group, ethyloxy group, n-butyloxy group, n-hexyl Oxy group, n-octyloxy group, 2-ethylhexyloxy group, n-propylamino group, n-butylamino group, n-hexylamino group, n-octylamino group, 2-ethyl Hexylamino group, diethylamino group, dibutylamino group, di (2-ethylhexyl) amino group, 2-hydroxyethylamino group, di (2-hydroxyethyl) amino group, 3- (2-hydroxyethylamino) propylamino group, 2-aminoethylamino group, 4-aminobutylamino group, 6-aminohexylamino group, di (3-aminopropyl) amino group, diethylaminoethylamino group, dimethylaminopropylamino group, diethylaminopropylamino group or N-methyl -N- (aminoethyl) amino group and the like can be mentioned.
さらに前記式（１）の具体例としては、例えば、以下の（Ｃ−１）〜（Ｃ−１２）が挙げられる。 Furthermore, specific examples of the formula (1) include the following (C-1) to (C-12).
また前記式（６）中において、少なくとも1つは含まれる重合性不飽和基および重合性不飽和基を有する基としては、式（１）で説明したのと同様の基が挙げられ、Ｒ12およびＲ13はそれぞれ独立して、例えば水素原子、塩素原子、メチル基、エチル基、メトキシ基、またはエトキシ基などであり、Ｒ9は例えばメチル基、エチル基、プロピル基、またはトリフルオロメチル基などであり、Ｒ10はシアノ基、カルバモイル基、スルホン基、またはスルホメチル基であり、Ｒ11は例えば前記式（Ｂ−１）〜（Ｂ−１２）、またはヒドロキシル基またはアミノ基の水素原子が（Ｂ−１）〜（Ｂ−１２）により置換された、−（Ｃ1〜Ｃ4）アルキレン−ＯＨ、−（Ｃ1〜Ｃ4）アルキレン−ＮＨ2などの基、もしくはメチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、３−イソプロポキシプロピル基、２−ヒドロキシエチル基、スルホエチル基、２−アミノエチル基、４−アミノブチル基、６−アミノヘキシル基、ジエチルアミノエチル基、ジメチルアミノプロピル基、またはジエチルアミノプロピル基などであり、Ｘ2については、例えば前記式（Ｂ−１）〜（Ｂ−１２）、またはヒドロキシル基またはアミノ基の水素原子が（Ｂ−１）〜（Ｂ−１２）により置換された、−（Ｃ1〜Ｃ4）アルキレン−ＯＨ、−（Ｃ1〜Ｃ4）アルキレン−ＮＨ2などにより置換された基、もしくはヒドロキシル基、アミノ基、２−ヒドロキシエチルオキシ基、２−ヒドロキシプロピルオキシ基、エチルオキシ基、ｎ−ブチルオキシ基、ｎ−ヘキシルオキシ基、ｎ−オクチルオキシ基、２−エチルヘキシルオキシ基、ｎ−プロピルアミノ基、ｎ−ブチルアミノ基、ｎ−ヘキシルアミノ基、ｎ−オクチルアミノ基、２−エチルヘキシルアミノ基、ジエチルアミノ基、ジブチルアミノ基、ジ（２−エチルヘキシル）アミノ基、２−ヒドロキシエチルアミノ基、ジ（２−ヒドロキシエチル）アミノ基、３−（２−ヒドロキシエチルアミノ）プロピルアミノ基、２−アミノエチルアミノ基、４−アミノブチルアミノ基、６−アミノヘキシルアミノ基、ジ（３−アミノプロピル）アミノ基、ジエチルアミノエチルアミノ基、またはＮ−メチル−Ｎ−（アミノエチル）アミノ基などが挙げられる。 In the formula (6), at least one of the polymerizable unsaturated group and the group having a polymerizable unsaturated group is the same as described in the formula (1), and R 12 And R 13 are each independently, for example, a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R 9 is, for example, a methyl group, an ethyl group, a propyl group, or a trifluoromethyl group. R 10 represents a cyano group, a carbamoyl group, a sulfone group, or a sulfomethyl group, and R 11 represents, for example, the above formulas (B-1) to (B-12), or a hydrogen atom of a hydroxyl group or an amino group (B-1) was replaced by ~ (B-12), - (C 1 ~C 4) alkylene -OH, - (C 1 ~C 4 ) groups such as alkylene -NH 2 or methyl group, an ethyl group Propyl Butyl group, hexyl group, octyl group, 2-ethylhexyl group, 3-isopropoxypropyl group, 2-hydroxyethyl group, sulfoethyl group, 2-aminoethyl group, 4-aminobutyl group, 6-aminohexyl group, diethylamino An ethyl group, a dimethylaminopropyl group, a diethylaminopropyl group, or the like, and for X 2 , for example, the hydrogen atom of the formula (B-1) to (B-12), or the hydroxyl group or amino group is (B-1 ) substituted by ~ (B-12), - (C 1 ~C 4) alkylene -OH, - (C 1 ~C 4 ) alkylene -NH 2 substituted groups due or hydroxyl group, an amino group, 2-hydroxyethyloxy group, 2-hydroxypropyloxy group, ethyloxy group, n-butyloxy group, n-hexyloxy N-octyloxy group, 2-ethylhexyloxy group, n-propylamino group, n-butylamino group, n-hexylamino group, n-octylamino group, 2-ethylhexylamino group, diethylamino group, dibutylamino group, Di (2-ethylhexyl) amino group, 2-hydroxyethylamino group, di (2-hydroxyethyl) amino group, 3- (2-hydroxyethylamino) propylamino group, 2-aminoethylamino group, 4-aminobutyl Examples thereof include an amino group, 6-aminohexylamino group, di (3-aminopropyl) amino group, diethylaminoethylamino group, and N-methyl-N- (aminoethyl) amino group.
さらに前記式（６）の具体例としては、例えば、以下の（Ｄ−１）〜（Ｄ−６６）が挙げられる。 Furthermore, specific examples of the formula (6) include the following (D-1) to (D-66).
また前記式（１１）の定義中に記載された重合性不飽和基を有する基としては、式（１）で説明したのと同様の基が挙げられる。さらに前記式（１１）中において、Ｒ23、Ｒ24、Ｒ25およびＲ26はそれぞれ独立して、例えば水素原子、塩素原子、メチル基、エチル基、メトキシ基、またはエトキシ基などであり、Ｒ27およびＲ28は例えばメチル基、エチル基、プロピル基、またはトリフルオロメチル基などがあり、Ｒ29およびＲ30はシアノ基、またはカルバモイル基であり、Ｘ3およびＸ4はそれぞれ独立して、例えば前記式（Ｂ−１）〜（Ｂ−１２）、またはヒドロキシル基またはアミノ基の水素原子が（Ｂ−１）〜（Ｂ−１２）により置換された、−（Ｃ1〜Ｃ4）アルキレン−ＯＨ、−（Ｃ1〜Ｃ4）アルキレン−ＮＨ2などにより置換された基、もしくはヒドロキシル基、アミノ基、２−ヒドロキシエチルオキシ基、２−ヒドロキシプロピルオキシ基、エチルオキシ基、ｎ−ブチルオキシ基、ｎ−ヘキシルオキシ基、ｎ−オクチルオキシ基、２−エチルヘキシルオキシ基、ｎ−プロピルアミノ基、ｎ−ブチルアミノ基、ｎ−ヘキシルアミノ基、ｎ−オクチルアミノ基、２−エチルヘキシルアミノ基、ジエチルアミノ基、ジブチルアミノ基、ジ（２−エチルヘキシル）アミノ基、２−ヒドロキシエチルアミノ基、ジ（２−ヒドロキシエチル）アミノ基、３−（２−ヒドロキシエチルアミノ）プロピルアミノ基、２−アミノエチルアミノ基、４−アミノブチルアミノ基、６−アミノヘキシルアミノ基、ジ（３−アミノプロピル）アミノ基、ジエチルアミノエチルアミノ基、またはＮ−メチル−Ｎ−（アミノエチル）アミノ基などがあり、Ｙは例えばエチレン基、プロピレン基、ブチレン基、ヘキシレン基、前記式（Ｂ−１）〜（Ｂ−１２）、またはヒドロキシル基またはアミノ基の水素原子が（Ｂ−１）〜（Ｂ−１２）により置換された、−（Ｃ1〜Ｃ4）アルキレン−ＯＨ、−（Ｃ1〜Ｃ4）アルキレン−ＮＨ2などにより置換された連結基、または下記式
また、前記式（１１）の定義中に記載されたアリーレン基としては、５〜１５個の炭素原子を含む芳香族単環式または二環式環、例えば、フェニレン基、ナフチレン基などが挙げられ、複素環としては、ヘテロ原子として２個の窒素原子を含む５〜１０員の飽和環式環、例えば、ピペラジンなどが挙げられる。 The arylene group described in the definition of the formula (11) includes an aromatic monocyclic or bicyclic ring containing 5 to 15 carbon atoms, such as a phenylene group and a naphthylene group. Examples of the heterocyclic ring include 5- to 10-membered saturated cyclic rings containing two nitrogen atoms as heteroatoms, such as piperazine.
さらに前記式（１１）の具体例としては、例えば、以下の（Ｆ−１）〜（Ｆ−２４）が挙げられる。 Further, specific examples of the formula (11) include the following (F-1) to (F-24).
また前記式（１７）の定義中に記載された重合性不飽和基を有する基としては、式（１）で説明したのと同様の基が挙げられる。さらに前記式（１７）中において、Ｒ40、Ｒ41、Ｒ42およびＲ43はそれぞれ独立して、例えば水素原子、塩素原子、メチル基、エチル基、メトキシ基、またはエトキシ基などであり、Ｒ44およびＲ45はそれぞれ独立して、例えばメチル基、エチル基、プロピル基、またはトリフルオロメチル基などであり、Ｒ46およびＲ47はそれぞれ独立して、シアノ基、またはカルバモイル基であり、Ｒ48およびＲ49はそれぞれ独立して、例えば前記式（Ｂ−１）〜（Ｂ−１２）、またはヒドロキシル基またはアミノ基の水素原子が（Ｂ−１）〜（Ｂ−１２）により置換された、−（Ｃ1〜Ｃ4）アルキレン−ＯＨ、−（Ｃ1〜Ｃ4）アルキレン−ＮＨ2などの基、もしくはメチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、３−イソプロポキシプロピル基、２−ヒドロキシエチル基、２−アミノエチル基、４−アミノブチル基、６−アミノヘキシル基、ジエチルアミノエチル基、ジメチルアミノプロピル基、またはジエチルアミノプロピル基などであり、Ｚは例えばエチレンジアミン基、プロピレンジアミン基、ブチレンジアミン基、ヘキシレンジアミン基、エチレンジオキシ基、プロピレンジオキシ基、メチルジカルボキシル基、エチルジカルボキシル基、プロピルジカルボキシル基、ヘキシルジカルボキシル基、ベンゼンジカルボキシル基、前記式（Ｂ−１）〜（Ｂ−１２）、またはヒドロキシル基またはアミノ基の水素原子が（Ｂ−１）〜（Ｂ−１２）により置換された、−（Ｃ1〜Ｃ4）アルキレン−ＯＨ、−（Ｃ1〜Ｃ4）アルキレン−ＮＨ2などにより置換された連結基、または下記式
また、前記式（１７）の定義中に記載されたアリーレン基としては、５〜１５個の炭素原子を含む芳香族単環式または二環式環、例えば、フェニレン基、ナフチレン基などが挙げられ、複素環としては、ヘテロ原子として２個の窒素原子を含む５〜１０員の飽和環式環、例えば、ピペラジンなどが挙げられる。 The arylene group described in the definition of the formula (17) includes an aromatic monocyclic or bicyclic ring containing 5 to 15 carbon atoms, such as a phenylene group and a naphthylene group. Examples of the heterocyclic ring include 5- to 10-membered saturated cyclic rings containing two nitrogen atoms as heteroatoms, such as piperazine.
さらに前記式（１７）の具体例としては、例えば、（Ｈ−１）〜（Ｈ−２８）が挙げられる。 Furthermore, specific examples of the formula (17) include (H-1) to (H-28).
本発明の前記式（１）、式（６）、式（１１）、および式（１７）で表されるアゾ色素は、公知の方法で容易に製造することができる。例えば、ジアゾ成分については４−（β−スルファトエチルスルホニル）アニリンとアミノ基またはヒドロキシル基を有する脂肪族炭化水素などとを特開２００２−３４８４９２に記載されているような公知の方法で製造することができ、ジアゾ化およびカップリング反応においても公知の方法で実施することができる。また重合性不飽和基との反応においては、アクリロイルクロリド、メタロイルクロリド、２−イソシアナートエチルアクリレート、２−イソシアナートエチルメタクリレート、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、グリシジルアクリレート、グリシジルメタクリレート、ビニルスルホニルクロリド、アリルスルホニルクロリド、メタリルスルホニルクロリドなどと公知の方法で実施することができる。 The azo dyes represented by formula (1), formula (6), formula (11), and formula (17) of the present invention can be easily produced by a known method. For example, for the diazo component, 4- (β-sulfatoethylsulfonyl) aniline and an aliphatic hydrocarbon having an amino group or a hydroxyl group are produced by a known method as described in JP-A-2002-348492. The diazotization and coupling reaction can also be carried out by known methods. In the reaction with a polymerizable unsaturated group, acryloyl chloride, metalloyl chloride, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate , Vinyl sulfonyl chloride, allyl sulfonyl chloride, methallyl sulfonyl chloride and the like can be carried out by a known method.
このようにして得られる反応液を濾過、水洗して無機塩を充分に取り除くことで脱塩処理を行った脱塩湿ケーキを得ることができる。無機塩が充分に取り除けていない場合は上記にて得られた湿ケーキをメタノール、アセトン、Ｎ,Ｎ−ジメチルホルムアミド等の有機溶剤を使用して脱塩処理を行うことにより脱塩湿ケーキを得ることができる。 The desalted wet cake subjected to the desalting treatment can be obtained by filtering and washing the reaction solution thus obtained to sufficiently remove inorganic salts. When the inorganic salt has not been sufficiently removed, the desalted wet cake is obtained by subjecting the wet cake obtained above to desalting using an organic solvent such as methanol, acetone, N, N-dimethylformamide or the like. be able to.
得られた脱塩湿ケーキを乾燥後、得られたアゾ化合物をインク化する溶解剤の具体例としては、トルエン、酢酸エチル、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、sec−ブタノール、tert−ブタノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ブチレングリコール、ジプロピレングリコール、チオジグリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、２−ピロリドン、Ｎ−メチル−２−ピロリドン、Ｎ,Ｎ−ジメチルホルムアミド、アセトン、メチルエチルケトン、テトラヒドロフランなどが挙げられる。 Specific examples of the solubilizing agent that inks the obtained azo compound after drying the obtained desalted wet cake include toluene, ethyl acetate, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate , Triethylene glycol monomethyl ether, triethylene glycol monomethyl ether acetate, propylene glycol Examples thereof include coal monomethyl ether, propylene glycol monomethyl ether acetate, 2-pyrrolidone, N-methyl-2-pyrrolidone, N, N-dimethylformamide, acetone, methyl ethyl ketone, and tetrahydrofuran.
具体的には、本発明の式（６）の化合物の一つである式（３０）で表されるアゾ色素の製造方法としては、例えば、式（２４）で表わされる化合物と式（２５）で表わされる化合物とを水中にて水酸化ナトリウム水溶液を添加して反応させることで、式（２６）で表される化合物が得られる。次に、式（２６）で表される化合物に鉱酸、亜硝酸ナトリウム水溶液を滴下し、過剰の亜硝酸を分解して、式（２７）で表わされる化合物とをソーダ灰を含む水溶液中で、水酸化ナトリウム水溶液でｐＨを７.０〜８.０に保持しながら反応させ、式（２８）で表わされる化合物を得る。得られた式（２８）で表わされる化合物を式（２９）で表わされる化合物と、テトラヒドロフラン中ピリジンの存在下で反応させ、得られた反応液を濃縮し、水に滴下して、式（３０）で表わされる化合物を得る。 Specifically, as a method for producing an azo dye represented by the formula (30) which is one of the compounds of the formula (6) of the present invention, for example, a compound represented by the formula (24) and the formula (25) A compound represented by the formula (26) is obtained by reacting the compound represented by the formula (26) with a sodium hydroxide aqueous solution in water. Next, a mineral acid and a sodium nitrite aqueous solution are dropped into the compound represented by the formula (26) to decompose excess nitrous acid, and the compound represented by the formula (27) is dissolved in an aqueous solution containing soda ash. The reaction is carried out while maintaining the pH at 7.0 to 8.0 with an aqueous sodium hydroxide solution to obtain the compound represented by formula (28). The compound represented by the formula (28) thus obtained is reacted with the compound represented by the formula (29) in the presence of pyridine in tetrahydrofuran, and the resulting reaction solution is concentrated and added dropwise to water. ) Is obtained.
また、式（２５）においてＲ19がＣ1〜Ｃ6のアミノアルキル基である化合物を用い、上記と同様の操作により、下記式（３１）の化合物を得ることができる。 In addition, a compound of the following formula (31) can be obtained by the same operation as above using a compound in which R 19 is a C 1 -C 6 aminoalkyl group in the formula (25).
また上記の製造方法は、目的とする最終生成物に応じて、種々変更が可能であり、例えば、上記式（３０）または上記式（３１）の化合物の製造方法において、式（２９）の化合物を例えば２−イソシアナートエチルアクリレートに変更し、テトラヒドロフラン中ヘキサメチレンジアミンおよびジラウリン酸ジブチルスズ（II）存在下で反応させることで、下記式（３２）または下記式（３３）の化合物が得られ、式（２９）の化合物を例えばp-スチレンスルホニルクロリドに変更し、テトラヒドロフラン中トリエチルアミン存在下で反応させることで、下記式（３４）または下記式（３５）の化合物が得られ、式（２９）の化合物を例えば２−ヒドロキシエチルアクリレートに変更し、ジメチルホルムアミド中テトラブチルアンモニウムブロミドおよび４−ｔｅｒｔ−ブチルピロカテコール存在下で反応させることで、下記式（３６）または下記式（３７）の化合物が得られ、式（２９）の化合物を例えばグリシジルアクリレートに変更し、ジメチルホルムアミド中テトラブチルアンモニウムブロミドおよび４−ｔｅｒｔ−ブチルピロカテコール存在下で反応させることで、下記式（３８）または下記式（３９）の化合物が得られる。 In addition, the above production method can be variously changed according to the target final product. For example, in the production method of the compound of the above formula (30) or the above formula (31), the compound of the formula (29) Is changed to, for example, 2-isocyanatoethyl acrylate and reacted in the presence of hexamethylenediamine and dibutyltin (II) dilaurate in tetrahydrofuran to obtain a compound of the following formula (32) or the following formula (33). By changing the compound of (29) to, for example, p-styrenesulfonyl chloride and reacting in tetrahydrofuran in the presence of triethylamine, a compound of the following formula (34) or the following formula (35) is obtained, and a compound of the formula (29) For example, 2-hydroxyethyl acrylate and tetrabutylammonium bromide in dimethylformamide. By reacting in the presence of amide and 4-tert-butylpyrocatechol, a compound of the following formula (36) or the following formula (37) is obtained. The compound of the formula (29) is changed to, for example, glycidyl acrylate, and dimethylformamide By reacting in the presence of tetrabutylammonium bromide and 4-tert-butylpyrocatechol, a compound of the following formula (38) or the following formula (39) is obtained.
また、式（３０）の化合物の製造方法において、式（２５）の化合物を添加することなく反応を行うことにより、式（６）の化合物の一つである式（４０）の化合物を得ることができる。 In the method for producing the compound of formula (30), the compound of formula (40) which is one of the compounds of formula (6) is obtained by performing the reaction without adding the compound of formula (25). Can do.
また上記式（３０）〜（４０）の化合物の製造方法と同処方で、式（２７）の化合物を下記式（４１）の化合物に変更することで、式（１１）に含まれる化合物を得ることができる。 Moreover, the compound contained in Formula (11) is obtained by changing the compound of Formula (27) into the compound of following Formula (41) by the same prescription with the manufacturing method of the compound of said Formula (30)-(40). be able to.
上記式（４１）の具体的な製造方法としては、例えば、ＮＨ2−Ｙ−ＮＨ2、シアノ酢酸エチル、アセト酢酸エチルの混合物をピペリジン存在下で反応させることにより、Ｒ27およびＲ28がメチル基、Ｒ29およびＲ30がシアノ基となる二量体ピリドン化合物が得られる。 As a specific production method of the above formula (41), for example, by reacting a mixture of NH 2 —Y—NH 2 , ethyl cyanoacetate and ethyl acetoacetate in the presence of piperidine, R 27 and R 28 are methylated. A dimeric pyridone compound is obtained in which the groups R 29 and R 30 are cyano groups.
また上記式（３０）〜（４０）の製造方法と同処方で、式（２６）の化合物を下記式（４２）の化合物に変更することで、式（１７）に含まれる化合物を得ることができる。 Moreover, the compound contained in Formula (17) is obtained by changing the compound of Formula (26) into the compound of following Formula (42) by the same formulation as the manufacturing method of said Formula (30)-(40). it can.
上記式（４２）の化合物については、上記式（２６）の化合物の製造方法と同処方で、式（２５）の化合物を複素環、ＨＯ−Ｒ53−ＯＨまたはＲ54ＨＮ−Ｌ2−ＮＨＲ55（Ｒ53は、式（１９）のものと同じ意味を表し、Ｌ2、Ｒ54、Ｒ55は、式（２０）のものと同じ意味を表す。）に変更し、前記化合物に対して式（２４）の化合物を二当量反応させることで得られる。 For compounds of formula (42), in the manufacturing method of the same formulation of the compound of the formula (26), a heterocyclic compound of formula (25), HO-R 53 -OH or R 54 HN-L 2 -NHR 55 (R 53 represents the same meaning as in formula (19), L 2, R 54, R 55 is. representing the same meaning as in formula (20)) was changed to, relative to the compound It can be obtained by reacting the compound of formula (24) with two equivalents.
本発明のアゾ化合物は特にインクジェット記録液用色素およびフェルトペンのインク用色素として非常に有用であり、記録液用色素として色調再現性が優れており、光学濃度が高く、色調がシャープで、かつ太陽光を初めとして種々の光に対しての変退色、耐水性、耐湿性といった画像堅牢性に優れており、かつ保存または使用時における高温または低温による色素溶解液の安定性に優れているため、噴出機（インクヘッド）の目詰まりもなく、噴出安定性が非常に良好である。さらにフェルトペンのインク用色素としても色調再現性が優れており、光学濃度が高く、色調がシャープで、かつ太陽光を初めとして種々の光に対しての変退色、耐水性、耐湿性といった画像堅牢性に優れており、かつ保存または使用時における高温または低温による色素溶解液の安定性に優れている。 The azo compound of the present invention is particularly useful as a dye for ink jet recording liquid and a dye for ink of a felt pen, has excellent color tone reproducibility as a dye for recording liquid, has high optical density, sharp color tone, and Excellent color fastness such as discoloration, water resistance and moisture resistance to various kinds of light including sunlight, and excellent stability of dye solution at high or low temperature during storage or use The jetting machine (ink head) is not clogged and the jetting stability is very good. Furthermore, it has excellent color tone reproducibility as a pigment for felt pen ink, has high optical density, sharp color tone, and images such as fading, water resistance, and moisture resistance to various types of light including sunlight. It has excellent fastness properties and excellent stability of the dye solution at high or low temperatures during storage or use.
また本発明のアゾ化合物は特にインクジェット記録液用色素およびフェルトペンのインク用色素として、特に優れた特性を有しているが、その他ボールペン、万年筆等の筆記具用の記録液用色素にも利用できる。
これら種々の性能に対し、本発明のアゾ化合物は従来に見られない優れた特徴を有すると言える。
The azo compound of the present invention has particularly excellent characteristics, particularly as a dye for ink jet recording liquids and a dye for felt pens, but can also be used for recording liquid dyes for writing instruments such as ballpoint pens and fountain pens. .
For these various performances, it can be said that the azo compound of the present invention has excellent characteristics not seen in the past.
以下に本発明を実施例により説明するが、本発明は実施例に限定されるものではない。なお実施例中の部および％はそれぞれ重量部および重量％を意味する。
［実施例１］
＜化合物（Ｄ−１０）の合成＞
４−（β−スルファトエチルスルホニル）アニリン １４１部を水 １７００部を加えた後、Ｎ−メチルアミノエタノール ３８部および水酸化ナトリウム ６０部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ４００部添加し、４０％亜硝酸ナトリウム水溶液 ８７部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で３０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In the examples, parts and% mean parts by weight and% by weight, respectively.
[Example 1]
<Synthesis of Compound (D-10)>
After 141 parts of 4- (β-sulfatoethylsulfonyl) aniline and 1700 parts of water were added, 38 parts of N-methylaminoethanol and 60 parts of sodium hydroxide were added and stirred at 80 ° C. for 3 hours. After cooling to room temperature, 400 parts of concentrated hydrochloric acid was added, and 87 parts of 40% sodium nitrite aqueous solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 30 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドン １０３部、水 １５００部、ソーダ灰 ３５部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで下記式（Ｉ−１）の色素２３０部を得た。
This diazotized product was dissolved in 103 parts of 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone, 1500 parts of water and 35 parts of soda ash in a 10% aqueous sodium hydroxide solution at pH = 7.0. It was added dropwise at 5 to 10 ° C. over 1 hour while maintaining ˜8.0. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and then the obtained wet cake was dried to obtain 230 parts of a dye of the following formula (I-1).
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１０）で表される色素 ２５.３部を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 25.3 parts of the pigment represented by the formula (D-10). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例２］
＜化合物（Ｄ−１１）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をテトラヒドロフラン５００部に溶解後、遮光しながらメタクリロイルクロリド ５.７部、ピリジン ４.３部を添加し、２０〜３０℃で３時間撹拌した。
[Example 2]
<Synthesis of Compound (D-11)>
After dissolving 23.8 parts of the dye of the above formula (I-1) synthesized in Example 1 in 500 parts of tetrahydrofuran, 5.7 parts of methacryloyl chloride and 4.3 parts of pyridine were added while shielding light, and 20 to 20 Stir at 30 ° C. for 3 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１１）で表される色素 ２６.１部を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 26.1 parts of the pigment represented by the formula (D-11). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例３］
＜化合物（Ｄ−１２）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をテトラヒドロフラン５００部に溶解後、ヘキサメチレンジアミン ０.０２部およびジラウリン酸ジブチルスズ（II）０.１部を添加した。そこに遮光しながら２−イソシアナートエチルアクリレート ７.８部をゆっくり添加し、４０℃で４時間撹拌した。
[Example 3]
<Synthesis of Compound (D-12)>
After dissolving 23.8 parts of the dye of the formula (I-1) synthesized in Example 1 in 500 parts of tetrahydrofuran, 0.02 part of hexamethylenediamine and 0.1 part of dibutyltin (II) dilaurate were added. . 7.8 parts of 2-isocyanate ethyl acrylate was slowly added thereto while shielding light, and stirred at 40 ° C. for 4 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１２）で表される色素 ２７.８部を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 27.8 parts of the pigment represented by the formula (D-12). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例４］
＜化合物（Ｄ−１３）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をテトラヒドロフラン ５００部に溶解後、ヘキサメチレンジアミン ０.０２部およびジラウリン酸ジブチルスズ（II）０.１部を添加した。そこに遮光しながら２−イソシアナートエチルメタクリレート ８.５部をゆっくり添加し、４０℃で４時間撹拌した。
[Example 4]
<Synthesis of Compound (D-13)>
After dissolving 23.8 parts of the dye of the formula (I-1) synthesized in Example 1 in 500 parts of tetrahydrofuran, 0.02 part of hexamethylenediamine and 0.1 part of dibutyltin dilaurate (II) were added. . Thereto was slowly added 8.5 parts of 2-isocyanatoethyl methacrylate while being shielded from light, and the mixture was stirred at 40 ° C. for 4 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下し た。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１３）で表される色素 ２７.８部を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 27.8 parts of the pigment represented by the formula (D-13). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例５］
＜化合物（Ｄ−１４）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をテトラヒドロフラン５００部に溶解後、遮光しながらｐ−スチレンスルホニルクロリド １０.６部、トリエチルアミン ５.３部を添加し、２０〜３０℃で３時間撹拌した。
[Example 5]
<Synthesis of Compound (D-14)>
After dissolving 23.8 parts of the dye of the above formula (I-1) synthesized in Example 1 in 500 parts of tetrahydrofuran, 10.6 parts of p-styrenesulfonyl chloride and 5.3 parts of triethylamine were added while shielding from light. It stirred at 20-30 degreeC for 3 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下し た。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１４）で表される色素 ２９.９部を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the resulting wet cake was dried to obtain 29.9 parts of the pigment represented by the formula (D-14). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例６］
＜化合物（Ｄ−１５）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をジメチルホルムアミド ２００部に溶解後、遮光しながらテトラブチルアンモニウムブロミド ０.２部、４−ｔｅｒｔ−ブチルピロカテコール ０.４部、２−ヒドロキシエチルアクリレート １７.４部を添加し、１２０〜１３０℃で５時間撹拌した。
[Example 6]
<Synthesis of Compound (D-15)>
After dissolving 23.8 parts of the dye of the above formula (I-1) synthesized in Example 1 in 200 parts of dimethylformamide, 0.2 part of tetrabutylammonium bromide and 4-tert-butylpyrocatechol 0 were protected from light. .4 parts and 17.4 parts of 2-hydroxyethyl acrylate were added and stirred at 120-130 ° C. for 5 hours.
得られた反応液を水 １０００部に滴下し、析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１５）で表される色素 ２５.８部を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。 The obtained reaction liquid was added dropwise to 1000 parts of water, and the precipitated dye was filtered off, washed with water, and the resulting wet cake was dried to obtain a dye represented by the formula (D-15) 25. 8 parts were obtained. The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例７］
＜化合物（Ｄ−１６）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をジメチルホルムアミド ２００部に溶解後、遮光しながらテトラブチルアンモニウムブロミド ０.２部、４−ｔｅｒｔ−ブチルピロカテコール ０.４部、２−ヒドロキシエチルメタクリレート１９.５部を添加し、１２０〜１３０℃で５時間撹拌した。
[Example 7]
<Synthesis of Compound (D-16)>
After dissolving 23.8 parts of the dye of the above formula (I-1) synthesized in Example 1 in 200 parts of dimethylformamide, 0.2 part of tetrabutylammonium bromide and 4-tert-butylpyrocatechol 0 were protected from light. .4 parts and 19.5 parts of 2-hydroxyethyl methacrylate were added and stirred at 120 to 130 ° C. for 5 hours.
得られた反応液を水 １０００部に滴下し、析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１６）で表される色素 ２５.８部を得た。この色素の最大吸収波長は４２１.５ｎｍ（酢酸エチル中）であった。 The obtained reaction liquid was added dropwise to 1000 parts of water, the precipitated dye was filtered off, washed with water, and then the resulting wet cake was dried to obtain the dye represented by the formula (D-16) 25. 8 parts were obtained. The maximum absorption wavelength of this dye was 421.5 nm (in ethyl acetate).
［実施例８］
＜化合物（Ｄ−１７）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をジメチルホルムアミド ２００部に溶解後、遮光しながらテトラブチルアンモニウムブロミド ０.２部、４−ｔｅｒｔ−ブチルピロカテコール ０.４部、グリシジルアクリレート １９.２部を添加し、１２０〜１３０℃で４時間撹拌した。
[Example 8]
<Synthesis of Compound (D-17)>
After dissolving 23.8 parts of the dye of the above formula (I-1) synthesized in Example 1 in 200 parts of dimethylformamide, 0.2 part of tetrabutylammonium bromide and 4-tert-butylpyrocatechol 0 were protected from light. .4 parts and 19.2 parts of glycidyl acrylate were added and stirred at 120-130 ° C. for 4 hours.
得られた反応液を水 １０００部に滴下し、析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１７）で表される色素 ２８.１部を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。 The obtained reaction liquid was added dropwise to 1000 parts of water, the precipitated dye was filtered off, washed with water, and then the wet cake obtained was dried to give the dye represented by the formula (D-17) 28. 1 part was obtained. The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例９］
＜化合物（Ｄ−１８）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をジメチルホルムアミド ２００部に溶解後、遮光しながらテトラブチルアンモニウムブロミド ０.２部、４−ｔｅｒｔ−ブチルピロカテコール ０.４部、グリシジルメタクリレート ２１.３部を添加し、１２０〜１３０℃で４時間撹拌した。
[Example 9]
<Synthesis of Compound (D-18)>
After dissolving 23.8 parts of the dye of the above formula (I-1) synthesized in Example 1 in 200 parts of dimethylformamide, 0.2 part of tetrabutylammonium bromide and 4-tert-butylpyrocatechol 0 were protected from light. .4 parts and 21.3 parts of glycidyl methacrylate were added and stirred at 120 to 130 ° C. for 4 hours.
得られた反応液を水 １０００部に滴下し、析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１８）で表される色素 ２８.７部を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。 The obtained reaction liquid was added dropwise to 1000 parts of water, and the precipitated dye was filtered off, washed with water, and the resulting wet cake was dried to give a dye represented by the formula (D-18) 28. 7 parts were obtained. The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例１０］
＜化合物（Ｄ−６４）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をテトラヒドロフラン５００部に溶解後、遮光しながらビニルスルホニルクロリド ７.０部、トリエチルアミン ５.３部を添加し、２０〜３０℃で３時間撹拌した。
[Example 10]
<Synthesis of Compound (D-64)>
After dissolving 23.8 parts of the dye of the formula (I-1) synthesized in Example 1 in 500 parts of tetrahydrofuran, 7.0 parts of vinylsulfonyl chloride and 5.3 parts of triethylamine were added while shielding from light. Stir at ~ 30 ° C for 3 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−
６４）で表される色素 ２６.１部を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and the resulting wet cake was dried to obtain the formula (D-
26.1 parts of the dye represented by (64) was obtained. The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例１１］
＜化合物（Ｄ−６５）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をテトラヒドロフラン５００部に溶解後、遮光しながらアリルスルホニルクロリド ７.７部、トリエチルアミン ５.３部を添加し、２０〜３０℃で３時間撹拌した。
[Example 11]
<Synthesis of Compound (D-65)>
After dissolving 23.8 parts of the dye of the above formula (I-1) synthesized in Example 1 in 500 parts of tetrahydrofuran, 7.7 parts of allylsulfonyl chloride and 5.3 parts of triethylamine were added while being protected from light. Stir at ~ 30 ° C for 3 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−６５）で表される色素 ２６.２部を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and the resulting wet cake was dried to obtain 26.2 parts of the pigment represented by the formula (D-65). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１２］
＜化合物（Ｄ−６６）の合成＞
実施例１にて合成された前記式（Ｉ−１）の色素 ２３.８部をテトラヒドロフラン５００部に溶解後、遮光しながらメタリルスルホニルクロリド７.８部、トリエチルアミン５.３部を添加し、２０〜３０℃で３時間撹拌した。
[Example 12]
<Synthesis of Compound (D-66)>
After dissolving 23.8 parts of the dye of the formula (I-1) synthesized in Example 1 in 500 parts of tetrahydrofuran, 7.8 parts of methallylsulfonyl chloride and 5.3 parts of triethylamine were added while shielding light. It stirred at 20-30 degreeC for 3 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−６６）で表される色素 ２６.５部を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 26.5 parts of the pigment represented by the formula (D-66). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１３］
＜化合物（Ｃ−1）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３５０部を加えた後、エチレンジアミン ６.３部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 13]
<Synthesis of Compound (C-1)>
After adding 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 6.3 parts of ethylenediamine and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 3 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物をジエチルアニリン １４.６部、水 ３００部、濃塩酸 １１部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ３７.４部を得た。
This diazotized product was added dropwise to a solution of 14.6 parts of diethylaniline, 300 parts of water and 11 parts of concentrated hydrochloric acid at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
The reaction solution was separated by filtration, washed with water, and then the resulting wet cake was dried to obtain 37.4 parts of a dry cake.
得られた乾燥ケーキ ２０.２部をテトラヒドロフラン ５００部に溶解後、遮光しながらアクリロイルクロリド ５.０部、ピリジン ４.３部を添加し、２０〜３０℃で２時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−１）で表される色素 ２０.６部を得た。この色素の最大吸収波長は４５７.０ｎｍ（酢酸エチル中）であった。
After dissolving 20.2 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 5.0 parts of acryloyl chloride and 4.3 parts of pyridine were added while shielding from light, and the mixture was stirred at 20 to 30 ° C. for 2 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 20.6 parts of the pigment represented by the formula (C-1). The maximum absorption wavelength of this dye was 457.0 nm (in ethyl acetate).
［実施例１４］
＜化合物（Ｃ−２）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３５０部を加えた
後、２８％アンモニア水 ６３部および水酸化ナトリウム １２部を添加し、８０℃で５時間撹拌した。常温まで冷却後、濃塩酸１２０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 14]
<Synthesis of Compound (C-2)>
After adding 350 parts of water to 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline, 63 parts of 28% aqueous ammonia and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 5 hours. After cooling to room temperature, 120 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物をフェノール ９.８部、水 ２００部、水酸化ナトリウム ４.３部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ２９.０部を得た。
This diazotized product was dissolved in a solution of 9.8 parts of phenol, 200 parts of water, and 4.3 parts of sodium hydroxide at 5 to 10 ° C. while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. The solution was added dropwise over 1 hour. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the resulting wet cake was dried to obtain 29.0 parts of a dry cake.
得られた乾燥ケーキ １５.３部をテトラヒドロフラン ５００部に溶解後、ヘキサメチレンジアミン ０.０２部およびジラウリン酸ジブチルスズ（II）０.１部を添加した。そこに遮光しながら２−イソシアナートエチルアクリレート ７.８部をゆっくり添加し、４０℃で４時間撹拌した。 After dissolving 15.3 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 0.02 part of hexamethylenediamine and 0.1 part of dibutyltin (II) dilaurate were added. 7.8 parts of 2-isocyanate ethyl acrylate was slowly added thereto while shielding light, and stirred at 40 ° C. for 4 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−２）で表される色素 ２１.４部を得た。この色素の最大吸収波長は４４９.５ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 21.4 parts of the pigment represented by the formula (C-2). The maximum absorption wavelength of this dye was 449.5 nm (in ethyl acetate).
［実施例１５］
＜化合物（Ｃ−３）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３５０部を加えた後、ジエタノールアミン １１部および水酸化ナトリウム １２部を添加し、８０℃で５時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 15]
<Synthesis of Compound (C-3)>
After adding 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 11 parts of diethanolamine and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 5 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物をフェニルＪ酸 ３１.７部、水 ５００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
撹拌後、トリ−ｎ−オクチルアミン ３６部、６２.５％硫酸 ３０部を添加し、７０〜８０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ７９.６部を得た。
This diazotized product was added dropwise to a solution of 31.7 parts of phenyl J acid, 500 parts of water, and 4.2 parts of sodium hydroxide at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
After stirring, 36 parts of tri-n-octylamine and 30 parts of 62.5% sulfuric acid were added and stirred at 70-80 ° C. for 2 hours.
The reaction solution was filtered off and washed with water, and then the resulting wet cake was dried to obtain 79.6 parts of a dry cake.
得られた乾燥ケーキ ４３.８部をテトラヒドロフラン ５００部に溶解後、遮光しながらアクリロイルクロリド １０.０部、ピリジン ８.６部を添加し、２０〜３０℃で２時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−３）で表される色素 ４２.４部を得た。この色素の最大吸収波長は５１０.０ｎｍ（酢酸エチル中）であった。
After dissolving 43.8 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 10.0 parts of acryloyl chloride and 8.6 parts of pyridine were added while shielding light, and stirred at 20 to 30 ° C. for 2 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the resulting wet cake was dried to obtain 42.4 parts of a pigment represented by the formula (C-3). The maximum absorption wavelength of this dye was 510.0 nm (in ethyl acetate).
［実施例１６］
＜化合物（Ｃ−４）の合成＞
２−メトキシ−５−メチル−４−（β−スルファトエチルスルホニル）アニリン ３２.５部を水 ３５０部を加えた後、水酸化ナトリウム １２部を添加し、８０℃で６時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を
５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 16]
<Synthesis of Compound (C-4)>
After adding 32.5 parts of 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 12 parts of sodium hydroxide was added and stirred at 80 ° C. for 6 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を１−ナフトール−３，６−ジスルホン酸 ３０.７部、水 ５００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で３時間撹拌した。
撹拌後、トリ−ｎ−オクチルアミン ７１部、６２.５％硫酸 ３０部を添加し、７０〜８０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ １１３.９部を得た。
This diazotized product was added dropwise to a solution of 30.7 parts of 1-naphthol-3,6-disulfonic acid, 500 parts of water, and 4.2 parts of sodium hydroxide at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 3 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
After stirring, 71 parts of tri-n-octylamine and 30 parts of 62.5% sulfuric acid were added and stirred at 70 to 80 ° C. for 2 hours.
The reaction solution was filtered off and washed with water, and then the resulting wet cake was dried to obtain 113.9 parts of a dry cake.
得られた乾燥ケーキ ６３.３部をテトラヒドロフラン ５００部に溶解後、ヘキサメチレンジアミン ０.０２部およびジラウリン酸ジブチルスズ（II）０.１部を添加した。そこに遮光しながら２−イソシアナートエチルアクリレート ７.８部をゆっくり添加し、４０℃で５時間撹拌した。 63.3 parts of the obtained dried cake was dissolved in 500 parts of tetrahydrofuran, 0.02 part of hexamethylenediamine and 0.1 part of dibutyltin (II) dilaurate were added. 7.8 parts of 2-isocyanatoethyl acrylate was slowly added thereto while shielding light, and stirred at 40 ° C. for 5 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−４）で表される色素 ６４.７部を得た。この色素の最大吸収波長は５１６.０ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 64.7 parts of the pigment represented by the formula (C-4). The maximum absorption wavelength of this dye was 516.0 nm (in ethyl acetate).
［実施例１７］
＜化合物（Ｃ−５）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３５０部を加えた後、水酸化ナトリウム １２部を添加し、８０℃で５時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 17]
<Synthesis of Compound (C-5)>
After adding 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 12 parts of sodium hydroxide was added and stirred at 80 ° C. for 5 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を下記式（Ｉ−２）の化合物３６.８部、水 ５００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ５６.８部を得た。
This diazotized product was added dropwise to a solution of 36.8 parts of the compound of the following formula (I-2), 500 parts of water, and 4.2 parts of sodium hydroxide at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
The reaction solution was filtered off and washed with water, and then the resulting wet cake was dried to obtain 56.8 parts of a dry cake.
得られた乾燥ケーキ ２８.９部をテトラヒドロフラン ５００部に溶解後、遮光しながらアクリロイルクロリド ５.０部、ピリジン ４.３部を添加し、２０〜３０℃で２時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−５）で表される色素 ３０.０部を得た。この色素の最大吸収波長は３９６.０ｎｍ（酢酸エチル中）であった。
After dissolving 28.9 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 5.0 parts of acryloyl chloride and 4.3 parts of pyridine were added while being shielded from light, and the mixture was stirred at 20 to 30 ° C. for 2 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 30.0 parts of the pigment represented by the formula (C-5). The maximum absorption wavelength of this dye was 396.0 nm (in ethyl acetate).
［実施例１８］
＜化合物（Ｃ−６）の合成＞
３−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３５０部を加えた後、Ｎ−メチルアミノエタノール ７.７部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 18]
<Synthesis of Compound (C-6)>
After adding 28.1 parts of 3- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 7.7 parts of N-methylaminoethanol and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 3 hours. . After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を下記式（Ｉ−３）の化合物３９.６部、水 ３００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ６３.６部を得た。
The diazotized product was added dropwise to a solution of 39.6 parts of the compound of the following formula (I-3), 300 parts of water and 4.2 parts of sodium hydroxide at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
The reaction solution was filtered off and washed with water, and then the resulting wet cake was dried to obtain 63.6 parts of a dry cake.
得られた乾燥ケーキ ３３.１部をテトラヒドロフラン ５００部に溶解後、遮光しながらメタクリロイルクロリド ５.７部、ピリジン ４.３部を添加し、２０〜３０℃で３時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−６）で表される色素 ３５.３部を得た。この色素の最大吸収波長は３９２.５ｎｍ（酢酸エチル中）であった。
After 33.1 parts of the obtained dry cake was dissolved in 500 parts of tetrahydrofuran, 5.7 parts of methacryloyl chloride and 4.3 parts of pyridine were added while shielding light, and stirred at 20 to 30 ° C. for 3 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 35.3 parts of the pigment represented by the formula (C-6). The maximum absorption wavelength of this dye was 392.5 nm (in ethyl acetate).
［実施例１９］
＜化合物（Ｃ−７）の合成＞
２−エトキシ−４−（β−スルファトエチルスルホニル）アニリン ３２.５部を水３５０部を加えた後、2-エチルヘキシルアミン １３.５部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 19]
<Synthesis of Compound (C-7)>
3-Ethoxy-4- (β-sulfatoethylsulfonyl) aniline (32.5 parts) was added with 350 parts of water, 13.5 parts of 2-ethylhexylamine and 12 parts of sodium hydroxide were added, and Stir for hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物をバツビツル酸 １３.０部、水 ３００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ４９.０部を得た。
This diazotized product was added dropwise to a solution of 13.0 parts of barbituric acid, 300 parts of water, and 4.2 parts of sodium hydroxide at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
The reaction solution was filtered off and washed with water, and then the resulting wet cake was dried to obtain 49.0 parts of a dry cake.
得られた乾燥ケーキ ２４.８部をテトラヒドロフラン ５００部に溶解後、遮光しながらアクリロイルクロリド ５.０部、ピリジン ４.３部を添加し、２０〜３０℃で６時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−７）で表される色素 ２６.４部を得た。この色素の最大吸収波長は３９９.０ｎｍ（酢酸
エチル中）であった。
After dissolving 24.8 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 5.0 parts of acryloyl chloride and 4.3 parts of pyridine were added while being shielded from light, and the mixture was stirred at 20 to 30 ° C. for 6 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 26.4 parts of the pigment represented by the formula (C-7). The maximum absorption wavelength of this dye was 399.0 nm (in ethyl acetate).
［実施例２０］
＜化合物（Ｃ−８）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３５０部を加えた後、３,３'−ジアミノジプロピルアミン １３.６部および水酸化ナトリウム １２部を添加し、８０℃で２時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 20]
<Synthesis of Compound (C-8)>
After adding 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 13.6 parts of 3,3′-diaminodipropylamine and 12 parts of sodium hydroxide were added at 80 ° C. Stir for 2 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物をＮ,Ｎ'−ジブチルバツビツル酸 ２４.２部、水 ３００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ５１.９部を得た。
This diazotized product was added dropwise to a solution of 24.2 parts of N, N′-dibutylbabituric acid, 300 parts of water and 4.2 parts of sodium hydroxide at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
The reaction solution was separated by filtration, washed with water, and then the resulting wet cake was dried to obtain 51.9 parts of a dry cake.
得られた乾燥ケーキ ２６.６部をテトラヒドロフラン ５００部に溶解後、遮光しながらアクリロイルクロリド １０.０部、ピリジン ８.６部を添加し、２０〜３０℃で１時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−８）で表される色素 ２９.７部を得た。この色素の最大吸収波長は４０４.０ｎｍ（酢酸エチル中）であった。
After dissolving 26.6 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 10.0 parts of acryloyl chloride and 8.6 parts of pyridine were added while shielding light, and the mixture was stirred at 20 to 30 ° C. for 1 hour.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 29.7 parts of the pigment represented by the formula (C-8). The maximum absorption wavelength of this dye was 404.0 nm (in ethyl acetate).
［実施例２１］
＜化合物（Ｃ−９）の合成＞
３−メチル−４−（β−スルファトエチルスルホニル）アニリン ２９.５部を水 ３５０部を加えた後、Ｎ−メチルエチレンジアミン ７.６部および水酸化ナトリウム １２部を添加し、８０℃で２時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 21]
<Synthesis of Compound (C-9)>
After adding 29.5 parts of 3-methyl-4- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 7.6 parts of N-methylethylenediamine and 12 parts of sodium hydroxide were added. Stir for hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−エチルヘキシル）−２−ピリドン ２６.５部、水 ３００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ５２.８部を得た。
This diazotized product was dissolved in a solution of 26.5 parts of 3-cyano-4-methyl-6-hydroxy-N- (2-ethylhexyl) -2-pyridone, 300 parts of water and 4.2 parts of sodium hydroxide in an amount of 5-10. The solution was added dropwise at 30 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
The reaction solution was filtered off and washed with water, and then the resulting wet cake was dried to obtain 52.8 parts of a dry cake.
得られた乾燥ケーキ ２７.２部をテトラヒドロフラン ５００部に溶解後、遮光しながらｐ−スチレンスルホニルクロリド １０.６部、トリエチルアミン ５.３部を添加し、２０〜３０℃で２時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水１０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−９）で表される色素 ３３.９部を得た。この色素の最大吸収波長は４２６.５ｎｍ（酢酸エチル中）であった。
After dissolving 27.2 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 10.6 parts of p-styrenesulfonyl chloride and 5.3 parts of triethylamine were added while shielding light, and the mixture was stirred at 20 to 30 ° C. for 2 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and then the obtained wet cake was dried to obtain 33.9 parts of a pigment represented by the formula (C-9). The maximum absorption wavelength of this dye was 426.5 nm (in ethyl acetate).
［実施例２２］
＜化合物（Ｃ−１０）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３５０部を加えた
後、Ｎ,Ｎ−ジエチルアミノエチルアミン １２.０部および水酸化ナトリウム １２部を添加し、８０℃で４時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 22]
<Synthesis of Compound (C-10)>
2- (β-sulfatoethylsulfonyl) aniline (28.1 parts) and water (350 parts) were added, N, N-diethylaminoethylamine (12.0 parts) and sodium hydroxide (12 parts) were added, and the mixture was stirred at 80 ° C. for 4 hours. did. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−ヒドロキシエチル）−２−ピリドン １９.８部、水 ３００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ４８.４部を得た。
The diazotized product was dissolved in a solution of 19.8 parts of 3-cyano-4-methyl-6-hydroxy-N- (2-hydroxyethyl) -2-pyridone, 300 parts of water and 4.2 parts of sodium hydroxide in 5 to 5 parts. The solution was added dropwise at 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
The reaction solution was filtered off and washed with water, and then the resulting wet cake was dried to obtain 48.4 parts of a dry cake.
得られた乾燥ケーキ ２５.２部をジメチルホルムアミド ２００部に溶解後、遮光しながらテトラブチルアンモニウムブロミド ０.２部、４−ｔｅｒｔ−ブチルピロカテコール
０.４部、グリシジルメタクリレート ２１.３部を添加し、１２０〜１３０℃で４時間撹拌した。
25.2 parts of the resulting dried cake was dissolved in 200 parts of dimethylformamide, and then 0.2 part of tetrabutylammonium bromide, 0.4 part of 4-tert-butylpyrocatechol, and 21.3 parts of glycidyl methacrylate were added while shielding from light. And stirred at 120-130 ° C. for 4 hours.
得られた反応液を水 １０００部に滴下し、析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−１０）で表される色素 ３０.５部を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。 The obtained reaction liquid was added dropwise to 1000 parts of water, and the precipitated dye was filtered off, washed with water, and the resulting wet cake was dried to obtain a dye represented by the formula (C-10) 30. 5 parts were obtained. The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例２３］
＜化合物（Ｃ−１１）の合成＞
３−メトキシ−４−（β−スルファトエチルスルホニル）アニリン ３１.１部を水３５０部を加えた後、水酸化ナトリウム １２部を添加し、８０℃で６時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 23]
<Synthesis of Compound (C-11)>
After 31.1 parts of 3-methoxy-4- (β-sulfatoethylsulfonyl) aniline was added with 350 parts of water, 12 parts of sodium hydroxide was added and stirred at 80 ° C. for 6 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドン ２１.０部、水 ３００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ４２.４部を得た。
This diazotized product was dissolved in a solution of 21.0 parts of 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone, 300 parts of water, and 4.2 parts of sodium hydroxide at 5 to 10 ° C. for 30 minutes. It was dripped over. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
The reaction solution was filtered off and washed with water, and then the resulting wet cake was dried to obtain 42.4 parts of a dry cake.
得られた乾燥ケーキ ２２.５部をジメチルホルムアミド ２００部に溶解後、遮光しながらテトラブチルアンモニウムブロミド ０.２部、４−ｔｅｒｔ−ブチルピロカテコール
０.４部、２−ヒドロキシエチルメタクリレート １９.５部を添加し、１２０〜１３０℃で５時間撹拌した。
22.5 parts of the obtained dry cake was dissolved in 200 parts of dimethylformamide, and then 0.2 parts of tetrabutylammonium bromide, 0.4 parts of 4-tert-butylpyrocatechol, and 19.5 of 2-hydroxyethyl methacrylate while being protected from light. Part was added and stirred at 120-130 ° C. for 5 hours.
得られた反応液を水 １０００部に滴下し、析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−１１）で表される色素 ２５.８部を得た。この色素の最大吸収波長は４２７.０ｎｍ（酢酸エチル中）であった。 The obtained reaction liquid was dropped into 1000 parts of water, the precipitated dye was filtered off, washed with water, and then the wet cake obtained was dried, thereby the dye represented by the formula (C-11) 25. 8 parts were obtained. The maximum absorption wavelength of this dye was 427.0 nm (in ethyl acetate).
［実施例２４］
＜化合物（Ｃ−１２）の合成＞
３−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３５０部を加えた後、２−エチルヘキシルアミン １３.４部および水酸化ナトリウム １２部を添加し、８０℃で４時間撹拌した。常温まで冷却後、濃塩酸８０部添加し、４０％亜硝酸ナトリウム
水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 24]
<Synthesis of Compound (C-12)>
After adding 28.1 parts of 3- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 13.4 parts of 2-ethylhexylamine and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 4 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of 40% sodium nitrite aqueous solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−ヒドロキシエチル）−２−ピリドン １９.８部、水 ３００部、水酸化ナトリウム ４.２部の溶解液に５〜１０℃で３０分かけて滴下した。滴下後、１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ５０.５部を得た。
The diazotized product was dissolved in a solution of 19.8 parts of 3-cyano-4-methyl-6-hydroxy-N- (2-hydroxyethyl) -2-pyridone, 300 parts of water and 4.2 parts of sodium hydroxide in 5 to 5 parts. The solution was added dropwise at 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution.
The reaction solution was separated by filtration, washed with water, and then the resulting wet cake was dried to obtain 50.5 parts of a dry cake.
得られた乾燥ケーキ ２５.９部をテトラヒドロフラン ５００部に溶解後、遮光しながらビニルスルホニルクロリド ７.０部、トリエチルアミン ５.３部を添加し、２０〜３０℃で３時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下し、
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｃ−１２）で表される色素 ２８.３部を得た。この色素の最大吸収波長は４１７.５ｎｍ（酢酸エチル中）であった。
25.9 parts of the obtained dried cake was dissolved in 500 parts of tetrahydrofuran, 7.0 parts of vinylsulfonyl chloride and 5.3 parts of triethylamine were added while shielding light, and the mixture was stirred at 20 to 30 ° C. for 3 hours.
The obtained reaction solution was concentrated to 100 parts in a vacuum, and the concentrated solution was dropped into 1000 parts of water,
The precipitated pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 28.3 parts of the pigment represented by the formula (C-12). The maximum absorption wavelength of this dye was 417.5 nm (in ethyl acetate).
［実施例２５］
＜化合物（Ｄ−１）の合成＞
４−（β−スルファトエチルスルホニル）アニリン １４１部を水 １７００部を加えた後、水酸化ナトリウム ６０部を添加し、８０℃で６時間撹拌した。常温まで冷却後、濃塩酸 ４００部添加し、４０％亜硝酸ナトリウム水溶液 ８７部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で３０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 25]
<Synthesis of Compound (D-1)>
After 141 parts of 4- (β-sulfatoethylsulfonyl) aniline and 1700 parts of water were added, 60 parts of sodium hydroxide was added and stirred at 80 ° C. for 6 hours. After cooling to room temperature, 400 parts of concentrated hydrochloric acid was added, and 87 parts of 40% sodium nitrite aqueous solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 30 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドン １０３部、水 １５００部、ソーダ灰 ３５部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで下記式（Ｉ−４）の色素 ２０５部を得た。
This diazotized product was dissolved in 103 parts of 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone, 1500 parts of water and 35 parts of soda ash in a 10% aqueous sodium hydroxide solution at pH = 7.0. It was added dropwise at 5 to 10 ° C. over 1 hour while maintaining ˜8.0. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and then the resulting wet cake was dried to obtain 205 parts of a dye of the following formula (I-4).
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−１）で表される色素 ２２.２部を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 22.2 parts of the pigment represented by the formula (D-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例２６］
＜化合物（Ｄ−２）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例２と同様
に行うことで式（Ｄ−２）の色素を得た。この色素の最大吸収波長は４２１.５ｎｍ（酢酸エチル中）であった。
[Example 26]
<Synthesis of Compound (D-2)>
The dye of the formula (D-2) was obtained in the same manner as in Example 2 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 421.5 nm (in ethyl acetate).
［実施例２７］
＜化合物（Ｄ−３）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｄ−３）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 27]
<Synthesis of Compound (D-3)>
The dye of the formula (D-3) was obtained in the same manner as in Example 3 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例２８］
＜化合物（Ｄ−４）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例４と同様に行うことで式（Ｄ−４）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 28]
<Synthesis of Compound (D-4)>
The dye of the formula (D-4) was obtained in the same manner as in Example 4 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例２９］
＜化合物（Ｄ−５）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例５と同様に行うことで式（Ｄ−５）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 29]
<Synthesis of Compound (D-5)>
The dye of the formula (D-5) was obtained in the same manner as in Example 5 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例３０］
＜化合物（Ｄ−６）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例６と同様に行うことで式（Ｄ−６）の色素を得た。この色素の最大吸収波長は４２１.５ｎｍ（酢酸エチル中）であった。
[Example 30]
<Synthesis of Compound (D-6)>
The dye of the formula (D-6) was obtained in the same manner as in Example 6 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 421.5 nm (in ethyl acetate).
［実施例３１］
＜化合物（Ｄ−７）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例７と同様に行うことで式（Ｄ−７）の色素を得た。この色素の最大吸収波長は４２２.０ｍ（酢酸エチル中）であった。
[Example 31]
<Synthesis of Compound (D-7)>
The dye of the formula (D-7) was obtained in the same manner as in Example 7 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 m (in ethyl acetate).
［実施例３２］
＜化合物（Ｄ−８）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例８と同様に行うことで式（Ｄ−８）の色素を得た。この色素の最大吸収波長は４２２.５ｍ（酢酸エチル中）であった。
[Example 32]
<Synthesis of Compound (D-8)>
The dye of formula (D-8) was obtained in the same manner as in Example 8 except that the dye of formula (I-4) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 422.5 m (in ethyl acetate).
［実施例３３］
＜化合物（Ｄ−９）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例９と同様に行うことで式（Ｄ−９）の色素を得た。この色素の最大吸収波長は４２３.０ｍ（酢酸エチル中）であった。
[Example 33]
<Synthesis of Compound (D-9)>
The dye of the formula (D-9) was obtained in the same manner as in Example 9 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 m (in ethyl acetate).
［実施例３４］
＜化合物（Ｄ−１９）の合成＞
Ｎ−メチルアミノエタノールに変えて２−エチルヘキシルアミンを、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−ヒドロキシエチル）−２−ピリドンを使用したこと以外は実施例１
と同様に行うことで下記式（Ｉ−５）の色素を得た。
[Example 34]
<Synthesis of Compound (D-19)>
Instead of N-methylaminoethanol, 2-ethylhexylamine is replaced with 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone and 3-cyano-4-methyl-6-hydroxy-N- (2 Example 1 except that -hydroxyethyl) -2-pyridone was used
The dye of the following formula (I-5) was obtained in the same manner as above.
［実施例３５］
＜化合物（Ｄ−２０）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−５）の色素を使用したこと以外は実施例２と同様に行うことで式（Ｄ−２０）の色素を得た。この色素の最大吸収波長は４２３.０ｍ（酢酸エチル中）であった。
[Example 35]
<Synthesis of Compound (D-20)>
The dye of the formula (D-20) was obtained in the same manner as in Example 2 except that the dye of the formula (I-5) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 m (in ethyl acetate).
［実施例３６］
＜化合物（Ｄ−２１）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−５）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｄ−２１）の色素を得た。この色素の最大吸収波長は４２１.５ｍ（酢酸エチル中）であった。
[Example 36]
<Synthesis of Compound (D-21)>
The dye of the formula (D-21) was obtained in the same manner as in Example 3 except that the dye of the formula (I-5) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 421.5 m (in ethyl acetate).
［実施例３７］
＜化合物（Ｄ−２２）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−５）の色素を使用したこと以外は実施例４と同様に行うことで式（Ｄ−２２）の色素を得た。この色素の最大吸収波長は４２２.５ｍ（酢酸エチル中）であった。
[Example 37]
<Synthesis of Compound (D-22)>
The dye of formula (D-22) was obtained in the same manner as in Example 4 except that the dye of formula (I-5) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 422.5 m (in ethyl acetate).
［実施例３８］
＜化合物（Ｄ−２３）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−５）の色素を使用したこと以外は実施例５と同様に行うことで式（Ｄ−２３）の色素を得た。この色素の最大吸収波長は４２３.０ｍ（酢酸エチル中）であった。
[Example 38]
<Synthesis of Compound (D-23)>
The dye of the formula (D-23) was obtained in the same manner as in Example 5 except that the dye of the formula (I-5) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 m (in ethyl acetate).
［実施例３９］
＜化合物（Ｄ−２４）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−５）の色素を使用したこと以外は実施例６と同様に行うことで式（Ｄ−２４）の色素を得た。この色素の最大吸収波長は４２２.０ｍ（酢酸エチル中）であった。
[Example 39]
<Synthesis of Compound (D-24)>
The dye of the formula (D-24) was obtained in the same manner as in Example 6 except that the dye of the formula (I-5) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 m (in ethyl acetate).
［実施例４０］
＜化合物（Ｄ−２５）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−５）の色素を使用したこと以外は実施例７と同様に行うことで式（Ｄ−２５）の色素を得た。この色素の最大吸収波長は４２２.０ｍ（酢酸エチル中）であった。
[Example 40]
<Synthesis of Compound (D-25)>
The dye of the formula (D-25) was obtained in the same manner as in Example 7 except that the dye of the formula (I-5) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 m (in ethyl acetate).
［実施例４１］
＜化合物（Ｄ−２６）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−５）の色素を使用したこと以外は実施例８と同様に行うことで式（Ｄ−２６）の色素を得た。この色素の最大吸収波長は４２２.５ｍ（酢酸エチル中）であった。
[Example 41]
<Synthesis of Compound (D-26)>
The dye of the formula (D-26) was obtained in the same manner as in Example 8 except that the dye of the formula (I-5) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 m (in ethyl acetate).
［実施例４２］
＜化合物（Ｄ−２７）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−５）の色素を使用したこと以外は実施例９と同様に行うことで式（Ｄ−２７）の色素を得た。この色素の最大吸収波長は４２２.５ｍ（酢酸エチル中）であった。
[Example 42]
<Synthesis of Compound (D-27)>
The dye of the formula (D-27) was obtained in the same manner as in Example 9 except that the dye of the formula (I-5) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 m (in ethyl acetate).
［実施例４３］
＜化合物（Ｄ−２８）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−ヒドロキシエチル）−２−ピリドン を使用したこと以外は実施例２５と同様に行うことで下記式（Ｉ−６）の色素を得た。
[Example 43]
<Synthesis of Compound (D-28)>
Using 3-cyano-4-methyl-6-hydroxy-N- (2-hydroxyethyl) -2-pyridone instead of 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone Was carried out in the same manner as in Example 25 to obtain a dye of the following formula (I-6).
［実施例４４］
＜化合物（Ｄ−２９）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−６）の色素を使用したこと以外は実施例２と同様に行うことで式（Ｄ−２９）の色素を得た。この色素の最大吸収波長は４２２.０ｍ（酢酸エチル中）であった。
[Example 44]
<Synthesis of Compound (D-29)>
The dye of the formula (D-29) was obtained in the same manner as in Example 2 except that the dye of the formula (I-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 m (in ethyl acetate).
［実施例４５］
＜化合物（Ｄ−３０）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−６）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｄ−３０）の色素を得た。この色素の最大吸収波長は４２２.５ｍ（酢酸エチル中）であった。
[Example 45]
<Synthesis of Compound (D-30)>
The dye of the formula (D-30) was obtained in the same manner as in Example 3 except that the dye of the formula (I-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 m (in ethyl acetate).
［実施例４６］
＜化合物（Ｄ−３１）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−６）の色素を使用したこと以外は実施例４と同様に行うことで式（Ｄ−３１）の色素を得た。この色素の最大吸収波長は４２２.５ｍ（酢酸エチル中）であった。
[Example 46]
<Synthesis of Compound (D-31)>
The dye of the formula (D-31) was obtained in the same manner as in Example 4 except that the dye of the formula (I-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 m (in ethyl acetate).
［実施例４７］
＜化合物（Ｄ−３２）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−６）の色素を使用したこと以外は実施例６と同様に行うことで式（Ｄ−３２）の色素を得た。この色素の最大吸収波長は４２２.０ｍ（酢酸エチル中）であった。
[Example 47]
<Synthesis of Compound (D-32)>
The dye of the formula (D-32) was obtained in the same manner as in Example 6 except that the dye of the formula (I-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 m (in ethyl acetate).
［実施例４８］
＜化合物（Ｄ−３３）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−６）の色素を使用したこと以外は実施例７と同様に行うことで式（Ｄ−３３）の色素を得た。この色素の最大吸収波長は４２２.５ｍ（酢酸エチル中）であった。
[Example 48]
<Synthesis of Compound (D-33)>
The dye of the formula (D-33) was obtained in the same manner as in Example 7 except that the dye of the formula (I-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 m (in ethyl acetate).
［実施例４９］
＜化合物（Ｄ−３４）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−６）の色素を使用したこと以外は実施例８と同様に行うことで式（Ｄ−３４）の色素を得た。この色素の最大吸収波長は４２１.５ｍ（酢酸エチル中）であった。
[Example 49]
<Synthesis of Compound (D-34)>
The dye of the formula (D-34) was obtained in the same manner as in Example 8 except that the dye of the formula (I-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 421.5 m (in ethyl acetate).
［実施例５０］
＜化合物（Ｄ−３５）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−６）の色素を使用したこと以外は実施例９と同様に行うことで式（Ｄ−３５）の色素を得た。この色素の最大吸収波長は４２２.０ｍ（酢酸エチル中）であった。
[Example 50]
<Synthesis of Compound (D-35)>
The dye of the formula (D-35) was obtained in the same manner as in Example 9 except that the dye of the formula (I-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 m (in ethyl acetate).
［実施例５１］
＜化合物（Ｄ−３６）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンに変えて３−シアノ−４−トリフルオロメチル−６−ヒドロキシ−Ｎ−（２−エチルヘキシル）−２−ピリドンを使用したこと以外は実施例２５と同様に行うことで下記式（Ｉ−７）の色素を得た。
[Example 51]
<Synthesis of Compound (D-36)>
Instead of 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone, 3-cyano-4-trifluoromethyl-6-hydroxy-N- (2-ethylhexyl) -2-pyridone was used. Except for this, the same procedure as in Example 25 was carried out to obtain a dye of the following formula (I-7).
［実施例５２］
＜化合物（Ｄ−３７）の合成＞
Ｎ−メチルアミノエタノールに変えてアンモニア水を、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを３−シアノ−４−エチル−６−ヒドロキシ−Ｎ−エチル−２−ピリドンを使用したこと以外は実施例１と同様に行うことで下記式（Ｉ−８）の色素を得た。
[Example 52]
<Synthesis of Compound (D-37)>
Instead of N-methylaminoethanol, aqueous ammonia was replaced with 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone and 3-cyano-4-ethyl-6-hydroxy-N-ethyl-2- Except having used pyridone, it carried out like Example 1 and the pigment | dye of a following formula (I-8) was obtained.
と同様に行うことで式（Ｄ−３７）の色素を得た。この色素の最大吸収波長は４２５.５ｎｍ（酢酸エチル中）であった。
The dye of formula (D-37) was obtained by carrying out in the same manner as above. The maximum absorption wavelength of this dye was 425.5 nm (in ethyl acetate).
［実施例５３］
＜化合物（Ｄ−３８）の合成＞
２−クロロ−４−（β−スルファトエチルスルホニル）アニリン ３１.６部を水 ３５０部を加えた後、２８％アンモニア水 ６３部および水酸化ナトリウム １２部を添加し、８０℃で５時間撹拌した。常温まで冷却後、濃塩酸 １２０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 53]
<Synthesis of Compound (D-38)>
2-chloro-4- (β-sulfatoethylsulfonyl) aniline (31.6 parts) and water (350 parts) were added, then 28% aqueous ammonia (63 parts) and sodium hydroxide (12 parts) were added, and the mixture was stirred at 80 ° C. for 5 hours. did. After cooling to room temperature, 120 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−カルバモイル−４−メチル−６−ヒドロキシ−Ｎ−ヘキシル−２−ピリドン ２５.２部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで乾燥ケーキ ４７.７部を得た。
This diazotate was dissolved in a solution of 25.2 parts of 3-carbamoyl-4-methyl-6-hydroxy-N-hexyl-2-pyridone, 300 parts of water, and 10 parts of soda ash in a 10% aqueous sodium hydroxide solution at pH = 7. While maintaining 0.0 to 8.0, the solution was added dropwise at 5 to 10 ° C. over 1 hour. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 47.7 parts of a dry cake.
得られた乾燥ケーキ ２４.９部をテトラヒドロフラン５００部に溶解後、遮光しながらメタクリロイルクロリド ５.７部、ピリジン ４.３部を添加し、２０〜３０℃で３時間撹拌した。 24.9 parts of the obtained dried cake was dissolved in 500 parts of tetrahydrofuran, and then 5.7 parts of methacryloyl chloride and 4.3 parts of pyridine were added while shielding from light, followed by stirring at 20 to 30 ° C. for 3 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−３８）で表される色素 ２６.５部を得た。この色素の最大吸収波長は４１９.５ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 26.5 parts of the pigment represented by the formula (D-38). The maximum absorption wavelength of this dye was 419.5 nm (in ethyl acetate).
［実施例５４］
＜化合物（Ｄ−３９）の合成＞
２−メトキシ−４−（β−スルファトエチルスルホニル）アニリン ３１.１部を水 ３５０部を加えた後、２８％アンモニア水 ６３部および水酸化ナトリウム １２部を添加し、８０℃で５時間撹拌した。常温まで冷却後、濃塩酸 １２０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 54]
<Synthesis of Compound (D-39)>
2-methyl-4- (β-sulfatoethylsulfonyl) aniline (31.1 parts) and water (350 parts) were added, and then 28% aqueous ammonia (63 parts) and sodium hydroxide (12 parts) were added and stirred at 80 ° C. for 5 hours. did. After cooling to room temperature, 120 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（３−イソプロポキシプロピル）−２−ピリドン ２５.３部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで乾燥ケーキ ４７.２部を得た。
This diazotized product was 10% hydroxylated in a solution of 25.3 parts of 3-cyano-4-methyl-6-hydroxy-N- (3-isopropoxypropyl) -2-pyridone, 300 parts of water and 10 parts of soda ash. While maintaining pH = 7.0 to 8.0 with an aqueous sodium solution, the solution was added dropwise at 5 to 10 ° C. over 1 hour. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 47.2 parts of a dry cake.
得られた乾燥ケーキ ２４.７部ををテトラヒドロフラン ５００部に溶解後、ヘキサメチレンジアミン ０.０２部およびジラウリン酸ジブチルスズ（II）０.１部を添加した。そこに遮光しながら２−イソシアナートエチルメタクリレート ８.５部をゆっくり添加し、４０℃で４時間撹拌した。 24.7 parts of the obtained dry cake was dissolved in 500 parts of tetrahydrofuran, and 0.02 part of hexamethylenediamine and 0.1 part of dibutyltin (II) dilaurate were added. Thereto was slowly added 8.5 parts of 2-isocyanatoethyl methacrylate while being shielded from light, and the mixture was stirred at 40 ° C. for 4 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−３９）で表される色素 ２９.０部を得た。この色素の最大吸収波長は４２８.０ｎｍ（酢
酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 29.0 parts of the pigment represented by the formula (D-39). The maximum absorption wavelength of this dye was 428.0 nm (in ethyl acetate).
［実施例５５］
＜化合物（Ｄ−４０）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンに変えて３−シアノ−４−エチル−６−ヒドロキシ−Ｎ−（２−アミノエチル）−２−ピリドンを使用したこと以外は実施例２５と同様に行うことで下記式（Ｉ−９）の色素を得た。
[Example 55]
<Synthesis of Compound (D-40)>
Using 3-cyano-4-ethyl-6-hydroxy-N- (2-aminoethyl) -2-pyridone instead of 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone Was carried out in the same manner as in Example 25 to obtain a dye of the following formula (I-9).
［実施例５６］
＜化合物（Ｄ−４１）の合成＞
Ｎ−メチルアミノエタノールに変えてアンモニア水を、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−ヒドロキシエチル）−２−ピリドンを使用したこと以外は実施例１と同様に行うことで下記式（Ｉ−９）の色素を得た。
[Example 56]
<Synthesis of Compound (D-41)>
Ammonia water is changed to N-methylaminoethanol, and 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone is changed to 3-cyano-4-methyl-6-hydroxy-N- (2 A dye of the following formula (I-9) was obtained in the same manner as in Example 1 except that -hydroxyethyl) -2-pyridone was used.
［実施例５７］
＜化合物（Ｄ−４２）の合成＞
２−エトキシ−４−（β−スルファトエチルスルホニル）アニリン ３２.５部を水 ３５０部を加えた後、水酸化ナトリウム １２部を添加し、８０℃で５時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 57]
<Synthesis of Compound (D-42)>
After adding 32.5 parts of 2-ethoxy-4- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 12 parts of sodium hydroxide was added and stirred at 80 ° C. for 5 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−スルホ−４−メチル−６−ヒドロキシ−Ｎ−メチル−２−ピリドン ２１.９部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。 This diazotized product was dissolved in a solution of 21.9 parts of 3-sulfo-4-methyl-6-hydroxy-N-methyl-2-pyridone, 300 parts of water and 10 parts of soda ash in a 10% aqueous sodium hydroxide solution at pH = 7. While maintaining 0.0 to 8.0, the solution was added dropwise at 5 to 10 ° C. over 1 hour. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
撹拌後、トリ−ｎ−オクチルアミン ３６部、６２.５％硫酸 ３０部を添加し、７０〜
８０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ７７.２部を得た。
After stirring, 36 parts of tri-n-octylamine and 30 parts of 62.5% sulfuric acid were added, and 70 to
Stir at 80 ° C. for 2 hours.
The reaction solution was filtered off and washed with water, and then the resulting wet cake was dried to obtain 77.2 parts of a dry cake.
得られた乾燥ケーキ ４１.５部をテトラヒドロフラン ５００部に溶解後、遮光しながらアクリロイルクロリド ５.０部、ピリジン ４.３部を添加し、２０〜３０℃で２時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−４２）で表される色素 ４２.９部を得た。この色素の最大吸収波長は４１３.０ｎｍ（酢酸エチル中）であった。
After dissolving 41.5 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 5.0 parts of acryloyl chloride and 4.3 parts of pyridine were added while shielding light, and the mixture was stirred at 20 to 30 ° C. for 2 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the obtained wet cake was dried to obtain 42.9 parts of a pigment represented by the formula (D-42). The maximum absorption wavelength of this dye was 413.0 nm (in ethyl acetate).
［実施例５８］
＜化合物（Ｄ−４３）の合成＞
２−メトキシ−５−メチル−４−（β−スルファトエチルスルホニル）アニリン ３２.５部を水 ３５０部を加えた後、Ｎ−メチルエチレンジアミン ７.８部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 58]
<Synthesis of Compound (D-43)>
After adding 32.5 parts of 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 7.8 parts of N-methylethylenediamine and 12 parts of sodium hydroxide were added, Stir at 80 ° C. for 3 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−スルホエチル）−２−ピリドン ２５.８部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。 This diazotized product was dissolved in a solution of 25.8 parts of 3-cyano-4-methyl-6-hydroxy-N- (2-sulfoethyl) -2-pyridone, 300 parts of water and 10 parts of soda ash in a 10% aqueous sodium hydroxide solution. The solution was added dropwise at 5 to 10 ° C. over 1 hour while maintaining pH = 7.0 to 8.0. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
撹拌後、トリ−ｎ−オクチルアミン ３６部、６２.５％硫酸 ３０部を添加し、７０〜８０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥し、乾燥ケーキ ８５.５部を得た。
After stirring, 36 parts of tri-n-octylamine and 30 parts of 62.5% sulfuric acid were added and stirred at 70-80 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the resulting wet cake was dried to obtain 85.5 parts of a dry cake.
得られた乾燥ケーキ ４９.６部をテトラヒドロフラン５００部に溶解後、遮光しながらメタクリロイルクロリド ５.７部、ピリジン ４.３部を添加し、２０〜３０℃で３時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−４３）で表される色素 ４２.９部を得た。この色素の最大吸収波長は４４０.０ｎｍ（酢酸エチル中）であった。
After dissolving 49.6 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 5.7 parts of methacryloyl chloride and 4.3 parts of pyridine were added while shielding light, and stirred at 20 to 30 ° C. for 3 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and then the resulting wet cake was dried to obtain 42.9 parts of a pigment represented by the formula (D-43). The maximum absorption wavelength of this dye was 440.0 nm (in ethyl acetate).
［実施例５９］
＜化合物（Ｄ−４４）の合成＞
３−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３５０部を加えた後、２−エチルヘキシルアミン １２.９部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １８部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 59]
<Synthesis of Compound (D-44)>
After adding 28.1 parts of 3- (β-sulfatoethylsulfonyl) aniline to 350 parts of water, 12.9 parts of 2-ethylhexylamine and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 3 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 18 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドン ２５.２部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５
〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで乾燥ケーキ ５０.１部を得た。
The diazotized product was dissolved in a solution of 25.2 parts of 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone, 300 parts of water and 10 parts of soda ash in a 10% aqueous sodium hydroxide solution at pH = 7. While maintaining 0.0 to 8.0, the solution was added dropwise at 5 to 10 ° C. over 1 hour. After dripping, 5
The mixture was stirred at -10 ° C for 2 hours.
The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 50.1 parts of a dry cake.
得られた乾燥ケーキ ２８.５部をテトラヒドロフラン５００部に溶解後、遮光しながらアクリロイルクロリド ５.０部、ピリジン ４.３部を添加し、２０〜３０℃で３時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｄ−４４）で表される色素 ２６.６部を得た。この色素の最大吸収波長は４１８.０ｎｍ（酢酸エチル中）であった。
After dissolving 28.5 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 5.0 parts of acryloyl chloride and 4.3 parts of pyridine were added while shielding light, and the mixture was stirred at 20 to 30 ° C. for 3 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 26.6 parts of the pigment represented by the formula (D-44). The maximum absorption wavelength of this dye was 418.0 nm (in ethyl acetate).
［実施例６０］
＜化合物（Ｄ−４５）の合成＞
Ｎ−メチルアミノエタノールに変えてＮ，Ｎ−ジエチルアミノエチルアミンを、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−ヒドロキシエチル）−２−ピリドンを使用したこと以外は実施例１と同様に行うことで下記式（Ｉ−１１）の色素を得た。
[Example 60]
<Synthesis of Compound (D-45)>
Instead of N-methylaminoethanol, N, N-diethylaminoethylamine, 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone, and 3-cyano-4-methyl-6-hydroxy-N- Except having used (2-hydroxyethyl) -2-pyridone, it carried out like Example 1 and the pigment | dye of the following formula (I-11) was obtained.
［実施例６１］
＜化合物（Ｄ−４６）の合成＞
Ｎ−メチルアミノエタノールに変えてｎ−ブチルアミンを、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを３−シアノ−４−トリフルオロメチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを使用したこと以外は実施例１と同様に行うことで下記式（Ｉ−１２）の色素を得た。
[Example 61]
<Synthesis of Compound (D-46)>
N-Butylamine instead of N-methylaminoethanol, 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone to 3-cyano-4-trifluoromethyl-6-hydroxy-N-butyl Except having used 2-pyridone, it carried out like Example 1 and the pigment | dye of the following formula (I-12) was obtained.
［実施例６２］
＜化合物（Ｄ−４７）の合成＞
Ｎ−メチルアミノエタノールに変えてジエタノールアミンを、３−シアノ−４−メチル
−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−エチル−２−ピリドンを使用したこと以外は実施例１と同様に行うことで下記式（Ｉ−１３）の色素を得た。
[Example 62]
<Synthesis of Compound (D-47)>
Diethanolamine instead of N-methylaminoethanol, 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone to 3-cyano-4-methyl-6-hydroxy-N-ethyl-2-pyridone The dye of the following formula (I-13) was obtained in the same manner as in Example 1 except that was used.
［実施例６３］
＜化合物（Ｄ−４８）の合成＞
Ｎ−メチルアミノエタノールに変えてアンモニア水を、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（３−ジエチルアミノプロピル）−２−ピリドンを使用したこと以外は実施例１と同様に行うことで下記式（Ｉ−１４）の色素を得た。
[Example 63]
<Synthesis of Compound (D-48)>
Instead of N-methylaminoethanol, aqueous ammonia was used, and 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone was replaced with 3-cyano-4-methyl-6-hydroxy-N- (3-diethylamino). A dye of the following formula (I-14) was obtained in the same manner as in Example 1 except that propyl) -2-pyridone was used.
［実施例６４］
＜化合物（Ｄ−４９）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−エチルヘキシル）−２−ピリドンを使用したこと以外は実施例２５と同様に行うことで下記式（Ｉ−１５）の色素を得た。
[Example 64]
<Synthesis of Compound (D-49)>
Implemented except that 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone was used instead of 3-cyano-4-methyl-6-hydroxy-N- (2-ethylhexyl) -2-pyridone The dye of the following formula (I-15) was obtained in the same manner as in Example 25.
［実施例６５］
＜化合物（Ｄ−５０）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１５）の色素を使用したこと以外は実施例６と同様に行うことで式（Ｄ−５０）の色素を得た。この色素の最大吸収波長は４２１.５ｎｍ（酢酸エチル中）であった。
[Example 65]
<Synthesis of Compound (D-50)>
The dye of formula (D-50) was obtained in the same manner as in Example 6 except that the dye of formula (I-15) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 421.5 nm (in ethyl acetate).
［実施例６６］
＜化合物（Ｄ−５１）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１５）の色素を使用したこと以外は実施例１と同様に行うことで式（Ｄ−５１）の色素を得た。この色素の最大吸収波長は４２１.５ｎｍ（酢酸エチル中）であった。
[Example 66]
<Synthesis of Compound (D-51)>
The dye of the formula (D-51) was obtained in the same manner as in Example 1 except that the dye of the formula (I-15) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 421.5 nm (in ethyl acetate).
［実施例６７］
＜化合物（Ｄ−５２）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１５）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｄ−５２）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 67]
<Synthesis of Compound (D-52)>
The dye of the formula (D-52) was obtained in the same manner as in Example 3 except that the dye of the formula (I-15) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例６８］
＜化合物（Ｄ−５３）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−エチルヘキシル）−２−ピリドンを使用したこと以外は実施例１と同様に行うことで下記式（Ｉ−１６）の色素を得た。
[Example 68]
<Synthesis of Compound (D-53)>
Implemented except that 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone was used instead of 3-cyano-4-methyl-6-hydroxy-N- (2-ethylhexyl) -2-pyridone By carrying out in the same manner as in Example 1, a dye of the following formula (I-16) was obtained.
［実施例６９］
＜化合物（Ｄ−５４）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１６）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｄ−５４）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 69]
<Synthesis of Compound (D-54)>
The dye of the formula (D-54) was obtained in the same manner as in Example 3 except that the dye of the formula (I-16) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例７０］
＜化合物（Ｄ−５５）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１６）の色素を使用したこと以外は実施例５と同様に行うことで式（Ｄ−５５）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 70]
<Synthesis of Compound (D-55)>
The dye of the formula (D-55) was obtained in the same manner as in Example 5 except that the dye of the formula (I-16) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例７１］
＜化合物（Ｄ−５６）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１６）の色素を使用したこと以外は実施例７と同様に行うことで式（Ｄ−５６）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 71]
<Synthesis of Compound (D-56)>
The dye of the formula (D-56) was obtained in the same manner as in Example 7 except that the dye of the formula (I-16) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例７２］
＜化合物（Ｄ−５７）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１６）の色素を使用したこと以外は実施例６と同様に行うことで式（Ｄ−５７）の色素を得た。この色素の最大吸収波長は４２１.５ｎｍ（酢酸エチル中）であった。
[Example 72]
<Synthesis of Compound (D-57)>
The dye of the formula (D-57) was obtained in the same manner as in Example 6 except that the dye of the formula (I-16) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 421.5 nm (in ethyl acetate).
［実施例７３］
＜化合物（Ｄ−５８）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１６）の色素を使用したこと以外は実施例９と同様に行うことで式（Ｄ−５８）の色素を得た。この色素の最大吸収波長は４２１.５ｎｍ（酢酸エチル中）であった。
[Example 73]
<Synthesis of Compound (D-58)>
The dye of the formula (D-58) was obtained in the same manner as in Example 9 except that the dye of the formula (I-16) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 421.5 nm (in ethyl acetate).
［実施例７４］
＜化合物（Ｄ−５９）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例１０と同様に行うことで式（Ｄ−５９）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 74]
<Synthesis of Compound (D-59)>
The dye of the formula (D-59) was obtained in the same manner as in Example 10 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例７５］
＜化合物（Ｄ−６０）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例１１と同様に行うことで式（Ｄ−６０）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 75]
<Synthesis of Compound (D-60)>
The dye of the formula (D-60) was obtained in the same manner as in Example 11 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例７６］
＜化合物（Ｄ−６１）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−４）の色素を使用したこと以外は実施例１２と同様に行うことで式（Ｄ−６１）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 76]
<Synthesis of Compound (D-61)>
The dye of the formula (D-61) was obtained in the same manner as in Example 12 except that the dye of the formula (I-4) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例７７］
＜化合物（Ｄ−６２）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−５）の色素を使用したこと以外は実施例１１と同様に行うことで式（Ｄ−６２）の色素を得た。この色素の最大吸収波長は４２１.５ｎｍ（酢酸エチル中）であった。
[Example 77]
<Synthesis of Compound (D-62)>
The dye of the formula (D-62) was obtained in the same manner as in Example 11 except that the dye of the formula (I-5) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 421.5 nm (in ethyl acetate).
［実施例７８］
＜化合物（Ｄ−６３）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−６）の色素を使用したこと以外は実施例１２と同様に行うことで式（Ｄ−６３）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 78]
<Synthesis of Compound (D-63)>
The dye of the formula (D-63) was obtained in the same manner as in Example 12 except that the dye of the formula (I-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例７９］
＜化合物（Ｆ−１）の合成＞
シアノ酢酸エチル ５６.５部、アセト酢酸エチル ６５.０部、３,３‘−ジアミノジプロピルアミン ６５.５部、ピペリジン ４２.５部の混合物を７５〜８０℃で１５時間撹拌。常温まで冷却後、水 ４００部および濃塩酸 １２０部を添加した。
析出物を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで下記式（Ｉ−１７）で表されるカップル成分 １４５.３部を得た。
[Example 79]
<Synthesis of Compound (F-1)>
A mixture of 56.5 parts of ethyl cyanoacetate, 65.0 parts of ethyl acetoacetate, 65.5 parts of 3,3′-diaminodipropylamine, and 42.5 parts of piperidine was stirred at 75-80 ° C. for 15 hours. After cooling to room temperature, 400 parts of water and 120 parts of concentrated hydrochloric acid were added.
The precipitate was filtered off, washed with water, and the wet cake obtained was dried to obtain 145.3 parts of a couple component represented by the following formula (I-17).
このジアゾ化物を式（Ｉ−１７）のカップル成分 ４０.０部、水 ６００部、ソーダ灰 ２０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで下記式（Ｆ−６）で表される色素 １００.９部を得た。
The diazotized product was dissolved in a solution of 40.0 parts of the couple component of formula (I-17), 600 parts of water and 20 parts of soda ash while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. The solution was added dropwise at 5 to 10 ° C. over 1 hour. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 100.9 parts of a dye represented by the following formula (F-6).
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｆ−１）で表される色素 ５２.４部を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 52.4 parts of the pigment represented by the formula (F-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例８０］
＜化合物（Ｆ−２）の合成＞
式（Ｉ−１）の色素に変えて式（Ｆ−６）の色素を使用したこと以外は実施例２と同様に行うことで式（Ｆ−２）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 80]
<Synthesis of Compound (F-2)>
The dye of the formula (F-2) was obtained in the same manner as in Example 2 except that the dye of the formula (F-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例８１］
＜化合物（Ｆ−３）の合成＞
式（Ｉ−１）の色素に変えて式（Ｆ−６）の色素を使用したこと以外は実施例９と同様に行うことで式（Ｆ−３）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 81]
<Synthesis of Compound (F-3)>
The dye of the formula (F-3) was obtained in the same manner as in Example 9 except that the dye of the formula (F-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例８２］
＜化合物（Ｆ−４）の合成＞
式（Ｉ−１）の色素に変えて式（Ｆ−６）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｆ−４）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 82]
<Synthesis of Compound (F-4)>
The dye of the formula (F-4) was obtained in the same manner as in Example 3 except that the dye of the formula (F-6) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例８３］
＜化合物（Ｆ−５）の合成＞
式（Ｉ−１）の色素に変えて式（Ｆ−６）の色素を使用したこと以外は実施例４と同様に行うことで式（Ｆ−５）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 83]
<Synthesis of Compound (F-5)>
The dye of formula (F-5) was obtained in the same manner as in Example 4 except that the dye of formula (F-6) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例８４］
＜化合物（Ｆ−６）の合成＞
実施例７９の処方にて式（Ｆ−６）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 84]
<Synthesis of Compound (F-6)>
The pigment | dye of the formula (F-6) was obtained by the prescription of Example 79. The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例８５］
＜化合物（Ｆ−７）の合成＞
３,３‘−ジアミノジプロピルアミンに変えて３,３‘−ジアミノ−Ｎ−メチルジプロピルアミンを使用したこと以外は実施例７９と同様に行うことで式（Ｆ−７）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 85]
<Synthesis of Compound (F-7)>
The dye of formula (F-7) was obtained in the same manner as in Example 79 except that 3,3′-diamino-N-methyldipropylamine was used instead of 3,3′-diaminodipropylamine. It was. The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例８６］
＜化合物（Ｆ−８）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ５６.２部を水 ７００部を加えた後、水酸化ナトリウム ２４部を添加し、８０℃で５時間撹拌した。常温まで冷却後、濃塩酸 １６０部添加し、４０％亜硝酸ナトリウム水溶液 ３６部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 86]
<Synthesis of Compound (F-8)>
After adding 700 parts of water to 56.2 parts of 4- (β-sulfatoethylsulfonyl) aniline, 24 parts of sodium hydroxide was added and stirred at 80 ° C. for 5 hours. After cooling to room temperature, 160 parts of concentrated hydrochloric acid was added, and 36 parts of a 40% sodium nitrite aqueous solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を式（Ｉ−１７）のカップル成分 ４０.０部、水 ６００部、ソーダ灰 ２０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで下記式（Ｉ−１８）で表される色素 ７９.６部を得た。
The diazotized product was dissolved in a solution of 40.0 parts of the couple component of formula (I-17), 600 parts of water and 20 parts of soda ash while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. The solution was added dropwise at 5 to 10 ° C. over 1 hour. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 79.6 parts of a dye represented by the following formula (I-18).
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｆ−８）で表される色素 １４.６部を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 14.6 parts of a pigment represented by the formula (F-8). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例８７］
＜化合物（Ｆ−９）の合成＞
３,３‘−ジアミノジプロピルアミン変えて３,３‘−ジアミノ−Ｎ−メチルジプロピルアミンを使用したこと以外は実施例７９と同様に行うことで下記式（Ｉ−１９）のカップル成分を得た。
[Example 87]
<Synthesis of Compound (F-9)>
A couple component of the following formula (I-19) was obtained in the same manner as in Example 79 except that 3,3′-diamino-N-methyldipropylamine was used instead of 3,3′-diaminodipropylamine. Obtained.
［実施例８８］
＜化合物（Ｆ−１０）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１８）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｆ−１０）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 88]
<Synthesis of Compound (F-10)>
The dye of formula (F-10) was obtained in the same manner as in Example 3 except that the dye of formula (I-18) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例８９］
＜化合物（Ｆ−１１）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２０）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｆ−１１）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 89]
<Synthesis of Compound (F-11)>
The dye of formula (F-11) was obtained in the same manner as in Example 3 except that the dye of formula (I-20) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例９０］
＜化合物（Ｆ−１２）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１８）の色素を使用したこと以外は実施例９と同様に行うことで式（Ｆ−１２）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 90]
<Synthesis of Compound (F-12)>
The dye of the formula (F-12) was obtained in the same manner as in Example 9 except that the dye of the formula (I-18) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例９１］
＜化合物（Ｆ−１３）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２０）の色素を使用したこと以外は実施例９と同様に行うことで式（Ｆ−１２）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 91]
<Synthesis of Compound (F-13)>
The dye of the formula (F-12) was obtained in the same manner as in Example 9 except that the dye of the formula (I-20) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例９２］
＜化合物（Ｆ−１４）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−１８）の色素を使用したこと以外は実施例６と同様に行うことで式（Ｆ−１４）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 92]
<Synthesis of Compound (F-14)>
The dye of the formula (F-14) was obtained in the same manner as in Example 6 except that the dye of the formula (I-18) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例９３］
＜化合物（Ｆ−１５）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２０）の色素を使用したこと以外は実施例６と同様に行うことで式（Ｆ−１５）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 93]
<Synthesis of Compound (F-15)>
The dye of formula (F-15) was obtained in the same manner as in Example 6 except that the dye of formula (I-20) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例９４］
＜化合物（Ｆ−１６）の合成＞
３,３‘−ジアミノジプロピルアミン変えてエチレンジアミンを使用したこと以外は実施例７９と同様に行うことで下記式（Ｉ−２１）のカップル成分を得た。
[Example 94]
<Synthesis of Compound (F-16)>
A couple component of the following formula (I-21) was obtained in the same manner as in Example 79 except that ethylenediamine was used instead of 3,3′-diaminodipropylamine.
［実施例９５］
＜化合物（Ｆ−１７）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３００部を加えた後、水酸化ナトリウム １２部を添加し、８０℃で６時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １７.４部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で３０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 95]
<Synthesis of Compound (F-17)>
After adding 300 parts of water to 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline, 12 parts of sodium hydroxide was added and stirred at 80 ° C. for 6 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 17.4 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 30 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を式（Ｉ−２１）のカップル成分 ３２.６部、水 ３００部、水酸化ナトリウム ３０部の溶解液を９５℃で１０時間撹拌したものに１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下し、第一カップル液を得た。 This diazotized product was prepared by stirring a solution of 32.6 parts of the couple component of formula (I-21), 300 parts of water and 30 parts of sodium hydroxide at 95 ° C. for 10 hours, and adding 10% aqueous sodium hydroxide solution to pH = 7. While maintaining 0.0 to 8.0, the solution was added dropwise at 5 to 10 ° C. over 1 hour to obtain a first couple liquid.
２−メトキシ−４−（β−スルファトエチルスルホニル）アニリン ３１.１部を水 ３００部を加えた後、ジエチルアミノエチルアミン １１.６部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０
％亜硝酸ナトリウム水溶液 １７.４部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で３０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
2-methyl-4- (β-sulfatoethylsulfonyl) aniline (31.1 parts), water (300 parts) were added, diethylaminoethylamine (11.6 parts) and sodium hydroxide (12 parts) were added, and the mixture was stirred at 80 ° C. for 3 hours. did. After cooling to room temperature, add 80 parts of concentrated hydrochloric acid and add 40
17.4 parts of a sodium nitrite aqueous solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 30 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を第一カップル液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで乾燥ケーキ ８５.３部を得た。
This diazotized product was added dropwise to the first couple liquid over 1 hour at 5 to 10 ° C. while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 85.3 parts of a dry cake.
得られた乾燥ケーキ ４６.６部をテトラヒドロフラン５００部に溶解後、遮光しながらアクリロイルクロリド ５.０部、ピリジン ４.３部を添加し、２０〜３０℃で３時間撹拌した。
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｆ−１７）で表される色素 ４３.９部を得た。この色素の最大吸収波長は４１６.５ｎｍ（酢酸エチル中）であった。
After dissolving 46.6 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 5.0 parts of acryloyl chloride and 4.3 parts of pyridine were added while being shielded from light, and the mixture was stirred at 20 to 30 ° C. for 3 hours.
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and then the obtained wet cake was dried to obtain 43.9 parts of a pigment represented by the formula (F-17). The maximum absorption wavelength of this dye was 416.5 nm (in ethyl acetate).
［実施例９６］
＜化合物（Ｆ−１８）の合成＞
３,３‘−ジアミノジプロピルアミン変えて１，２−ジアミノプロパンを使用したこと以外は実施例７９と同様に行うことで下記式（Ｉ−２３）のカップル成分を得た。
[Example 96]
<Synthesis of Compound (F-18)>
A couple component of the following formula (I-23) was obtained in the same manner as in Example 79 except that 1,2-diaminopropane was used in place of 3,3′-diaminodipropylamine.
このジアゾ化物を式Ｓ（Ｉ−２３）のカップル成分 ３４.０部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下し、第一カップル液を得た。 This diazotized product was kept at pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution in a solution of 34.0 parts of the couple component of formula S (I-23), 300 parts of water and 10 parts of soda ash. Then, it was added dropwise at 5 to 10 ° C. over 1 hour to obtain a first couple liquid.
２−メトキシ−５−メチル−４−（β−スルファトエチルスルホニル）アニリン ３２.３部を水 ３００部を加えた後、２−エチルヘキシルアミン １２.９部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １７.４部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で３０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。 After adding 32.3 parts of 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) aniline to 300 parts of water, 12.9 parts of 2-ethylhexylamine and 12 parts of sodium hydroxide were added, Stir at 80 ° C. for 3 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 17.4 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 30 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を第一カップル液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで乾燥ケーキ ８５.６部を得た。
This diazotized product was added dropwise to the first couple liquid over 1 hour at 5 to 10 ° C. while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 85.6 parts of a dry cake.
得られた乾燥ケーキ ４５.９部をジメチルホルムアミド ２００部に溶解後、遮光しながらテトラブチルアンモニウムブロミド ０.２部、４−ｔｅｒｔ−ブチルピロカテコール
０.４部、グリシジルメタクリレート ２１.３部を添加し、１２０〜１３０℃で４時間撹拌した。
得られた反応液を水 １０００部に滴下し、析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｆ−１８）で表される色素 ４７.２部を得た。この色素の最大吸収波長は４３０.５ｎｍ（酢酸エチル中）であった。
After 45.9 parts of the resulting dried cake was dissolved in 200 parts of dimethylformamide, 0.2 part of tetrabutylammonium bromide, 0.4 part of 4-tert-butylpyrocatechol, and 21.3 parts of glycidyl methacrylate were added while shielding from light. And stirred at 120-130 ° C. for 4 hours.
The obtained reaction liquid was dropped into 1000 parts of water, and the precipitated dye was filtered off, washed with water, and then the resulting wet cake was dried to give a dye represented by the formula (F-18) 47. Two parts were obtained. The maximum absorption wavelength of this dye was 430.5 nm (in ethyl acetate).
［実施例９７］
＜化合物（Ｆ−１９）の合成＞
３,３‘−ジアミノジプロピルアミン変えてｐ−キシリレンジアミンを使用したこと以外は実施例７９と同様に行うことで下記式（Ｉ−２４）のカップル成分を得た。
[Example 97]
<Synthesis of Compound (F-19)>
A couple component of the following formula (I-24) was obtained in the same manner as in Example 79 except that p-xylylenediamine was used in place of 3,3′-diaminodipropylamine.
このジアゾ化物を式Ｓ（Ｉ−２４）のカップル成分 ４０.２部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下し、第一カップル液を得た。 This diazotized product was kept at pH = 7.0-8.0 with a 10% aqueous sodium hydroxide solution in a solution of 40.2 parts of the couple of formula S (I-24), 300 parts of water and 10 parts of soda ash. Then, it was added dropwise at 5 to 10 ° C. over 1 hour to obtain a first couple liquid.
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３００部を加えた後、２−エチルヘキシルアミン １２.９部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １７.４部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で３０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。 After adding 300 parts of water to 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline, 12.9 parts of 2-ethylhexylamine and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 3 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 17.4 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 30 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を第一カップル液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｆ−１９）で表される色素 １００.７部を得た。この色素の最大吸収波長は４２６.０ｎｍ（酢酸エチル中）であった。
This diazotized product was added dropwise to the first couple liquid over 1 hour at 5 to 10 ° C. while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 100.7 parts of a dye represented by the formula (F-19). The maximum absorption wavelength of this dye was 426.0 nm (in ethyl acetate).
［実施例９８］
＜化合物（Ｆ−２０）の合成＞
３,３‘−ジアミノジプロピルアミン変えて１，４−ビス（３−アミノプロピル）ピペ
ラジンを使用したこと以外は実施例７９と同様に行うことで下記式（Ｉ−２５）のカップル成分を得た。
[Example 98]
<Synthesis of Compound (F-20)>
A couple component of the following formula (I-25) is obtained by carrying out in the same manner as in Example 79 except that 1,4-bis (3-aminopropyl) piperazine is used in place of 3,3′-diaminodipropylamine. It was.
［実施例９９］
＜化合物（Ｆ−２１）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３００部を加えた後、Ｎ−メチルアミノエタノール ７.５部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １７.４部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で３０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
Example 99
<Synthesis of Compound (F-21)>
After adding 300 parts of water to 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline, 7.5 parts of N-methylaminoethanol and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 3 hours. . After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 17.4 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 30 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を式（Ｉ−２５）のカップル成分 ４６.６部、水 ３００部、水酸化ナトリウム ３０部の溶解液を９５℃で１０時間撹拌したものに１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下し、第一カップル液を得た。 The diazotized product was prepared by stirring a solution of 46.6 parts of the couple component of formula (I-25), 300 parts of water and 30 parts of sodium hydroxide at 95 ° C. for 10 hours, and adding 10% aqueous sodium hydroxide solution to pH = 7. While maintaining 0.0 to 8.0, the solution was added dropwise at 5 to 10 ° C. over 1 hour to obtain a first couple liquid.
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ３００部を加えた後、Ｎ−メチルエチレンジアミン ７.４部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 ８０部添加し、４０％亜硝酸ナトリウム水溶液 １７.４部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で３０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。 After adding 300 parts of water to 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline, 7.4 parts of N-methylethylenediamine and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 3 hours. After cooling to room temperature, 80 parts of concentrated hydrochloric acid was added, and 17.4 parts of a 40% aqueous sodium nitrite solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 30 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を第一カップル液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで乾燥ケーキ ９５.１部を得た。
This diazotized product was added dropwise to the first couple liquid over 1 hour at 5 to 10 ° C. while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction liquid was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 95.1 parts of a dry cake.
得られた乾燥ケーキ ５０.２部をテトラヒドロフラン５００部に溶解後、遮光しながらメタクリロイルクロリド ５.７部、ピリジン ４.３部を添加し、２０〜３０℃で３時間撹拌した。
次いでアクリロイルクロリド ５.０部、ピリジン ４.３部を添加し、２０〜３０℃で３時間撹拌した。
After dissolving 50.2 parts of the obtained dry cake in 500 parts of tetrahydrofuran, 5.7 parts of methacryloyl chloride and 4.3 parts of pyridine were added while shielding light, and the mixture was stirred at 20 to 30 ° C. for 3 hours.
Subsequently, 5.0 parts of acryloyl chloride and 4.3 parts of pyridine were added and stirred at 20-30 ° C. for 3 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｆ−２１）で表される色素 ４８.２部を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The deposited pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 48.2 parts of the pigment represented by the formula (F-21). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１００］
＜化合物（Ｆ−２２）の合成＞
式（Ｉ−１）の色素に変えて式（Ｆ−６）の色素を使用したこと以外は実施例１０と同様に行うことで式（Ｆ−２２）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 100]
<Synthesis of Compound (F-22)>
The dye of formula (F-22) was obtained in the same manner as in Example 10 except that the dye of formula (F-6) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１０１］
＜化合物（Ｆ−２３）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２０）の色素を使用したこと以外は実施例１１と同様に行うことで式（Ｆ−２３）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 101]
<Synthesis of Compound (F-23)>
The dye of formula (F-23) was obtained in the same manner as in Example 11 except that the dye of formula (I-20) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例１０２］
＜化合物（Ｆ−２４）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２２）の色素を使用したこと以外は実施例１２と同様に行うことで式（Ｆ−２４）の色素を得た。この色素の最大吸収波長は４２３.５ｎｍ（酢酸エチル中）であった。
[Example 102]
<Synthesis of Compound (F-24)>
The dye of formula (F-24) was obtained in the same manner as in Example 12 except that the dye of formula (I-22) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 423.5 nm (in ethyl acetate).
［実施例１０３］
＜化合物（Ｈ−１）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ５６.２部を水 ７００部を加えた後、ピペラジン ８.４部および水酸化ナトリウム ２４部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 １６０部添加し、４０％亜硝酸ナトリウム水溶液 ３６部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 103]
<Synthesis of Compound (H-1)>
After adding 700 parts of water to 56.2 parts of 4- (β-sulfatoethylsulfonyl) aniline, 8.4 parts of piperazine and 24 parts of sodium hydroxide were added and stirred at 80 ° C. for 3 hours. After cooling to room temperature, 160 parts of concentrated hydrochloric acid was added, and 36 parts of a 40% sodium nitrite aqueous solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドン ５０.４部、水 ６００部、ソーダ灰 ２０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。 This diazotized product was dissolved in a solution of 50.4 parts of 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone, 600 parts of water and 20 parts of soda ash in a 10% aqueous sodium hydroxide solution at pH = 7. While maintaining 0.0 to 8.0, the solution was added dropwise at 5 to 10 ° C. over 1 hour. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｈ−１）で表される色素 ８３.９部を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。 The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 83.9 parts of a dye represented by the formula (H-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例１０４］
＜化合物（Ｈ−２）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｈ−２）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 104]
<Synthesis of Compound (H-2)>
Example 103, except that 3-cyano-4-methyl-6-hydroxy-N-butyl-2-pyridone was used instead of 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone The dye of formula (H-2) was obtained by carrying out in the same manner as above. The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１０５］
＜化合物（Ｈ−３）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−エチルヘキシル）−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｈ−３）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 105]
<Synthesis of Compound (H-3)>
Other than using 3-cyano-4-methyl-6-hydroxy-N- (2-ethylhexyl) -2-pyridone instead of 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone Was carried out in the same manner as in Example 103 to obtain the dye of formula (H-3). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１０６］
＜化合物（Ｈ−４）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（３−イソプロポキシプロピル）−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｈ−４）の色素を得た。この色素の最大吸収波長は４２１.５ｎｍ（酢酸エチル中）であった。
[Example 106]
<Synthesis of Compound (H-4)>
Instead of 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone, 3-cyano-4-methyl-6-hydroxy-N- (3-isopropoxypropyl) -2-pyridone was used. Except for this, the dye of formula (H-4) was obtained in the same manner as in Example 103. The maximum absorption wavelength of this dye was 421.5 nm (in ethyl acetate).
［実施例１０７］
＜化合物（Ｈ−５）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−ヒドロキシエチル）−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｉ−２６）の色素を得た。
[Example 107]
<Synthesis of Compound (H-5)>
The use of 3-cyano-4-methyl-6-hydroxy-N- (2-hydroxyethyl) -2-pyridone instead of 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone The dye of formula (I-26) was obtained in the same manner as in Example 103 except for the above.
［実施例１０８］
＜化合物（Ｈ−６）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２６）の色素を使用したこと以外は実施例６と同様に行うことで式（Ｈ−６）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 108]
<Synthesis of Compound (H-6)>
The dye of the formula (H-6) was obtained in the same manner as in Example 6 except that the dye of the formula (I-26) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例１０９］
＜化合物（Ｈ−７）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２６）の色素を使用したこと以外は実施例９と同様に行うことで式（Ｈ−７）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 109]
<Synthesis of Compound (H-7)>
The dye of the formula (H-7) was obtained in the same manner as in Example 9 except that the dye of the formula (I-26) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１１０］
＜化合物（Ｈ−８）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２６）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｈ−８）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 110]
<Synthesis of Compound (H-8)>
The dye of the formula (H-8) was obtained in the same manner as in Example 3 except that the dye of the formula (I-26) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１１１］
＜化合物（Ｈ−９）の合成＞
ピペラジンに変えて１，４−ビス（３−アミノプロピル）ピペラジンを、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ブチル−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｈ−９）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 111]
<Synthesis of Compound (H-9)>
Instead of piperazine, 1,4-bis (3-aminopropyl) piperazine is replaced with 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone and 3-cyano-4-methyl-6- The dye of the formula (H-9) was obtained in the same manner as in Example 103 except that hydroxy-N-butyl-2-pyridone was used. The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例１１２］
＜化合物（Ｈ−１０）の合成＞
ピペラジンに変えて１，４−ビス（３−アミノプロピル）ピペラジンを、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−エチルヘキシル）−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｈ−１０）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 112]
<Synthesis of Compound (H-10)>
Instead of piperazine, 1,4-bis (3-aminopropyl) piperazine is replaced with 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone and 3-cyano-4-methyl-6- The dye of formula (H-10) was obtained in the same manner as in Example 103 except that hydroxy-N- (2-ethylhexyl) -2-pyridone was used. The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１１３］
＜化合物（Ｈ−１１）の合成＞
ピペラジンに変えて１，４−ビス（３−アミノプロピル）ピペラジンを、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−ヒドロキシエチル）−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｉ−２７）の色素を得た。
[Example 113]
<Synthesis of Compound (H-11)>
Instead of piperazine, 1,4-bis (3-aminopropyl) piperazine is replaced with 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone and 3-cyano-4-methyl-6- The dye of formula (I-27) was obtained in the same manner as in Example 103 except that hydroxy-N- (2-hydroxyethyl) -2-pyridone was used.
［実施例１１４］
＜化合物（Ｈ−１２）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２７）の色素を使用したこと以外は実施例６と同様に行うことで式（Ｈ−１２）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 114]
<Synthesis of Compound (H-12)>
The dye of the formula (H-12) was obtained in the same manner as in Example 6 except that the dye of the formula (I-27) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１１５］
＜化合物（Ｈ−１３）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２７）の色素を使用したこと以外は実施例９と同様に行うことで式（Ｈ−１３）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 115]
<Synthesis of Compound (H-13)>
The dye of formula (H-13) was obtained in the same manner as in Example 9 except that the dye of formula (I-27) was used instead of the dye of formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例１１６］
＜化合物（Ｈ−１４）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２７）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｈ−１４）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 116]
<Synthesis of Compound (H-14)>
The dye of the formula (H-14) was obtained in the same manner as in Example 3 except that the dye of the formula (I-27) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１１７］
＜化合物（Ｈ−１５）の合成＞
式（Ｉ−１）の色素に変えて式（Ｈ−１０）の色素を使用したこと以外は実施例１と同様に行うことで式（Ｈ−１５）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ
（酢酸エチル中）であった。
[Example 117]
<Synthesis of Compound (H-15)>
The dye of the formula (H-15) was obtained in the same manner as in Example 1 except that the dye of the formula (H-10) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye is 422.0 nm.
(In ethyl acetate).
［実施例１１８］
＜化合物（Ｈ−１６）の合成＞
ピペラジンに変えて１，４−ビス（３−アミノプロピル）ピペラジンを使用したこと以外は実施例１０３と同様に行うことで式（Ｉ−２８）の色素を得た。
[Example 118]
<Synthesis of Compound (H-16)>
The dye of the formula (I-28) was obtained in the same manner as in Example 103 except that 1,4-bis (3-aminopropyl) piperazine was used instead of piperazine.
［実施例１１９］
＜化合物（Ｈ−１７）の合成＞
式（Ｉ−１）の色素に変えて式（Ｈ−９）の色素を使用したこと以外は実施例３と同様に行うことで式（Ｈ−１７）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 119]
<Synthesis of Compound (H-17)>
The dye of the formula (H-17) was obtained in the same manner as in Example 3 except that the dye of the formula (H-9) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例１２０］
＜化合物（Ｈ−１８）の合成＞
２−メトキシ−４−（β−スルファトエチルスルホニル）アニリン ６２.２部を水 ７００部を加えた後、ｐ−キシリレンジアミン １３.６部および水酸化ナトリウム ２４部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 １６０部添加し、４０％亜硝酸ナトリウム水溶液 ３６部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 120]
<Synthesis of Compound (H-18)>
2-methoxy-4- (β-sulfatoethylsulfonyl) aniline (62.2 parts), water (700 parts) were added, p-xylylenediamine (13.6 parts) and sodium hydroxide (24 parts) were added, and the mixture was heated at 80 ° C. Stir for 3 hours. After cooling to room temperature, 160 parts of concentrated hydrochloric acid was added, and 36 parts of a 40% sodium nitrite aqueous solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−エチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドン ２０.６部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。 This diazotized product was dissolved in a solution of 20.6 parts of 3-cyano-4-ethyl-6-hydroxy-N-propyl-2-pyridone, 300 parts of water and 10 parts of soda ash in a 10% aqueous sodium hydroxide solution at pH = 7. While maintaining 0.0 to 8.0, the solution was added dropwise at 5 to 10 ° C. over 1 hour.
次いで３−カルバモイル−４−メチル−６−ヒドロキシ−Ｎ−（２−エチルヘキシル）−２−ピリドン ２８.０部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。 Subsequently, 3-carbamoyl-4-methyl-6-hydroxy-N- (2-ethylhexyl) -2-pyridone (28.0 parts), water (300 parts), and soda ash (10 parts) were dissolved in a 10% aqueous sodium hydroxide solution at pH = The solution was added dropwise at 5 to 10 ° C. over 1 hour while maintaining 7.0 to 8.0. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｈ−１８）で表される色素 ９７.４部を得た。この色素の最大吸収波長は４２８.０ｎｍ（酢酸エチル中）であった。 The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 97.4 parts of a dye represented by the formula (H-18). The maximum absorption wavelength of this dye was 428.0 nm (in ethyl acetate).
［実施例１２１］
＜化合物（Ｈ−１９）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ２８.１部を水 ７００部を加えた後、ｐ−キシリレンジアミン １３.６部および水酸化ナトリウム １２部を添加し、８０
℃で３時間撹拌した。
[Example 121]
<Synthesis of Compound (H-19)>
After adding 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline to 700 parts of water, 13.6 parts of p-xylylenediamine and 12 parts of sodium hydroxide were added.
Stir at 0 ° C. for 3 hours.
次いで３−（β−スルファトエチルスルホニル）アニリン ２８.１部および水酸化ナトリウム １２部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 １６０部添加し、４０％亜硝酸ナトリウム水溶液 ３６部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。 Next, 28.1 parts of 3- (β-sulfatoethylsulfonyl) aniline and 12 parts of sodium hydroxide were added and stirred at 80 ° C. for 3 hours. After cooling to room temperature, 160 parts of concentrated hydrochloric acid was added, and 36 parts of a 40% sodium nitrite aqueous solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−トリフルオロメチル−６−ヒドロキシ−Ｎ−（２−ジエチルアミノエチル）−２−ピリドン ３０.０部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。 The diazotized product was dissolved in 10% water in a solution of 30.0 parts of 3-cyano-4-trifluoromethyl-6-hydroxy-N- (2-diethylaminoethyl) -2-pyridone, 300 parts of water and 10 parts of soda ash. The solution was added dropwise at 5 to 10 ° C. over 1 hour while maintaining pH = 7.0 to 8.0 with an aqueous sodium oxide solution.
次いで３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−エチルヘキシル）−２−ピリドン ２６.２部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。 Next, a solution of 26.2 parts of 3-cyano-4-methyl-6-hydroxy-N- (2-ethylhexyl) -2-pyridone, 300 parts of water, and 10 parts of soda ash was dissolved in 10% aqueous sodium hydroxide solution at pH = The solution was added dropwise at 5 to 10 ° C. over 1 hour while maintaining 7.0 to 8.0. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで乾燥ケーキ ９８.３部を得た。
乾燥ケーキ ２７.２部をジメチルホルムアミド ２００部に溶解後、遮光しながらテトラブチルアンモニウムブロミド ０.２部、４−ｔｅｒｔ−ブチルピロカテコール ０.４部、グリシジルメタクリレート ２１.３部を添加し、１２０〜１３０℃で４時間撹拌した。
The reaction solution was separated by filtration, washed with water, and the resulting wet cake was dried to obtain 98.3 parts of a dry cake.
After dissolving 27.2 parts of the dried cake in 200 parts of dimethylformamide, 0.2 part of tetrabutylammonium bromide, 0.4 part of 4-tert-butylpyrocatechol and 21.3 parts of glycidyl methacrylate were added while being shielded from light. Stir at ~ 130 ° C for 4 hours.
得られた反応液を水 １０００部に滴下し、析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｈ−１９）で表される色素 ３２.９部を得た。この色素の最大吸収波長は４３１.５ｎｍ（酢酸エチル中）であった。 The obtained reaction solution was added dropwise to 1000 parts of water, and the precipitated dye was filtered off, washed with water, and the resulting wet cake was dried to obtain a dye represented by the formula (H-19) 32. 9 parts were obtained. The maximum absorption wavelength of this dye was 431.5 nm (in ethyl acetate).
［実施例１２２］
＜化合物（Ｈ−２０）の合成＞
ピペラジンに変えて３，３‘−ジアミノジプロピルアミンを、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（３−イソプロポキシプロピル）−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｈ−２０）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 122]
<Synthesis of Compound (H-20)>
Instead of piperazine, 3,3′-diaminodipropylamine is replaced with 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone and 3-cyano-4-methyl-6-hydroxy-N The dye of formula (H-20) was obtained in the same manner as in Example 103 except that-(3-isopropoxypropyl) -2-pyridone was used. The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例１２３］
＜化合物（Ｈ−２１）の合成＞
ピペラジンに変えて３，３‘−ジアミノ−Ｎ−メチルジプロピルアミンを、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−エチルヘキシル）−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｈ−２１）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 123]
<Synthesis of Compound (H-21)>
Instead of piperazine, 3,3′-diamino-N-methyldipropylamine is replaced with 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone and 3-cyano-4-methyl-6 The dye of formula (H-21) was obtained in the same manner as in Example 103 except that -hydroxy-N- (2-ethylhexyl) -2-pyridone was used. The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１２４］
＜化合物（Ｈ−２２）の合成＞
２−メトキシ−５−メチル−４−（β−スルファトエチルスルホニル）アニリン ６５.０部を水 ７００部を加えた後、３，３‘−ジアミノ−Ｎ−メチルジプロピルアミン １４.５部および水酸化ナトリウム ２４部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 １６０部添加し、４０％亜硝酸ナトリウム水溶液 ３６部を５〜１０℃で３０
分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 124]
<Synthesis of Compound (H-22)>
2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) aniline (65.0 parts) was added with 700 parts of water, and then 14.5 parts of 3,3′-diamino-N-methyldipropylamine and 24 parts of sodium hydroxide was added and stirred at 80 ° C. for 3 hours. After cooling to room temperature, 160 parts of concentrated hydrochloric acid was added, and 36 parts of 40% aqueous sodium nitrite solution was added at 30 ° C. at 5 to 10 ° C.
It was added dropwise over a period of minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドン １９.４部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。 This diazotized product was dissolved in a solution of 19.4 parts of 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone, 300 parts of water and 10 parts of soda ash in a 10% aqueous sodium hydroxide solution at pH = 7. While maintaining 0.0 to 8.0, the solution was added dropwise at 5 to 10 ° C. over 1 hour.
次いで３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−ヘキシル−２−ピリドン ２３.４部、水 ３００部、ソーダ灰 １０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで乾燥ケーキ ９７.３部を得た。
Next, a solution of 23.4 parts of 3-cyano-4-methyl-6-hydroxy-N-hexyl-2-pyridone, 300 parts of water and 10 parts of soda ash was dissolved in 10% aqueous sodium hydroxide solution at pH = 7.0. The solution was added dropwise at 5 to 10 ° C. over 1 hour while maintaining 8.0. After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 97.3 parts of a dry cake.
乾燥ケーキ ２６.２部をテトラヒドロフラン ５００部に溶解後、ヘキサメチレンジアミン ０.０２部およびジラウリン酸ジブチルスズ（II）０.１部を添加した。そこに遮光しながら２−イソシアナートエチルメタクリレート ８.５部をゆっくり添加し、４０℃で４時間撹拌した。 After 26.2 parts of the dried cake was dissolved in 500 parts of tetrahydrofuran, 0.02 part of hexamethylenediamine and 0.1 part of dibutyltin (II) dilaurate were added. Thereto was slowly added 8.5 parts of 2-isocyanatoethyl methacrylate while being shielded from light, and the mixture was stirred at 40 ° C. for 4 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下し た。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｈ−２２）で表される色素 ２７.８部を得た。この色素の最大吸収波長は４３１.０ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and then the wet cake obtained was dried to obtain 27.8 parts of the pigment represented by the formula (H-22). The maximum absorption wavelength of this dye was 431.0 nm (in ethyl acetate).
［実施例１２５］
＜化合物（Ｈ−２３）の合成＞
式（Ｉ−１５）の色素 ９４.８部をテトラヒドロフラン５００部に溶解後、遮光しながらマロニルクロリド １４.１部、ピリジン １６.０部を添加し、２０〜３０℃で３時間撹拌した。
[Example 125]
<Synthesis of Compound (H-23)>
After dissolving 94.8 parts of the dye of the formula (I-15) in 500 parts of tetrahydrofuran, 14.1 parts of malonyl chloride and 16.0 parts of pyridine were added while being protected from light, and stirred at 20 to 30 ° C. for 3 hours.
得られた反応液を真空にて１００部まで濃縮し、濃縮液を水 １０００部に滴下した。
析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｈ−２３）で表される色素 ９１.７部を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
The resulting reaction solution was concentrated to 100 parts in vacuo, and the concentrated solution was added dropwise to 1000 parts of water.
The precipitated pigment was separated by filtration, washed with water, and the obtained wet cake was dried to obtain 91.7 parts of a pigment represented by the formula (H-23). The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１２６］
＜化合物（Ｈ−２４）の合成＞
４−（β−スルファトエチルスルホニル）アニリン ５６.２部を水 ７００部を加えた後、水酸化ナトリウム ２４部を添加し、８０℃で３時間撹拌した。常温まで冷却後、濃塩酸 １６０部添加し、４０％亜硝酸ナトリウム水溶液 ３６部を５〜１０℃で３０分かけて滴下した。滴下後、５〜１０℃で４０分撹拌し、スルファミン酸にて過剰の亜硝酸を分解し、ジアゾ化物を得た。
[Example 126]
<Synthesis of Compound (H-24)>
After adding 700 parts of water to 56.2 parts of 4- (β-sulfatoethylsulfonyl) aniline, 24 parts of sodium hydroxide was added and stirred at 80 ° C. for 3 hours. After cooling to room temperature, 160 parts of concentrated hydrochloric acid was added, and 36 parts of a 40% sodium nitrite aqueous solution was added dropwise at 5 to 10 ° C. over 30 minutes. After dropping, the mixture was stirred at 5 to 10 ° C. for 40 minutes, and excessive nitrous acid was decomposed with sulfamic acid to obtain a diazotized product.
このジアゾ化物を３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−オクチル−２−ピリドン ２６.２部、３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−アミノエチル）−２−ピリドン １９.３部、水 ６００部、ソーダ灰 ２０部の溶解液に１０％水酸化ナトリウム水溶液でｐＨ＝７.０〜８.０を保持しながら５〜１０℃で１時間かけて滴下した。
滴下後、５〜１０℃で２時間撹拌した。
反応液を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで乾燥ケーキ ８
３.２部を得た。
This diazotized compound was converted to 26.2 parts of 3-cyano-4-methyl-6-hydroxy-N-octyl-2-pyridone, 3-cyano-4-methyl-6-hydroxy-N- (2-aminoethyl) -2. -A solution containing 19.3 parts of pyridone, 600 parts of water and 20 parts of soda ash was added dropwise at 5 to 10 ° C over 1 hour while maintaining pH = 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. .
After dropping, the mixture was stirred at 5 to 10 ° C. for 2 hours.
The reaction solution was separated by filtration, washed with water, and the resulting wet cake was dried to dry cake 8
3.2 parts were obtained.
乾燥ケーキ ４４.０部をジメチルホルムアミド ２００部に溶解後、遮光しながらテトラブチルアンモニウムブロミド ０.２部、４−ｔｅｒｔ−ブチルピロカテコール ０.４部、グリシジルメタクリレート ２１.３部を添加し、１２０〜１３０℃で４時間撹拌した。 After dissolving 44.0 parts of the dried cake in 200 parts of dimethylformamide, 0.2 part of tetrabutylammonium bromide, 0.4 part of 4-tert-butylpyrocatechol and 21.3 parts of glycidyl methacrylate were added while being protected from light. Stir at ~ 130 ° C for 4 hours.
冷却後、スクシニルクロリド ７.８部、ピリジン ７.９部を添加後、２０〜３０℃で３時間撹拌した。
得られた反応液を水 １０００部に滴下し、析出した色素を濾過にて濾別し、水洗後、得られた湿ケーキを乾燥することで式（Ｈ−２４）で表される色素 ４４.５部を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
After cooling, 7.8 parts of succinyl chloride and 7.9 parts of pyridine were added, followed by stirring at 20 to 30 ° C. for 3 hours.
The obtained reaction solution was added dropwise to 1000 parts of water, and the precipitated dye was filtered off, washed with water, and then the resulting wet cake was dried to give a dye represented by the formula (H-24) 44. 5 parts were obtained. The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［実施例１２７］
＜化合物（Ｈ−２５）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−オクチル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−エチル−２−ピリドンを、スクシニルクロリドに変えてテレフタロイルクロリドを使用したこと以外は実施例１２６と同様に行うことで式（Ｈ−２５）の色素を得た。この色素の最大吸収波長は４２２.５ｎｍ（酢酸エチル中）であった。
[Example 127]
<Synthesis of Compound (H-25)>
Change 3-cyano-4-methyl-6-hydroxy-N-octyl-2-pyridone to 3-cyano-4-methyl-6-hydroxy-N-ethyl-2-pyridone and succinyl chloride to terephthalo The dye of formula (H-25) was obtained in the same manner as in Example 126 except that yl chloride was used. The maximum absorption wavelength of this dye was 422.5 nm (in ethyl acetate).
［実施例１２８］
＜化合物（Ｈ−２６）の合成＞
式（Ｉ−１）の色素に変えて式（Ｉ−２６）の色素を使用したこと以外は実施例１０と同様に行うことで式（Ｈ−２６）の色素を得た。この色素の最大吸収波長は４２３.０ｎｍ（酢酸エチル中）であった。
[Example 128]
<Synthesis of Compound (H-26)>
The dye of the formula (H-26) was obtained in the same manner as in Example 10 except that the dye of the formula (I-26) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 423.0 nm (in ethyl acetate).
［実施例１２９］
＜化合物（Ｈ−２７）の合成＞
３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−プロピル−２−ピリドンに変えて３−シアノ−４−メチル−６−ヒドロキシ−Ｎ−（２−アミノエチル）−２−ピリドンを使用したこと以外は実施例１０３と同様に行うことで式（Ｉ−２９）の色素を得た。
[Example 129]
<Synthesis of Compound (H-27)>
The use of 3-cyano-4-methyl-6-hydroxy-N- (2-aminoethyl) -2-pyridone instead of 3-cyano-4-methyl-6-hydroxy-N-propyl-2-pyridone The dye of formula (I-29) was obtained in the same manner as in Example 103 except that.
［実施例１３０］
＜化合物（Ｈ−２８）の合成＞
式（Ｉ−１）の色素に変えて式（Ｈ−２１）の色素を使用したこと以外は実施例１２と同様に行うことで式（Ｈ−２８）の色素を得た。この色素の最大吸収波長は４２２.０ｎｍ（酢酸エチル中）であった。
[Example 130]
<Synthesis of Compound (H-28)>
The dye of the formula (H-28) was obtained in the same manner as in Example 12 except that the dye of the formula (H-21) was used instead of the dye of the formula (I-1). The maximum absorption wavelength of this dye was 422.0 nm (in ethyl acetate).
［比較例１〜１３］
下記式（Ｊ−１）〜（Ｊ−１３）の色素を公知の処方にて合成を行い、比較用サンプルとした。
[Comparative Examples 1 to 13]
The pigment | dyes of following formula (J-1)-(J-13) were synthesize | combined by the well-known prescription, and it was set as the sample for a comparison.
〔色素の評価〕
（Ａ）色素の溶解性
上記実施例１〜１３０で得られた色素を恒温槽を用いて、２５℃に保ちながら酢酸エチルへの溶解度を測定し、結果を表１に示す。また比較例１〜１３で得られた色素についても同様に２５℃に保ちながら酢酸エチルへの溶解度を測定し、結果を表１に示す。判定基準については以下の基準により評価した。
(Evaluation of dye)
(A) Solubility of the dye The solubility of the dye obtained in Examples 1 to 130 in ethyl acetate was measured using a thermostat while maintaining the temperature at 25 ° C. Table 1 shows the results. Further, the dyes obtained in Comparative Examples 1 to 13 were similarly measured for solubility in ethyl acetate while being kept at 25 ° C., and the results are shown in Table 1. Judgment criteria were evaluated according to the following criteria.
◎ 酢酸エチルへの溶解度が２０％（ｗ／ｗ）以上ある。
○ 酢酸エチルへの溶解度が１５％（ｗ／ｗ）以上ある。
△ 酢酸エチルへの溶解度が１０％（ｗ／ｗ）以上ある。
× 酢酸エチルへの溶解度が１０％（ｗ／ｗ）未満である。
A solubility in ethyl acetate is 20% (w / w) or more.
○ Solubility in ethyl acetate is 15% (w / w) or more.
Δ Solubility in ethyl acetate is 10% (w / w) or more.
X Solubility in ethyl acetate is less than 10% (w / w).
（Ｂ）色素溶解液の調製
上記実施例１〜１３０で得られた色素 １０部を酢酸エチル ９０部で溶解し、得られた色素溶液を０.４５μｍのメンブランフィルターで濾過を行うことにより色素溶解液を調製した。また比較例１〜１３で得られた色素についても同様に処理を行い、色素溶解液を調製した。
(B) Preparation of dye solution 10 parts of the dye obtained in Examples 1 to 130 were dissolved in 90 parts of ethyl acetate, and the resulting dye solution was filtered through a 0.45 μm membrane filter to dissolve the dye. A liquid was prepared. Moreover, it processed similarly about the pigment | dye obtained by Comparative Examples 1-13, and the pigment | dye solution was prepared.
（Ｃ）色素溶解液の耐熱安定性
上記（Ｂ）で得られた色素溶解液を溶解直後に酢酸エチル溶媒で１００ｐｐｍ（色素分で１０ｐｐｍ）に調液し、分光光度計 Ｕ−２９１０（ＨＩＴＡＣＨＩ社製）で吸光度を測定する。
(C) Heat-resistant stability of the dye solution The dye solution obtained in the above (B) was adjusted to 100 ppm (10 ppm for the dye content) with an ethyl acetate solvent immediately after dissolution, and a spectrophotometer U-2910 (HITACHI) Measure the absorbance.
上記（Ｂ）で得られた色素溶解液を密閉状態で恒温器内に６０℃で３０日間放置し、再度酢酸エチル溶媒で１００ｐｐｍ（色素分で１０ｐｐｍ）に調液し、分光光度計 Ｕ−２９１０（ＨＩＴＡＣＨＩ社製）で吸光度を測定し、結果を表１に示す。判定基準については以下の基準により評価した。 The dye-dissolved solution obtained in the above (B) was allowed to stand in a thermostat at 60 ° C. for 30 days in a sealed state, and again adjusted to 100 ppm (10 ppm for the dye content) with an ethyl acetate solvent, and a spectrophotometer U-2910 Absorbance was measured by (manufactured by HITACHI), and the results are shown in Table 1. Judgment criteria were evaluated according to the following criteria.
◎ 耐熱試験後の吸光度が耐熱試験前の９８％以上ある。
○ 耐熱試験後の吸光度が耐熱試験前の９５％以上ある。
△ 耐熱試験後の吸光度が耐熱試験前の９０％以上ある。
× 耐熱試験後の吸光度が耐熱試験前の９０％未満となる。
◎ Absorbance after heat test is 98% or more before heat test.
○ The absorbance after the heat test is 95% or more before the heat test.
Δ: Absorbance after heat test is 90% or more before heat test.
X Absorbance after the heat test is less than 90% before the heat test.
（Ｄ）色素溶解液の耐冷安定性
上記（Ｂ）で得られた色素溶解液をインキュベーター内に−１０℃で９０日放置し、色素の析出度合いを目視にて判断し、結果を表１に示す。判定基準については以下の基準により評価した。
(D) Cooling stability of the dye solution The dye solution obtained in (B) above is left in an incubator for 90 days at −10 ° C., the degree of dye precipitation is determined visually, and the results are shown in Table 1. Show. Judgment criteria were evaluated according to the following criteria.
◎ 低温試験後に色素の析出が全くない。
○ 低温試験後に色素の析出がほぼない。
△ 低温試験後に色素の析出が少しある。
× 低温試験後に色素の析出が著しくある。
◎ No pigment deposition after low temperature test.
○ There is almost no pigment deposition after the low temperature test.
Δ: There is little pigment deposition after the low temperature test.
X Significant precipitation of pigment after low temperature test.
（Ｅ）インクジェットプリント
上記（Ｂ）で得られた色素溶解液をインクジェットプリンター（キヤノン社製 ＰＩＸＵＳ ｉＰ４３００）用インクカートリッジに充填し、同プリンターにて普通紙（キヤノン社製：キヤノン普通紙・ホワイト Ａ４）を用い、縦１５ｃｍ×横１０ｃｍの範囲を塗り潰し、テストサンプルとした。
(E) Inkjet printing The dye solution obtained in (B) above is filled in an ink cartridge for an inkjet printer (PIXUS iP4300, manufactured by Canon Inc.), and plain paper (manufactured by Canon Inc .: Canon plain paper / white A4) is used in the printer. ) Was used to fill a 15 cm long × 10 cm wide range to obtain a test sample.
（Ｆ）記録画像の耐光性試験
（Ｅ）でプリントした各テストサンプルの印字濃度を反射濃度測色計（Ｍａｃｂｅｔｈ
ＣＯＬＯＲ−ＥＹＥ ３０００）で測定する。次にスタンダード紫外線ロングライフ・フェードメーターＦＡＬ−３（スガ試験機社製）を用いて、６０℃で５０時間照射後、再び印字濃度を測定し、結果を表１に示す。判定基準については以下の基準により評価した。
(F) Light resistance test of recorded image The print density of each test sample printed in (E) is measured by a reflection density colorimeter (Macbeth).
COLOR-EYE 3000). Next, using a standard ultraviolet long life fade meter FAL-3 (manufactured by Suga Test Instruments Co., Ltd.), the print density was measured again after irradiation for 50 hours at 60 ° C. Table 1 shows the results. Judgment criteria were evaluated according to the following criteria.
◎ 照射後の印字濃度が照射前の９０％以上ある。
○ 照射後の印字濃度が照射前の８０％以上ある。
△ 照射後の印字濃度が照射前の７０％以上ある。
× 照射後の印字濃度が照射前の７０％未満となる。
◎ Print density after irradiation is 90% or more before irradiation.
○ The print density after irradiation is 80% or more before irradiation.
Δ: Print density after irradiation is 70% or more before irradiation.
X Print density after irradiation is less than 70% before irradiation.
（Ｇ）記録画像の耐水性試験
（Ｅ）でプリントした各テストサンプルの印字濃度を反射濃度測色計（Ｍａｃｂｅｔｈ
ＣＯＬＯＲ−ＥＹＥ ３０００）で測定する。次に各テストサンプルを２５℃イオン交換水に１時間浸漬させ充分水分を取り除いたものを１日間温風乾燥させた後、再び印字濃度を測定し、結果を表１に示す。判定基準については以下の基準により評価した。
(G) Water resistance test of recorded image Print density of each test sample printed in (E) is measured by reflection density colorimeter (Macbeth).
COLOR-EYE 3000). Next, each test sample was immersed in 25 ° C. ion-exchanged water for 1 hour to sufficiently remove moisture, and then dried with warm air for 1 day, and then the print density was measured again. The results are shown in Table 1. Judgment criteria were evaluated according to the following criteria.
◎ 浸漬後の印字濃度が浸漬前の９５％以上ある。
○ 浸漬後の印字濃度が浸漬前の９０％以上ある。
△ 浸漬後の印字濃度が浸漬前の８５％以上ある。
× 浸漬後の印字濃度が浸漬前の８０％未満となる。
◎ The printing density after immersion is 95% or more before immersion.
○ The printing density after immersion is 90% or more before immersion.
Δ: The printing density after immersion is 85% or more before immersion.
X Print density after immersion is less than 80% before immersion.
（Ｈ）記録画像の耐湿性試験
（Ｅ）でプリントした各テストサンプルの印字濃度を反射濃度測色計（Ｍａｃｂｅｔｈ
ＣＯＬＯＲ−ＥＹＥ ３０００）で測定する。次に恒温恒湿器（アドバンテック東洋社製）を用いて５０℃、９０％ＲＨで５日放置した後、試験前後の色素の滲みを目視により判定した。結果を表１に示す。判定基準については以下の基準により評価した。
(H) Humidity resistance test of recorded image The print density of each test sample printed in (E) is measured by a reflection density colorimeter (Macbeth).
COLOR-EYE 3000). Next, using a thermo-hygrostat (manufactured by Advantech Toyo Co., Ltd.), it was allowed to stand at 50 ° C. and 90% RH for 5 days, and then the bleeding of the dye before and after the test was judged visually. The results are shown in Table 1. Judgment criteria were evaluated according to the following criteria.
◎ 色素の未印字部への滲みが全く見られない。
○ 色素の未印字部への滲みが僅かに見られる。
△ 色素の未印字部への滲みがやや見られる。
× 色素の未印字部への滲みがかなり見られる。
◎ No bleeding of the dye on the unprinted area is observed.
○ Slight bleeding on the unprinted area of the dye is observed.
Δ: Some blurring of the dye on the unprinted area is observed.
× The bleeding of the dye on the unprinted part is considerably observed.
表１より本発明のアゾ化合物は従来のアゾ化合物（比較例）と比較して、耐光性、耐水性、耐湿性、保存安定性において優れているおり、高品質な画像が保たれるという優れた効果を奏することが確認された。 From Table 1, the azo compound of the present invention is superior in light resistance, water resistance, moisture resistance, and storage stability as compared with the conventional azo compound (comparative example), and excellent in that a high-quality image is maintained. It was confirmed that there was an effect.
Claims (5)
Ｄ−（Ａ）n （１）
〔Ｄは、下記式（Ａ−１）〜（Ａ−８）
Ｒ 10 はシアノ基、カルバモイル基、スルホン基、またはスルホメチル基を表し、
Ｒ 11 は水素、Ｃ 1 〜Ｃ 10 のアルキル基、Ｃ 2 〜Ｃ 8 のアルコキシアルキル基、Ｃ 1 〜Ｃ 4 の
ヒドロキシアルキル基、Ｃ 2 〜Ｃ 4 のスルホアルキル基、重合性不飽和基を有する基、または下記式（７）
Ｒ 15 およびＲ 16 はそれぞれ独立して、水素、Ｃ 1 〜Ｃ 4 のアルキル基、Ｃ 1 〜Ｃ 3 のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表し、
Ｒ 27 およびＲ 28 はそれぞれ独立して、Ｃ 1 〜Ｃ 4 のアルキル基、またはトリフルオロメチル基を表し、
Ｒ 29 およびＲ 30 はそれぞれ独立して、シアノ基、またはカルバモイル基を表し、
ＹはＣ 2 〜Ｃ 6 のアルキレン基、または下記式（１５）
Ｌ 1 はアリーレン基、複素環基、酸素原子、または下記式（１６）
Ｒ 60 はヒドロキシル基、アミノ基、Ｃ 1 〜Ｃ 4 のアルキルアミノ基、またはアセチルアミノ基を表し、
Ｒ 61 およびＲ 62 はそれぞれ独立して、水素、Ｃ 1 〜Ｃ 3 のアルキル基、Ｃ 1 〜Ｃ 3 のアルコキシル基、アミノ基、ヒドロキシル基、アセチルアミノ基、またはハロゲン基を表し、
Ｒ 63 はヒドロキシル基、またはＣ 1 〜Ｃ 10 のアルキルアミノ基を表し、
Ｒ 64 はヒドロキシル基、アミノ基、Ｃ 1 〜Ｃ 4 のアルキルアミノ基、Ｃ 1 〜Ｃ 4 のジアルキルアミノ基、またはアセチルアミノ基を表し、
Ｒ 65 は水素、ヒドロキシル基、アミノ基、Ｃ 1 〜Ｃ 4 のアルキルアミノ基、Ｃ 1 〜Ｃ 4 のジアルキルアミノ基、アセチルアミノ基、フェニルアミノ基、またはベンゾイルアミノ基を表し、
Ｒ 66 はヒドロキシル基、またはＣ 1 〜Ｃ 10 のアルキルアミノ基を表し、
Ｒ 67 およびＲ 68 はそれぞれ独立して、ヒドロキシル基、またはアミノ基を表し、
Ｒ 69 はヒドロキシル基、またはＣ 1 〜Ｃ 10 のアルキルアミノ基を表し、
Ｒ 70 は水素、アミノ基、またはカルボキシル基を表し、
Ｒ 71 およびＲ 72 はそれぞれ独立して、水素、Ｃ 1 〜Ｃ 3 のアルキル基、Ｃ 1 〜Ｃ 3 のアルコキシル基、またはハロゲン基を表し、
Ｒ 73 はヒドロキシル基、Ｃ 1 〜Ｃ 10 のアルキルアミノ基、またはＣ 1 〜Ｃ 10 のアルキルアミノエチル基を表し、
Ｒ 74 は水素、またはＣ 1 〜Ｃ 10 のアルキル基を表し、
Ｒ 75 およびＲ 76 はそれぞれ独立して、水素、またはＣ 1 〜Ｃ 10 のアルキル基を表し、
そして、式（Ａ−１）、（Ａ−３）〜（Ａ−６）にスルホン基が含まれる場合、そのス
ルホン基は−ＳＯ 3 ＨまたはＣ 1 〜Ｃ 8 のアルキルアミン塩、Ｃ 1 〜Ｃ 16 のジアルキルアミン塩、もしくはＣ 1 〜Ｃ 24 のトリアルキルアミン塩である]
から選択され、
Ａは下記式（２）
Ｘ1は下記式（３）または下記式（４）
Ｒ7およびＲ8はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表す｝を表す]を表し、
ｎは１〜４の整数を表し、またｎが２〜４の場合はＡのそれぞれは同一でも異なっても良く、かつ式（１）には少なくとも１つの重合性不飽和基を有する基が含まれ、
ここで、重合性不飽和基を有する基は、−Ｃ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−ＳＯ 2 −アリーレン−（Ｃ 2 〜Ｃ 4 ）アルケニル基、−Ｃ（＝Ｏ）ＮＨ−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 6 ）アルキレン（ＯＨ）−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、もしくは−ＳＯ 2 −（Ｃ 2 〜Ｃ 6 ）アルケニル基、または−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＨのヒドロキシル基の水素原子もしくは−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＮＨ 2 のアミノ基の水素原子が、−Ｃ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−ＳＯ 2 −アリーレン−（Ｃ 2 〜Ｃ 4 ）アルケニル基、−Ｃ（＝Ｏ）ＮＨ−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 6 ）アルキレン（ＯＨ）−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、もしくは−ＳＯ 2 −（Ｃ 2 〜Ｃ 6 ）アルケニル基で置換された基を表す〕で表されるアゾ化合物。 Following formula (1)
D- (A) n (1)
[D is the following formula (A-1) to (A-8)
R 10 represents a cyano group, a carbamoyl group, a sulfone group, or a sulfomethyl group,
R 11 represents hydrogen, an alkyl group of C 1 -C 10, an alkoxyalkyl group of C 2 -C 8, of C 1 -C 4
Hydroxyalkyl group, a sulfoalkyl group of C 2 -C 4, groups having a polymerizable unsaturated group or the following formula (7)
R 15 and R 16 each independently represents hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group).
R 27 and R 28 each independently represent an alkyl group or a trifluoromethyl group, a C 1 -C 4,
R 29 and R 30 each independently represents a cyano group or a carbamoyl group,
Y is an alkylene group of C 2 -C 6 or the following formula (15)
L 1 represents an arylene group, a heterocyclic group, an oxygen atom, or the following formula (16)
R 60 represents a hydroxyl group, an amino group, a C 1 -C 4 alkylamino group, or an acetylamino group;
R 61 and R 62 each independently represent hydrogen, a C 1 -C 3 alkyl group, a C 1 -C 3 alkoxyl group, an amino group, a hydroxyl group, an acetylamino group, or a halogen group;
R 63 represents a hydroxyl group or a C 1 -C 10 alkylamino group,
R 64 represents a hydroxyl group, an amino group, a C 1 -C 4 alkylamino group, a C 1 -C 4 dialkylamino group, or an acetylamino group;
R 65 represents hydrogen, hydroxyl group, an amino group, an alkylamino group of C 1 -C 4, a dialkylamino group of C 1 -C 4, an acetylamino group, phenylamino group or benzoylamino group,
R 66 represents a hydroxyl group or a C 1 -C 10 alkylamino group;
R 67 and R 68 each independently represent a hydroxyl group or an amino group;
R 69 represents an alkylamino group of the hydroxyl group or C 1 ~C 10,,
R 70 represents hydrogen, an amino group, or a carboxyl group,
R 71 and R 72 each independently represent hydrogen, a C 1 -C 3 alkyl group, a C 1 -C 3 alkoxyl group, or a halogen group;
R 73 represents a hydroxyl group, a C 1 -C 10 alkylamino group, or a C 1 -C 10 alkylaminoethyl group,
R 74 represents hydrogen or a C 1 to C 10 alkyl group,
R 75 and R 76 each independently represent hydrogen or a C 1 -C 10 alkyl group;
When the formulas (A-1) and (A-3) to (A-6) contain a sulfone group,
The ruphone group is —SO 3 H or a C 1 -C 8 alkylamine salt, a C 1 -C 16 dialkylamine salt, or a C 1 -C 24 trialkylamine salt.
Selected from
A is the following formula (2)
X 1 is the following formula (3) or the following formula (4)
R 7 and R 8 each independently represent hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group. Represents
n represents an integer of 1 to 4, and when n is 2 to 4, each A may be the same or different, and the formula (1) includes a group having at least one polymerizable unsaturated group. It is,
Here, a group having a polymerizable unsaturated group, -C (= O) - ( C 2 ~C 6) alkenyl group, -SO 2 - arylene - (C 2 ~C 4) alkenyl group, -C (= O) NH- (C 1 ~C 4 ) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 4) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 -C 6) alkylene (OH) -OC (= O) - (C 2 ~C 6) alkenyl group, or -SO 2 - (C 2 ~C 6 ) alkenyl group or, The hydrogen atom of the hydroxyl group of — (C 1 -C 4 ) alkylene-OH or the hydrogen atom of the amino group of — (C 1 -C 4 ) alkylene-NH 2 is —C (═O) — (C 2 -C 6) alkenyl, -SO 2 - arylene - (C 2 ~C 4) alkenyl group, -C (= O) NH- ( C 1 ~C 4) Al Len -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 4) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 6) alkylene (OH) -OC (= O) - (C 2 ~C 6) alkenyl group, or -SO 2 - (C 2 ~C 6 ) azo represented by represents] a substituted group an alkenyl group Compound.
Ｒ10はシアノ基、カルバモイル基、スルホン基、またはスルホメチル基を表し、
Ｒ11は水素、Ｃ1〜Ｃ10のアルキル基、Ｃ2〜Ｃ8のアルコキシアルキル基、Ｃ1〜Ｃ4のヒドロキシアルキル基、Ｃ2〜Ｃ4のスルホアルキル基、重合性不飽和基を有する基、または下記式（７）
Ｒ15およびＲ16はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表し、
Ｒ12およびＲ13はそれぞれ独立して、水素、ハロゲン、Ｃ1〜Ｃ3のアルキル基、またはＣ1〜Ｃ3のアルコキシル基を表し、
Ｘ2は下記式（８）または下記式（９）
Ｒ21およびＲ22はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表す｝を表し、かつ式（６）には少なくとも１つの重合性不飽和基を有する基が含まれ、
ここで、重合性不飽和基を有する基は、−Ｃ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−ＳＯ 2 −アリーレン−（Ｃ 2 〜Ｃ 4 ）アルケニル基、−Ｃ（＝Ｏ）ＮＨ−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 6 ）アルキレン（ＯＨ）−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、もしくは−ＳＯ 2 −（Ｃ 2 〜Ｃ 6 ）アルケニル基、または−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＨのヒドロキシル基の水素原子もしくは−（Ｃ 1 〜Ｃ 4 ）アル
キレン−ＮＨ 2 のアミノ基の水素原子が、−Ｃ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−ＳＯ 2 −アリーレン−（Ｃ 2 〜Ｃ 4 ）アルケニル基、−Ｃ（＝Ｏ）ＮＨ−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 6 ）アルキレン（ＯＨ）−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、もしくは−ＳＯ 2 −（Ｃ 2 〜Ｃ 6 ）アルケニル基で置換された基を表す〕で表される請求項１記載のアゾ化合物。 Following formula (6)
R 10 represents a cyano group, a carbamoyl group, a sulfone group, or a sulfomethyl group,
R 11 represents hydrogen, a C 1 -C 10 alkyl group, a C 2 -C 8 alkoxyalkyl group, a C 1 -C 4 hydroxyalkyl group, a C 2 -C 4 sulfoalkyl group, or a polymerizable unsaturated group. Or a group having the following formula (7)
R 15 and R 16 each independently represents hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group).
R 12 and R 13 each independently represent hydrogen, halogen, a C 1 -C 3 alkyl group, or a C 1 -C 3 alkoxyl group;
X 2 is the following formula (8) or the following formula (9)
R 21 and R 22 each independently represent hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group)} And the formula (6) includes a group having at least one polymerizable unsaturated group ,
Here, a group having a polymerizable unsaturated group, -C (= O) - ( C 2 ~C 6) alkenyl group, -SO 2 - arylene - (C 2 ~C 4) alkenyl group, -C (= O) NH- (C 1 ~C 4 ) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 4) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 -C 6) alkylene (OH) -OC (= O) - (C 2 ~C 6) alkenyl group, or -SO 2 - (C 2 ~C 6 ) alkenyl group or, -(C 1 -C 4 ) alkylene-OH hydroxyl group hydrogen atom or- (C 1 -C 4 ) al
The hydrogen atom of the amino group of xylene-NH 2 is —C (═O) — (C 2 -C 6 ) alkenyl group, —SO 2 -arylene- (C 2 -C 4 ) alkenyl group, —C (═O ) NH- (C 1 ~C 4) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 4) alkylene -OC (= O) - (C 2 ~C 6 ) alkenyl, - (C 1 ~C 6) alkylene (OH) -OC (= O) - (C 2 ~C 6) alkenyl group, or -SO 2 - (C 2 ~C 6 ) substituted by an alkenyl group azo compound according to claim 1, represented by the representative of the group].
Ｒ27およびＲ28はそれぞれ独立して、Ｃ1〜Ｃ4のアルキル基、またはトリフルオロメチル基を表し、
Ｒ29およびＲ30はそれぞれ独立して、シアノ基、またはカルバモイル基を表し、
Ｘ3およびＸ4はそれぞれ独立して、下記式（１２）または下記式（１３）
Ｒ35 およびＲ36はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表す｝を表し、
ＹはＣ2〜Ｃ6のアルキレン基、または下記式（１５）
Ｌ1はアリーレン基、複素環基、酸素原子、または下記式（１６）
ここで、重合性不飽和基を有する基は、−Ｃ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−ＳＯ 2 −アリーレン−（Ｃ 2 〜Ｃ 4 ）アルケニル基、−Ｃ（＝Ｏ）ＮＨ−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 6 ）アルキレン（ＯＨ）−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、もしくは−ＳＯ 2 −（Ｃ 2 〜Ｃ 6 ）アルケニル基、または−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＨのヒドロキシル基の水素原子もしくは−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＮＨ 2 のアミノ基の水素原子が、−Ｃ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−ＳＯ 2 −アリーレン−（Ｃ 2 〜Ｃ 4 ）アルケニル基、−Ｃ（＝Ｏ）ＮＨ−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 6 ）アルキレン（ＯＨ）−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、もしくは−ＳＯ 2 −（Ｃ 2 〜Ｃ 6 ）アルケニル基で置換された基を表す〕で表される請求項１記載のアゾ化合物。 Following formula (11)
R 27 and R 28 each independently represent an alkyl group or a trifluoromethyl group, a C 1 -C 4,
R 29 and R 30 each independently represents a cyano group or a carbamoyl group,
X 3 and X 4 each independently represent the following formula (12) or the following formula (13)
R 35 and R 36 each independently represent hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group)}
Y is an alkylene group of C 2 -C 6 or the following formula (15)
L 1 represents an arylene group, a heterocyclic group, an oxygen atom, or the following formula (16)
Here, a group having a polymerizable unsaturated group, -C (= O) - ( C 2 ~C 6) alkenyl group, -SO 2 - arylene - (C 2 ~C 4) alkenyl group, -C (= O) NH- (C 1 ~C 4 ) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 4) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 -C 6) alkylene (OH) -OC (= O) - (C 2 ~C 6) alkenyl group, or -SO 2 - (C 2 ~C 6 ) alkenyl group or, The hydrogen atom of the hydroxyl group of — (C 1 -C 4 ) alkylene-OH or the hydrogen atom of the amino group of — (C 1 -C 4 ) alkylene-NH 2 is —C (═O) — (C 2 -C 6) alkenyl, -SO 2 - arylene - (C 2 ~C 4) alkenyl group, -C (= O) NH- ( C 1 ~C 4) Al Len -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 4) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 6) alkylene (OH) -OC (= O) - (C 2 ~C 6) alkenyl group, or -SO 2 - (C 2 ~C 6 ) according represented by represents] a substituted group an alkenyl group Item 2. An azo compound according to Item 1.
Ｒ44およびＲ45はそれぞれ独立して、Ｃ1〜Ｃ4のアルキル基、またはトリフルオロメチル基を表し、
Ｒ46およびＲ47はそれぞれ独立して、シアノ基、またはカルバモイル基を表し、
Ｒ48およびＲ49はそれぞれ独立して、水素、Ｃ1〜Ｃ10のアルキル基、Ｃ2〜Ｃ8のアルコキシアルキル基、Ｃ1〜Ｃ4のヒドロキシアルキル基、重合性不飽和基を有する基、または下記式（１８）
Ｒ51およびＲ52はそれぞれ独立して、水素、Ｃ1〜Ｃ4のアルキル基、Ｃ1〜Ｃ3のヒドロキシアルキル基、または重合性不飽和基を有する基を表す）を表し、
Ｚは複素環基、下記式（１９）または下記式（２０）
Ｒ54およびＲ55はそれぞれ独立して、水素、Ｃ1〜Ｃ10のアルキル基、Ｃ1〜Ｃ4のヒドロキシアルキル基、または重合性不飽和基を有する基を表し、
Ｌ2はＣ2〜Ｃ6のアルキレン基、または下記式（２２）
Ｌ3はアリーレン基、複素環基、酸素原子、または下記式（２３）
ここで、重合性不飽和基を有する基は、−Ｃ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−ＳＯ 2 −アリーレン−（Ｃ 2 〜Ｃ 4 ）アルケニル基、−Ｃ（＝Ｏ）ＮＨ−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 6 ）アルキレン（ＯＨ）−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、もしくは−ＳＯ 2 −（Ｃ 2 〜Ｃ 6 ）アルケニル基、または−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＨのヒドロキシル基の水素原子もしくは−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＮＨ 2 のアミノ基の水素原子が、−Ｃ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−ＳＯ 2 −アリーレン−（Ｃ 2 〜Ｃ 4 ）アルケニル基、−Ｃ（＝Ｏ）ＮＨ−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 4 ）アルキレン−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、−（Ｃ 1 〜Ｃ 6 ）アルキレン（ＯＨ）−ＯＣ（＝Ｏ）−（Ｃ 2 〜Ｃ 6 ）アルケニル基、もしくは−ＳＯ 2 −（Ｃ 2 〜Ｃ 6 ）アルケニル基で置換された基を表す〕で表されるアゾ化合物。 Following formula (17)
R 44 and R 45 each independently represents a C 1 -C 4 alkyl group or a trifluoromethyl group;
R 46 and R 47 each independently represent a cyano group or a carbamoyl group,
R 48 and R 49 are each independently hydrogen, a C 1 -C 10 alkyl group, a C 2 -C 8 alkoxyalkyl group, a C 1 -C 4 hydroxyalkyl group, or a group having a polymerizable unsaturated group. Or the following formula (18)
R 51 and R 52 each independently represent hydrogen, a C 1 -C 4 alkyl group, a C 1 -C 3 hydroxyalkyl group, or a group having a polymerizable unsaturated group).
Z is a heterocyclic group, the following formula (19) or the following formula (20)
R 54 and R 55 each independently represent hydrogen, a C 1 -C 10 alkyl group, a C 1 -C 4 hydroxyalkyl group, or a group having a polymerizable unsaturated group;
L 2 is a C 2 to C 6 alkylene group, or the following formula (22)
L 3 represents an arylene group, a heterocyclic group, an oxygen atom, or the following formula (23)
Here, a group having a polymerizable unsaturated group, -C (= O) - ( C 2 ~C 6) alkenyl group, -SO 2 - arylene - (C 2 ~C 4) alkenyl group, -C (= O) NH- (C 1 ~C 4 ) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 4) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 -C 6) alkylene (OH) -OC (= O) - (C 2 ~C 6) alkenyl group, or -SO 2 - (C 2 ~C 6 ) alkenyl group or, The hydrogen atom of the hydroxyl group of — (C 1 -C 4 ) alkylene-OH or the hydrogen atom of the amino group of — (C 1 -C 4 ) alkylene-NH 2 is —C (═O) — (C 2 -C 6) alkenyl, -SO 2 - arylene - (C 2 ~C 4) alkenyl group, -C (= O) NH- ( C 1 ~C 4) Al Len -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 4) alkylene -OC (= O) - (C 2 ~C 6) alkenyl, - (C 1 ~C 6) alkylene (OH) -OC (= O) - (C 2 ~C 6) alkenyl group, or -SO 2 - (C 2 ~C 6 ) azo represented by represents] a substituted group an alkenyl group Compound.
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