JP7527920B2 - Xanthene dye, dye composition, colorant for anodized aluminum, coloring method, and method for producing the dye - Google Patents
Xanthene dye, dye composition, colorant for anodized aluminum, coloring method, and method for producing the dye Download PDFInfo
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- JP7527920B2 JP7527920B2 JP2020165788A JP2020165788A JP7527920B2 JP 7527920 B2 JP7527920 B2 JP 7527920B2 JP 2020165788 A JP2020165788 A JP 2020165788A JP 2020165788 A JP2020165788 A JP 2020165788A JP 7527920 B2 JP7527920 B2 JP 7527920B2
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- aluminum
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- 239000000975 dye Substances 0.000 title claims description 107
- 229910052782 aluminium Inorganic materials 0.000 title claims description 91
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 91
- 239000003086 colorant Substances 0.000 title claims description 44
- 239000000203 mixture Substances 0.000 title claims description 35
- 239000001018 xanthene dye Substances 0.000 title claims description 23
- 238000004040 coloring Methods 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 109
- 125000001424 substituent group Chemical group 0.000 claims description 93
- 125000003277 amino group Chemical group 0.000 claims description 20
- 125000001624 naphthyl group Chemical group 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 229910000838 Al alloy Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000002252 acyl group Chemical group 0.000 claims description 10
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 8
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 claims description 5
- -1 n-octyl Chemical group 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000004043 dyeing Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- 150000001721 carbon Chemical group 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000007743 anodising Methods 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- XTWQOSYEUVHDIT-CQRHUGCQSA-M sodium 3alpha,7alpha-dihydroxy-5beta-cholane-24-sulfonate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCCS([O-])(=O)=O)C)[C@@]2(C)CC1 XTWQOSYEUVHDIT-CQRHUGCQSA-M 0.000 description 4
- 125000004436 sodium atom Chemical group 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 150000002641 lithium Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000006039 1-hexenyl group Chemical group 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- QIWIPKRMEQMLMX-UHFFFAOYSA-N 2-(3,6-dichloroxanthen-10-ium-9-yl)benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1C1=C(C=CC(Cl)=C2)C2=[O+]C2=C1C=CC(Cl)=C2 QIWIPKRMEQMLMX-UHFFFAOYSA-N 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000004623 carbolinyl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001352 cyclobutyloxy group Chemical group C1(CCC1)O* 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
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- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
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- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- OOYIOIOOWUGAHD-UHFFFAOYSA-L disodium;2',4',5',7'-tetrabromo-4,5,6,7-tetrachloro-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [Na+].[Na+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(Br)=C([O-])C(Br)=C1OC1=C(Br)C([O-])=C(Br)C=C21 OOYIOIOOWUGAHD-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 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 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 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 1
- 239000012860 organic pigment Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004308 pyranonyl group Chemical group O1C(C(=CC=C1)*)=O 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- UWMZZSRDUVJJDP-UHFFFAOYSA-M sodium 2-[3-(2-methylanilino)-6-(2-methyl-4-sulfonatoanilino)xanthen-10-ium-9-yl]benzoate Chemical compound [Na+].Cc1ccccc1Nc1ccc2c(-c3ccccc3C([O-])=O)c3ccc(Nc4ccc(cc4C)S([O-])(=O)=O)cc3[o+]c2c1 UWMZZSRDUVJJDP-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000005033 thiopyranyl group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/243—Chemical after-treatment using organic dyestuffs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Materials For Photolithography (AREA)
- Plural Heterocyclic Compounds (AREA)
- Optical Filters (AREA)
Description
本発明は、陽極酸化アルミニウム用着色剤に適したキサンテン系色素および染料組成物に関する。また、該色素および染料組成物を用いる陽極酸化アルミニウムの着色方法、ならびに該色素の製造方法に関する。 The present invention relates to a xanthene dye and dye composition suitable for use as a colorant for anodized aluminum. It also relates to a method for coloring anodized aluminum using the dye and dye composition, and a method for producing the dye.
従来、アルミニウム（その酸化物または合金も含む）表面への着色方法として、水および適当な酸を含む電解液中でアルミニウムを陽極として通電（陽極酸化）し、表面に多孔質の酸化アルミニウム皮膜（アルマイト皮膜）を形成させた後、有機色素（または有機染料）を着色剤として表面を着色する方法が用いられている（特許文献１～５）。 Conventionally, a method for coloring the surface of aluminum (including its oxides or alloys) has been used in which aluminum is used as the anode in an electrolyte containing water and a suitable acid (anodic oxidation), a porous aluminum oxide film (anodized film) is formed on the surface, and then an organic pigment (or organic dye) is used as a coloring agent to color the surface (Patent Documents 1 to 5).
近年の多種多様な着色アルミニウム製品の需要に応じるために、様々な色の染料に対応可能な着色方法（特許文献４）が開発されている。例えば、陽極酸化アルミニウム用着色剤として紫色系のキサンテン系色素が知られている（特許文献４、５など）が、色相や耐光性が不十分であり、混色を必要とせず単一の色素で耐光性が良好な色素が求められている。 In order to meet the recent demand for a wide variety of colored aluminum products, a coloring method that can accommodate dyes of various colors (Patent Document 4) has been developed. For example, purple xanthene dyes are known as colorants for anodized aluminum (Patent Documents 4, 5, etc.), but their hue and lightfastness are insufficient, and there is a demand for a single dye that does not require color mixing and has good lightfastness.
また、アルマイト皮膜用の含クロム染料（特許文献１～３など）は、耐光性や耐熱性にも優れ、汎用的に使用されてきたが、近年、環境面から、クロムなどの重金属を含まない、様々な色相を有する色素が求められている。 Chromium-containing dyes for anodized aluminum coatings (Patent Documents 1 to 3, etc.) have excellent light and heat resistance and have been widely used, but in recent years, from an environmental perspective, there has been a demand for pigments with a variety of hues that do not contain heavy metals such as chromium.
クロムを含まず、所望の色相を有する色素は限られており、所望の色相を有する新規な構造の色素の開発は有用である。 There are only a limited number of pigments that do not contain chromium and have the desired hue, so it would be useful to develop pigments with novel structures that have the desired hue.
本発明が解決しようとする課題は、アルミニウム、アルミニウム酸化物またはアルミニウム合金の表面に、クロムなどの重金属を含まない、かつ、単色で紫色系を呈する陽極酸化皮膜を形成することのできる新規なキサンテン系色素、該色素を含有する染料組成物、該染料組成物からなる陽極酸化アルミニウム用着色剤および着色方法、ならびに該色素の製造方法を提供することである。 The problem that the present invention aims to solve is to provide a novel xanthene dye that is free of heavy metals such as chromium and capable of forming a monochromatic purple-hued anodized film on the surface of aluminum, aluminum oxide, or aluminum alloy, a dye composition containing the dye, a colorant for anodized aluminum comprising the dye composition, a coloring method, and a method for producing the dye.
上記課題を解決するため、発明者らはアルミニウム陽極酸化用の色素（染料）を鋭意検討した結果、特定の構造を有するキサンテン系色素を陽極酸化アルミニウム用着色剤として用いることにより、陽極酸化アルミニウム上に、単色で紫色系を呈する陽極酸化皮膜を形成することができることを見出した。すなわち本発明は、以下の内容で構成されている。 In order to solve the above problems, the inventors conducted extensive research into pigments (dyes) for anodizing aluminum, and discovered that by using a xanthene pigment with a specific structure as a coloring agent for anodized aluminum, it is possible to form a monochromatic purple anodized film on anodized aluminum. That is, the present invention is comprised of the following:
１．下記一般式（１）で表されるキサンテン系色素。 1. A xanthene dye represented by the following general formula (1):
［式（１）中、Ｒ１およびＲ２はそれぞれ独立に、
置換基を有していてもよい炭素原子数６～３０のナフチル基、
または、置換基を有していてもよい炭素原子数６～３０のフェニル基を表す。
ただし、Ｒ１およびＲ２のうち少なくとも１個は、
置換基を有していてもよい炭素原子数６～３０のナフチル基である。]
[In formula (1), R 1 and R 2 each independently represent
a naphthyl group having 6 to 30 carbon atoms which may have a substituent;
Or it represents a phenyl group having 6 to 30 carbon atoms which may have a substituent.
However, at least one of R 1 and R 2 is
and a naphthyl group having 6 to 30 carbon atoms which may have a substituent.]
２．前記一般式（１）において、Ｒ１またはＲ２が下記一般式（２）～（４）で表されるいずれか一種の１価基であるキサンテン系色素。 2. A xanthene dye in which, in the general formula (1), R 1 or R 2 is any one of monovalent groups represented by the following general formulas (2) to (4):
［式（２）～（４）中、Ｒ３～Ｒ２１は、それぞれ独立に、―Ｈ、―ＯＨ、―ＣＯＯＭ、―ＮＯ２、―ＮＯ、―ＣＮ、―ＳＯ３Ｍ、―ＳＨ、
置換基を有していてもよい炭素原子数０～２０のアミノ基、
置換基を有していてもよい炭素原子数０～２０のスルホニル基、
置換基を有していてもよい炭素原子数１～２０の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数３～２０のシクロアルキル基、
置換基を有していてもよい炭素原子数１～２０の直鎖状もしくは分岐状のアルコキシ基、
置換基を有していてもよい炭素原子数３～２０のシクロアルコキシ基、
置換基を有していてもよい炭素原子数２～２０の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数１～２０のアシル基、
置換基を有していてもよい炭素原子数６～２０の芳香族炭化水素基、または
置換基を有していてもよい炭素原子数２～２０の複素環基を表す。
Ｍは、水素原子またはアルカリ金属原子を表す。］
[In formulas (2) to (4), R 3 to R 21 each independently represent —H, —OH, —COOM, —NO 2 , —NO, —CN, —SO 3 M, —SH,
an amino group having 0 to 20 carbon atoms which may have a substituent;
a sulfonyl group having 0 to 20 carbon atoms which may have a substituent;
a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent;
a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent;
a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent;
a cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,
a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent;
an acyl group having 1 to 20 carbon atoms which may have a substituent;
It represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent.
M represents a hydrogen atom or an alkali metal atom.
３．前記一般式（２）または（３）において、Ｒ３～Ｒ１６が、それぞれ独立に、―Ｈ、―ＳＯ３Ｈまたは―ＳＯ３Ｎａであるキサンテン系色素。 3. A xanthene dye represented by the above general formula (2) or (3), in which R 3 to R 16 are each independently —H, —SO 3 H, or —SO 3 Na.
４．前記一般式（４）において、Ｒ１７～Ｒ２１が、それぞれ独立に、―Ｈ、炭素原子数１～１０の直鎖状もしくは分岐状のアルキル基、または置換基を有していてもよい炭素原子数０～１０のアミノ基であるキサンテン系色素。 4. A xanthene colorant represented by the general formula (4), wherein R 17 to R 21 are each independently —H, a linear or branched alkyl group having 1 to 10 carbon atoms, or an amino group having 0 to 10 carbon atoms which may have a substituent.
５．前記キサンテン系色素を含有する染料組成物。 5. A dye composition containing the xanthene dye.
６．前記染料組成物を含有する陽極酸化アルミニウム用着色剤。 6. A colorant for anodized aluminum containing the dye composition.
７．前記キサンテン系色素を、０．０２～１０質量％含有する染料組成物を用いることを特徴とする、陽極酸化アルミニウム、陽極酸化アルミニウム酸化物または陽極酸化アルミニウム合金の着色方法。 7. A method for coloring anodized aluminum, anodized aluminum oxide, or anodized aluminum alloy, comprising using a dye composition containing 0.02 to 10 mass % of the xanthene dye.
８．キサンテン系色素の製造方法であって、
工程１のみを行うこと、または、工程１の次に工程２を行うこと、を特徴とする製造方法。
工程１：下記式（５）で表される化合物と、
下記一般式（２ａ）または（３ａ）で表される化合物を反応させること。
工程２：前記工程１で得られた中間体と、
下記一般式（２ａ）、（３ａ）または（４ａ）で表される化合物を反応させること。
8. A method for producing a xanthene dye, comprising the steps of:
A manufacturing method characterized by carrying out only step 1, or carrying out step 1 followed by step 2.
Step 1: reacting a compound represented by the following formula (5) with
Reacting a compound represented by the following general formula (2a) or (3a):
Step 2: The intermediate obtained in step 1,
Reacting a compound represented by the following general formula (2a), (3a) or (4a):
［式（２ａ）、（３ａ）または（４ａ）中、Ｒ３～Ｒ２１は、前記一般式（２）～（４）の定義と同意義を示す。］ [In formula (2a), (3a) or (4a), R 3 to R 21 have the same meanings as defined in formulae (2) to (4).]
本発明により、アルミニウム、アルミニウム酸化物またはアルミニウム合金の表面に、クロムなどの重金属を含まない、かつ、単色で紫色系を呈する陽極酸化皮膜を形成することのできる新規なキサンテン系色素、該色素を含有する染料組成物、該染料組成物からなる陽極酸化アルミニウム用着色剤および着色方法、ならびに該色素の製造方法を提供することができる。 The present invention provides a novel xanthene dye capable of forming a monochromatic purple-hued anodized coating on the surface of aluminum, aluminum oxide, or aluminum alloy, which does not contain heavy metals such as chromium, a dye composition containing the dye, a colorant for anodized aluminum comprising the dye composition, a coloring method, and a method for producing the dye.
以下、本発明の実施の形態について詳細に説明する。なお、本発明は以下の実施形態に限定されず、その要旨の範囲内で種々変形して実施することができる。以下、前記一般式（１）で表されるキサンテン系色素について具体的に説明するが、本発明はこれらに限定されない。 The following describes in detail the embodiments of the present invention. Note that the present invention is not limited to the following embodiments, and can be practiced with various modifications within the scope of the gist of the invention. Below, the xanthene dye represented by the general formula (1) is specifically described, but the present invention is not limited thereto.
本発明に係るキサンテン系色素は、下記一般式（１）で表される。一般式（１）において、Ｒ１およびＲ２はそれぞれ独立に、「置換基を有していてもよい炭素原子数６～３０のナフチル基」または「置換基を有していてもよい炭素原子数６～３０のフェニル基」を表す。ただし、Ｒ１およびＲ２のうち少なくとも１個は、「置換基を有していてもよい炭素原子数６～３０のナフチル基」である。具体的には、Ｒ１が「置換基を有していてもよい炭素原子数６～３０のフェニル基」である場合には、Ｒ２は「置換基を有していてもよい炭素原子数６～３０のナフチル基」である。また、Ｒ２が「置換基を有していてもよい炭素原子数６～３０のフェニル基」である場合には、Ｒ１は「置換基を有していてもよい炭素原子数６～３０のナフチル基」である。さらに、Ｒ１およびＲ２の両方が「置換基を有していてもよい炭素原子数６～３０のナフチル基」であってよい。 The xanthene dye according to the present invention is represented by the following general formula (1). In general formula (1), R 1 and R 2 each independently represent a "naphthyl group having 6 to 30 carbon atoms which may have a substituent" or a "phenyl group having 6 to 30 carbon atoms which may have a substituent". However, at least one of R 1 and R 2 is a "naphthyl group having 6 to 30 carbon atoms which may have a substituent". Specifically, when R 1 is a "phenyl group having 6 to 30 carbon atoms which may have a substituent", R 2 is a "naphthyl group having 6 to 30 carbon atoms which may have a substituent". In addition, when R 2 is a "phenyl group having 6 to 30 carbon atoms which may have a substituent", R 1 is a "naphthyl group having 6 to 30 carbon atoms which may have a substituent". Furthermore, both R 1 and R 2 may be "naphthyl groups having 6 to 30 carbon atoms which may have a substituent".
一般式（１）において、「置換基を有していてもよい炭素原子数６～３０のナフチル基」における「炭素原子数」は、例えば、１０～３０、１０～２５、１０～２０、１０～１８、１０～１５、又は１０～１２であってよく、１０であってもよい。一般式（１）において、「置換基を有していてもよい炭素原子数６～３０のフェニル基」における「炭素原子数」は、例えば、６～２５、６～２０又は６～１８であってよい。 In general formula (1), the "number of carbon atoms" in the "naphthyl group having 6 to 30 carbon atoms, which may have a substituent" may be, for example, 10 to 30, 10 to 25, 10 to 20, 10 to 18, 10 to 15, or 10 to 12, or may be 10. In general formula (1), the "number of carbon atoms" in the "phenyl group having 6 to 30 carbon atoms, which may have a substituent" may be, for example, 6 to 25, 6 to 20, or 6 to 18.
一般式（１）において、「置換基を有していてもよい炭素原子数６～３０のナフチル基」または「置換基を有していてもよい炭素原子数６～３０のフェニル基」における「置換基」としては、具体的に、
水酸基（―ＯＨ）、―ＣＯＯＭ（Ｍは、リチウム原子（Ｌｉ）、ナトリウム原子（Ｎａ）、カリウム原子（Ｋ）などのアルカリ金属原子）、カルボキシル基（―ＣＯＯＨ）、ニトロ基（―ＮＯ２）、ニトロソ基（―ＮＯ）、シアノ基（―ＣＮ）、―ＳＯ３Ｍ（Ｍは、リチウム原子（Ｌｉ）、ナトリウム原子（Ｎａ）、カリウム原子（Ｋ）などのアルカリ金属原子）、スルホン酸基（―ＳＯ３Ｈ）、チオール基（―ＳＨ）、
無置換アミノ基；―ＮＨ―を介して炭素原子数０～２０の基が結合した一置換アミノ基；―Ｎ＜を介して炭素原子数０～２０の基が結合した二置換アミノ基；
スルホンアミド（―Ｓ（＝Ｏ）２―ＮＨ２）基、メシル基、トシル基などのスルホニル基（―Ｓ（＝Ｏ）２―）を有する基；
メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、ペンチル基、ｎ－ヘキシル基、イソヘキシル基、ヘプチル基、ｎ－オクチル基、ｔ－オクチル基、イソオクチル基、ノニル基、デシル基などの直鎖状もしくは分岐状のアルキル基;
シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、シクロドデシル基などのシクロアルキル基；
メトキシ基、エトキシ基、プロポキシ基、ｔ－ブトキシ基、ｎ－ペンチルオキシ基、ｎ－ヘキシルオキシ基などの直鎖状もしくは分岐状のアルコキシ基；
シクロプロポキシ基、シクロブトキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基などのシクロアルコキシ基；
ビニル基、１－プロペニル基、アリル基、１－ブテニル基、２－ブテニル基、１－ペンテニル基、１－ヘキセニル基、イソプロペニル基、イソブテニル基、またはこれらのアルケニル基が複数結合した直鎖状もしくは分岐状のアルケニル基；
ホルミル基、アセチル基、プロピオニル基、アクリリル基、ベンゾイル基などのアシル基；
フェニル基、ナフチル基、アントリル基、フェナントリル基、ピレニル基、トリフェニレニル基、インデニル基、フルオレニル基などの芳香族炭化水素基；
ピリジル基、ピリミジニル基、トリアジニル基、ピロリル基、イミダゾリル基、ピラゾリル基、トリアゾリル基、ピラジニル基、ピリダジニル基、ピペリジニル基、ピペラジニル基、キノリル基、イソキノリル基、ナフチリジニル基、インドリル基、ベンゾイミダゾリル基、カルバゾニル基、カルボリニル基、アクリジニル基、フェナントロリニル基、フェナントリジニル基、ヒダントイン基、フラニル基、ベンゾフラニル基、ジベンゾフラニル基、ピラニル基、クマリニル基、イソベンゾフラニル基、キサンテニル基、オキサントレニル基、ピラノニル基、チエニル基、チオピラニル基、ベンゾチエニル基、ジベンゾチエニル基、チオキサンテニル基、オキサゾリル基、ベンゾオキサゾリル基、モルホリニル基、チアゾリル基、ベンゾチアゾリル基などの複素環基；
シクロプロペニル基、シクロブテニル基、シクロペンテニル基、シクロヘキセニル基、シクロヘプテニル基、（１，３－もしくは１，４－）シクロヘキサジエニル基、１，５－シクロオクタジエニル基などの環状オレフィン基；などがあげられる。
これらの「置換基」は、１つのみ含まれてもよく、複数含まれてもよく、複数含まれる場合は互いに同一でも異なっていてもよい。また、これら「置換基」は前記例示した置換基を有していてもよい。なお、「置換基」が炭素原子を含む場合、その炭素原子は、上記の「炭素原子数６～３０」に算入される。
In the general formula (1), specific examples of the "substituent" in the "naphthyl group having 6 to 30 carbon atoms which may have a substituent" or the "phenyl group having 6 to 30 carbon atoms which may have a substituent" include:
Hydroxyl group (-OH), -COOM (M is an alkali metal atom such as lithium atom (Li), sodium atom (Na), potassium atom (K) etc.), carboxyl group (-COOH), nitro group (-NO 2 ), nitroso group (-NO), cyano group (-CN), -SO 3 M (M is an alkali metal atom such as lithium atom (Li), sodium atom (Na), potassium atom (K) etc.), sulfonic acid group (-SO 3 H), thiol group (-SH),
An unsubstituted amino group; a monosubstituted amino group having a group of 0 to 20 carbon atoms bonded via —NH—; a disubstituted amino group having a group of 0 to 20 carbon atoms bonded via —N<;
a group having a sulfonyl group (-S(=O) 2 -) such as a sulfonamide (-S(=O) 2 -NH 2 ) group, a mesyl group, or a tosyl group;
linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, n-hexyl, isohexyl, heptyl, n-octyl, t-octyl, isooctyl, nonyl, and decyl groups;
cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group;
linear or branched alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, an n-pentyloxy group, or an n-hexyloxy group;
cycloalkoxy groups such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group;
a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 1-hexenyl group, an isopropenyl group, an isobutenyl group, or a linear or branched alkenyl group in which a plurality of these alkenyl groups are bonded;
acyl groups such as a formyl group, an acetyl group, a propionyl group, an acrylyl group, and a benzoyl group;
Aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, an indenyl group, or a fluorenyl group;
heterocyclic groups such as a pyridyl group, a pyrimidinyl group, a triazinyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a pyrazinyl group, a pyridazinyl group, a piperidinyl group, a piperazinyl group, a quinolyl group, an isoquinolyl group, a naphthyridinyl group, an indolyl group, a benzimidazolyl group, a carbazonyl group, a carbolinyl group, an acridinyl group, a phenanthrolinyl group, a phenanthridinyl group, a hydantoin group, a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a pyranyl group, a coumarinyl group, an isobenzofuranyl group, a xanthenyl group, an oxanthrenyl group, a pyranonyl group, a thienyl group, a thiopyranyl group, a benzothienyl group, a dibenzothienyl group, a thioxanthenyl group, an oxazolyl group, a benzoxazolyl group, a morpholinyl group, a thiazolyl group, and a benzothiazolyl group;
Examples include cyclic olefin groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a (1,3- or 1,4-)cyclohexadienyl group, and a 1,5-cyclooctadienyl group.
These "substituents" may be contained in only one or more, and when more than one is contained, they may be the same or different. Furthermore, these "substituents" may have the above-mentioned substituents. When the "substituent" contains a carbon atom, the carbon atom is counted in the above "6 to 30 carbon atoms".
一般式（１）で表されるキサンテン系色素において、Ｒ１またはＲ２が下記一般式（２）～（４）で表されるいずれか一種の１価基であることが好ましい。一般式（２）で表される１価基はＲ３～Ｒ９で表される基を有するナフチル基であり、一般式（３）で表される１価基は、Ｒ１０～Ｒ１６で表される基を有するナフチル基であり、一般式（４）で表される１価基は、Ｒ１７～Ｒ２１で表される基を有するフェニル基であり、それぞれ破線部は連結部を表す。 In the xanthene dye represented by general formula (1), R1 or R2 is preferably any one of the monovalent groups represented by the following general formulae (2) to (4): The monovalent group represented by general formula (2) is a naphthyl group having groups represented by R3 to R9 , the monovalent group represented by general formula (3) is a naphthyl group having groups represented by R10 to R16 , and the monovalent group represented by general formula (4) is a phenyl group having groups represented by R17 to R21 , and the dashed lines in each group represent linking portions.
一般式（２）～（４）において、Ｒ３～Ｒ２１は、それぞれ独立に、―Ｈ、―ＯＨ、―ＣＯＯ－、―ＣＯＯＭ、―ＮＯ２、―ＮＯ、―ＣＮ、―ＳＯ３Ｍ、―ＳＨ、
置換基を有していてもよい炭素原子数０～２０のアミノ基、
置換基を有していてもよい炭素原子数０～２０のスルホニル基、
置換基を有していてもよい炭素原子数１～２０の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数３～２０のシクロアルキル基、
置換基を有していてもよい炭素原子数１～２０の直鎖状もしくは分岐状のアルコキシ基、
置換基を有していてもよい炭素原子数３～２０のシクロアルコキシ基、
置換基を有していてもよい炭素原子数２～２０の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数１～２０のアシル基、
置換基を有していてもよい炭素原子数６～２０の芳香族炭化水素基、または
置換基を有していてもよい炭素原子数２～２０の複素環基であることが好ましい。
ここで、Ｍは、水素原子（Ｈ）；リチウム原子（Ｌｉ）、ナトリウム原子（Ｎａ）、カリウム原子（Ｋ）などのアルカリ金属原子を表し、Ｍとしては、水素原子、ナトリウム原子であることが好ましい。なお、Ｒ３～Ｒ２１が炭素原子を含む場合、その炭素原子は、一般式（１）中の「置換基を有していてもよい炭素原子数６～３０のナフチル基」または「置換基を有していてもよい炭素原子数６～３０のフェニル基」における「炭素原子数６～３０」に算入される。
In the general formulae (2) to (4), R 3 to R 21 each independently represent —H, —OH, —COO − , —COOM, —NO 2 , —NO, —CN, —SO 3 M, —SH,
an amino group having 0 to 20 carbon atoms which may have a substituent;
a sulfonyl group having 0 to 20 carbon atoms which may have a substituent;
a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent;
a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent;
a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent;
a cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,
a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent;
an acyl group having 1 to 20 carbon atoms which may have a substituent;
It is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent.
Here, M represents a hydrogen atom (H) or an alkali metal atom such as a lithium atom (Li), a sodium atom (Na) or a potassium atom (K), and M is preferably a hydrogen atom or a sodium atom. When R 3 to R 21 contain a carbon atom, the carbon atom is counted as "6 to 30 carbon atoms" in the "naphthyl group having 6 to 30 carbon atoms which may have a substituent" or the "phenyl group having 6 to 30 carbon atoms which may have a substituent" in general formula (1).
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「置換基を有していてもよい炭素原子数０～２０のアミノ基」としては、無置換アミノ基（―ＮＨ２）、一置換アミノ基、二置換アミノ基などがあげられる。一置換アミノ基または二置換アミノ基における炭素原子数は、例えば、１～２０であり、１～１０であってよく、２～６であってよい。置換基を有していてもよい炭素原子数０～２０のアミノ基は、―ＮＨ―または―Ｎ＜を介して、後述する炭素原子数６～２０の芳香族炭化水素基、炭素原子数１～２０のアシル基、炭素原子数２～２０の複素環基が結合した基であってもよい。一置換アミノ基としては、エチルアミノ基、アセチルアミノ基、フェニルアミノ基などがあげられる。二置換アミノ基としては、ジメチルアミノ基、ジエチルアミノ基、ジブチルアミノ基などの炭素原子数２～２０のジアルキルアミノ基；ジフェニルアミノ基、アセチルフェニルアミノ基などがあげられる。 In the general formulae (2) to (4), examples of the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by R 3 to R 21 include an unsubstituted amino group (-NH 2 ), a monosubstituted amino group, a disubstituted amino group, and the like. The number of carbon atoms in the monosubstituted amino group or disubstituted amino group is, for example, 1 to 20, or may be 1 to 10 or 2 to 6. The amino group having 0 to 20 carbon atoms which may have a substituent may be a group to which an aromatic hydrocarbon group having 6 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms is bonded via -NH- or -N<, as described below. Examples of the monosubstituted amino group include an ethylamino group, an acetylamino group, and a phenylamino group. Examples of the disubstituted amino group include a dialkylamino group having 2 to 20 carbon atoms, such as a dimethylamino group, a diethylamino group, and a dibutylamino group; a diphenylamino group, and an acetylphenylamino group.
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「炭素原子数０～２０の置換基を有していてもよいスルホニル基」は、―ＳＯ２―Ｒ１００（もしくは―Ｓ（＝Ｏ）２―Ｒ１００）で表される置換基Ｒ１００を有するスルホニル基を表すもの意味する。Ｒ１００は、炭素原子を含む基であってもよく、炭素原子を含まない基であってもよい。Ｒ１００が炭素を含む基である場合、Ｒ１００の炭素原子数は、１～２０であり、１～１０であってよく、１～７であってよい。炭素原子数０～２０の置換基を有していてもよいスルホニル基としては、スルホンアミド基（―Ｓ（＝Ｏ）２―ＮＨ２）、メシル基、トシル基などがあげられる。 In the general formulae (2) to (4), the "sulfonyl group which may have a substituent having 0 to 20 carbon atoms" represented by R 3 to R 21 means a sulfonyl group having a substituent R 100 represented by -SO 2 -R 100 (or -S(=O) 2 -R 100 ). R 100 may be a group containing a carbon atom or a group not containing a carbon atom. When R 100 is a group containing carbon, the number of carbon atoms of R 100 is 1 to 20, optionally 1 to 10, or optionally 1 to 7. Examples of the sulfonyl group which may have a substituent having 0 to 20 carbon atoms include a sulfonamide group (-S(=O) 2 -NH 2 ), a mesyl group, and a tosyl group.
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「置換基を有していてもよい炭素原子数１～２０の直鎖状もしくは分岐状のアルキル基」における「炭素原子数１～２０の直鎖状もしくは分岐状のアルキル基」としては、具体的に、メチル基、エチル基、ｎ－プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基などの直鎖状のアルキル基；イソプロピル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、イソオクチル基、ｔ－オクチル基などの分岐状のアルキル基があげられる。 In the general formulas (2) to (4), specific examples of the "straight-chain or branched alkyl group having 1 to 20 carbon atoms" in the "straight-chain or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R 3 to R 21 include straight-chain alkyl groups such as methyl group, ethyl group, n-propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group; and branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group, and t-octyl group.
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「置換基を有していてもよい炭素原子数３～２０のシクロアルキル基」における「炭素原子数３～２０のシクロアルキル基」としては、具体的に、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、シクロドデシル基などがあげられる。 In the general formulas (2) to (4), specific examples of the "cycloalkyl group having 3 to 20 carbon atoms" in the "cycloalkyl group having 3 to 20 carbon atoms which may have a substituent" represented by R to R21 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group.
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「置換基を有していてもよい炭素原子数１～２０の直鎖状もしくは分岐状のアルコキシ基」における「炭素原子数１～２０の直鎖状もしくは分岐状のアルコキシ基」としては、具体的に、メトキシ基、エトキシ基、プロポキシ基、ｎ－ブトキシ基、ｎ－ペンチルオキシ基、ｎ－ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、ノニルオキシ基、デシルオキシ基などの直鎖状のアルコキシ基；イソプロポキシ基、イソブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、イソオクチルオキシ基、ｔ－オクチルオキシ基などの分岐状のアルコキシ基があげられる。 In the general formulas (2) to (4), specific examples of the "straight-chain or branched alkoxy group having 1 to 20 carbon atoms" in the "straight-chain or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" represented by R 3 to R 21 include straight-chain alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy; and branched alkoxy groups such as isopropoxy, isobutoxy, s-butoxy, t-butoxy, isooctyloxy, and t-octyloxy.
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「置換基を有していてもよい炭素原子数３～２０のシクロアルコキシ基」における「炭素原子数３～２０のシクロアルコキシ基」としては、具体的に、シクロプロポキシ基、シクロブトキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基などがあげられる。 In the general formulas (2) to (4), specific examples of the "cycloalkoxy group having 3 to 20 carbon atoms" in the "cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent" represented by R to R21 include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc.
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「置換基を有していてもよい炭素原子数２～２０の直鎖状もしくは分岐状のアルケニル基」における「炭素原子数２～２０の直鎖状もしくは分岐状のアルケニル基」としては、具体的に、ビニル基、アリル基、イソプロペニル基、２－ブテニル基、１－ヘキセニル基、または、これらのアルケニル基が複数結合した直鎖状もしくは分岐状の基があげられる。 In the general formulas (2) to (4), specific examples of the "straight-chain or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by R to R 21 include a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, a 1-hexenyl group, or a straight-chain or branched group in which a plurality of these alkenyl groups are bonded.
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「置換基を有していてもよい炭素原子数１～２０のアシル基」は、―（Ｃ＝Ｏ）―Ｒ１０１で表される基である。置換基Ｒ１０１は、炭素原子を含む基であってもよく、炭素原子を含まない基であってもよい。置換基Ｒ１０１が、炭素原子を含む基である場合、置換基Ｒ１０１の炭素原子数は、例えば、１～２０であってよく、１～１０であってよい。置換基Ｒ１０１としては、例えば、―Ｈ、―ＣＨ３、―ＣＨ２ＣＨ２ＣＨ３、―ＣＨ＝ＣＨ２、―Ｃ６Ｈ５（フェニル基）などがあげられる。「置換基を有していてもよい炭素原子数１～２０のアシル基」における「炭素原子数１～２０のアシル基」としては、具体的に、ホルミル基、アセチル基、プロピオニル基、アクリリル基、ベンゾイル基などがあげられる。 In the general formulae (2) to (4), the "acyl group having 1 to 20 carbon atoms which may have a substituent" represented by R 3 to R 21 is a group represented by -(C=O)-R 101. The substituent R 101 may be a group containing a carbon atom or a group not containing a carbon atom. When the substituent R 101 is a group containing a carbon atom, the number of carbon atoms of the substituent R 101 may be, for example, 1 to 20, or 1 to 10. Examples of the substituent R 101 include -H, -CH 3 , -CH 2 CH 2 CH 3 , -CH=CH 2 , and -C 6 H 5 (phenyl group). Specific examples of the "acyl group having 1 to 20 carbon atoms" in the "acyl group having 1 to 20 carbon atoms which may have a substituent" include a formyl group, an acetyl group, a propionyl group, an acrylyl group, and a benzoyl group.
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「置換基を有していてもよい炭素原子数６～２０の芳香族炭化水素基」における「炭素原子数６～３０の芳香族炭化水素基」としては、具体的に、フェニル基、ベンゾイル基、ナフチル基、ビフェニル基、アントリル基、フェナントリル基、ピレニル基、トリフェニレニル基、インデニル基、フルオレニル基などがあげられ、アシル基やアミノ基を介していてもよい。ここで、本発明における「芳香族炭化水素基」とは、芳香族炭化水素基および縮合多環芳香族基を表すものとし、これらの中でも、フェニル基またはナフチル基が好ましい。 In general formulas (2) to (4), examples of the "aromatic hydrocarbon group having 6 to 30 carbon atoms" in the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" represented by R 3 to R 21 include a phenyl group, a benzoyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, an indenyl group, a fluorenyl group, etc., which may be connected via an acyl group or an amino group. Here, the "aromatic hydrocarbon group" in the present invention represents an aromatic hydrocarbon group and a condensed polycyclic aromatic group, and among these, a phenyl group or a naphthyl group is preferred.
一般式（２）～（４）において、Ｒ３～Ｒ２１で表される「置換基を有していてもよい炭素原子数２～２０の複素環基」における「炭素原子数２～２０の複素環基」としては、具体的に、ピリジル基、ピリミジニル基、トリアジニル基、ピロリル基、イミダゾリル基、ピラゾリル基、トリアゾリル基、キノリル基、イソキノリル基、ナフチリジニル基、インドリル基、ベンゾイミダゾリル基、カルバゾニル基、カルボリニル基、アクリジニル基、フェナントロリニル基、ヒダントイン基、フラニル基、ベンゾフラニル基、ジベンゾフラニル基、チエニル基、ベンゾチエニル基、ジベンゾチエニル基、オキサゾリル基、ベンゾオキサゾリル基、チアゾリル基、ベンゾチアゾリル基などがあげられる。 In the general formulas (2) to (4), specific examples of the "heterocyclic group having 2 to 20 carbon atoms" in the "heterocyclic group having 2 to 20 carbon atoms which may have a substituent" represented by R 3 to R 21 include a pyridyl group, a pyrimidinyl group, a triazinyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a quinolyl group, an isoquinolyl group, a naphthyridinyl group, an indolyl group, a benzimidazolyl group, a carbazonyl group, a carbolinyl group, an acridinyl group, a phenanthrolinyl group, a hydantoin group, a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, and a benzothiazolyl group.
一般式（２）～（４）においてＲ３～Ｒ２１で表される、
「置換基を有する炭素原子数０～２０のアミノ基」、
「置換基を有する炭素原子数０～２０のスルホニル基」、
「置換基を有する炭素原子数１～２０の直鎖状もしくは分岐状のアルキル基」、
「置換基を有する炭素原子数３～２０のシクロアルキル基」、
「置換基を有する炭素原子数１～２０の直鎖状もしくは分岐状のアルコキシ基」、
「置換基を有する炭素原子数３～２０のシクロアルコキシ基」、
「置換基を有する炭素原子数２～２０の直鎖状もしくは分岐状のアルケニル基」、
「置換基を有する炭素原子数１～２０のアシル基」、
「置換基を有する炭素原子数６～２０の芳香族炭化水素基」または
「置換基を有する炭素原子数２～２０の複素環基」における「置換基」としては、
前記した、一般式（１）における「置換基を有していてもよい炭素原子数６～３０のナフチル基」または「置換基を有していてもよい炭素原子数６～３０のフェニル基」における「置換基」としてあげたものと同じものがあげられる。これらの「置換基」は、１つのみ含まれてもよく、複数含まれてもよく、複数含まれる場合は互いに同一でも異なっていてもよい。また、これら「置換基」は前記例示した置換基を有していてもよい。なお、「置換基」が炭素原子を含む場合、その炭素原子は、上記の「炭素原子数０～２０」、「炭素原子数１～２０」、「炭素原子数２～２０」、「炭素原子数３～２０」および「炭素原子数６～２０」に算入される。さらに、これらの置換基同士が単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成していてもよい。
In the general formulas (2) to (4), represented by R 3 to R 21 ,
"A substituted amino group having 0 to 20 carbon atoms,"
"A substituted sulfonyl group having 0 to 20 carbon atoms",
"A linear or branched alkyl group having 1 to 20 carbon atoms and having a substituent,"
"A cycloalkyl group having 3 to 20 carbon atoms and having a substituent,"
"A substituted linear or branched alkoxy group having 1 to 20 carbon atoms",
"A cycloalkoxy group having 3 to 20 carbon atoms and having a substituent",
"A substituted linear or branched alkenyl group having 2 to 20 carbon atoms",
"A substituted acyl group having 1 to 20 carbon atoms,"
Examples of the "substituent" in the "substituted aromatic hydrocarbon group having 6 to 20 carbon atoms" or the "substituted heterocyclic group having 2 to 20 carbon atoms" include:
Examples of the "substituent" in the "naphthyl group having 6 to 30 carbon atoms which may have a substituent" or the "phenyl group having 6 to 30 carbon atoms which may have a substituent" in the general formula (1) described above include the same ones as those exemplified above. Only one of these "substituents" may be included, or multiple substituents may be included, and when multiple substituents are included, they may be the same or different from each other. Furthermore, these "substituents" may have the substituents exemplified above. When the "substituent" includes a carbon atom, the carbon atom is included in the above-mentioned "0 to 20 carbon atoms", "1 to 20 carbon atoms", "2 to 20 carbon atoms", "3 to 20 carbon atoms" and "6 to 20 carbon atoms". Furthermore, these substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.
一般式（２）または（３）において、Ｒ３～Ｒ１６は、それぞれ独立に、―Ｈ、―ＳＯ３Ｈまたは―ＳＯ３Ｎａであることが好ましい。 In formula (2) or (3), it is preferable that R 3 to R 16 each independently represent —H, —SO 3 H or —SO 3 Na.
Ｒ３～Ｒ９のうち少なくとも１個は、―ＳＯ３Ｍであってよく、Ｒ５が―ＳＯ３Ｍであってよい。Ｒ１０～Ｒ１６のうち少なくとも１個は、―ＳＯ３Ｍであってよく、Ｒ１２又はＲ１３が―ＳＯ３Ｍであってよい。 At least one of R 3 to R 9 may be —SO 3 M, and R 5 may be —SO 3 M. At least one of R 10 to R 16 may be —SO 3 M, and R 12 or R 13 may be —SO 3 M.
一般式（４）において、Ｒ１７～Ｒ２１は、それぞれ独立に、―Ｈ、炭素原子数１～１０の直鎖状もしくは分岐状のアルキル基、または置換基を有していてもよい炭素原子数０～１０のアミノ基であることが好ましい。 In general formula (4), it is preferable that R 17 to R 21 each independently represent —H, a linear or branched alkyl group having 1 to 10 carbon atoms, or an amino group having 0 to 10 carbon atoms which may have a substituent.
一般式（１）で表される本発明のキサンテン系色素である化合物（以下、単に色素（１）とも表す）は、生じ得るすべての立体異性体、互変異性体を包含するものとする。色素（１）の具体例を以下の式に示すが、本発明はこれらに限定されない。なお、構造式中では水素原子を一部省略して記載している。 The compound which is the xanthene dye of the present invention represented by general formula (1) (hereinafter also referred to simply as dye (1)) is intended to include all possible stereoisomers and tautomers. Specific examples of dye (1) are shown in the following formulas, but the present invention is not limited to these. Note that some hydrogen atoms are omitted in the structural formula.
一般式（１）で表される本発明のキサンテン系色素（色素（１））の製造方法の一例を以下に示すが、この方法に限定されない。本発明の製造方法は、具体的に、
下記の「工程１」のみを行うことによって色素（１）を製造する方法、または、
前記「工程１」の次に下記の「工程２」を行うことによって色素（１）を製造する方法、である。
工程１：下記式（５）で表される化合物と、
下記一般式（２ａ）または（３ａ）で表される化合物を反応させること。
工程２：前記工程１で得られた中間体と、
下記一般式（２ａ）、（３ａ）または（４ａ）で表される化合物を反応させること。
An example of a method for producing the xanthene dye (dye (1)) of the present invention represented by general formula (1) is shown below, but the method is not limited to this method. Specifically, the production method of the present invention includes the following steps:
A method for producing dye (1) by carrying out only the following "Step 1", or
The dye (1) is produced by carrying out the above-mentioned "step 1" followed by the following "step 2".
Step 1: reacting a compound represented by the following formula (5) with
Reacting a compound represented by the following general formula (2a) or (3a):
Step 2: The intermediate obtained in step 1,
Reacting a compound represented by the following general formula (2a), (3a) or (4a):
［式（２ａ）、（３ａ）または（４ａ）中、Ｒ３～Ｒ２１は、前記一般式（２）～（４）の定義と同意義を示す。］ [In formula (2a), (3a) or (4a), R 3 to R 21 have the same meanings as defined in formulae (2) to (4).]
以下、「工程１」を説明する。出発原料である前記式（５）（３，６－ジクロロ－９－（２－スルホナトフェニル）キサンチリウム）と、前記一般式（２ａ）または（３ａ）で表される、相当する基（Ｒ３～Ｒ１６）を有するナフチルアミン誘導体とを、これらの原料を溶解する任意の溶媒中、適切な温度および反応時間などの条件で反応させることにより、目的とするキサンテン系色素、または、その中間体を得ることができる。
なお、上記溶媒としては、特に限定されないが、具体的には、酢酸エチル、酢酸－ｎ－ブチルなどのエステル類；ジエチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、エチレングリコールモノエチルエーテル（エチルセロソルブ）などのエーテル類；プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）などのエーテルエステル類；アセトン、シクロヘキサノンなどのケトン類；メタノール、エタノール、２－プロパノールなどのアルコール類；ジアセトンアルコール（ＤＡＡ）など；ベンゼン、トルエン、キシレンなどの芳香族炭化水素類；Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、Ｎ－メチルピロリドン（ＮＭＰ）などのアミド類；ジメチルスルホキシド（ＤＭＳＯ）などがあげられる。これらの溶媒は、単独で用いても、２種類以上混合して用いてもよい。これらの中でも、Ｎ－メチルピロリドンが好ましい。
"Step 1" will be explained below. The starting material, 3,6-dichloro-9-(2-sulfonatophenyl)xanthylium, is reacted with a naphthylamine derivative having the corresponding groups (R 3 to R 16 ), represented by the general formula (2a) or (3a), in any solvent capable of dissolving these starting materials, under suitable conditions such as appropriate temperature and reaction time, to obtain the desired xanthene colorant or an intermediate thereof.
The solvent is not particularly limited, but specific examples thereof include esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether, propylene glycol monomethyl ether (PGME), and ethylene glycol monoethyl ether (ethyl cellosolve); ether esters such as propylene glycol monomethyl ether acetate (PGMEA); ketones such as acetone and cyclohexanone; alcohols such as methanol, ethanol, and 2-propanol; diacetone alcohol (DAA); aromatic hydrocarbons such as benzene, toluene, and xylene; amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); and dimethyl sulfoxide (DMSO). These solvents may be used alone or in combination of two or more. Among these, N-methylpyrrolidone is preferred.
以下、「工程２」を説明する。前記「工程１」を行った後、得られた中間体と、前記一般式（２ａ）、（３ａ）または（４ａ）で表される、相当する基（Ｒ３～Ｒ１６）を有するナフチルアミン誘導体化合物、または、相当する基（Ｒ１７～Ｒ２１）を有するアニリン誘導体化合物とを、これらの原料を溶解する任意の溶媒中、適切な温度および反応時間などの条件で反応させることにより、目的とするキサンテン系色素を得ることができる。上記溶媒としては、工程１であげたものと同じものを使用でき、これらの中でも、Ｎ－メチルピロリドンが好ましい。 "Step 2" will be explained below. After carrying out the above-mentioned "Step 1", the intermediate obtained is reacted with a naphthylamine derivative compound having the corresponding groups (R 3 to R 16 ) represented by the above-mentioned general formula (2a), (3a) or (4a), or an aniline derivative compound having the corresponding groups (R 17 to R 21 ), in any solvent capable of dissolving these raw materials, under suitable conditions such as suitable temperature and reaction time, to obtain the desired xanthene colorant. As the above-mentioned solvent, the same solvents as those listed in Step 1 can be used, and among these, N-methylpyrrolidone is preferable.
前記色素（１）の製造方法である工程１または工程２において、出発原料である前記式（５）と、前記一般式（２ａ）、（３ａ）または（４ａ）との仕込みモル比は、式（５）１ｍｏｌに対し、一般式（２ａ）、（３ａ）または（４ａ）が２～２０倍モル当量であるのが好ましい。 In step 1 or 2 of the method for producing dye (1), the molar ratio of the starting materials, formula (5) and formula (2a), (3a) or (4a), is preferably 2 to 20 molar equivalents of formula (2a), (3a) or (4a) per 1 mol of formula (5).
前記色素（１）は、カラムクロマトグラフィーによる精製；シリカゲル、活性炭、活性白土などによる吸着精製；溶媒による再結晶や酸などを用いた各種の晶析法などの公知の方法で精製することができる。 The dye (1) can be purified by known methods such as purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc.; recrystallization using a solvent, or various crystallization methods using an acid, etc.
本発明の色素（１）、その中間体、または、前記工程１もしくは工程２で得られた各種生成物の同定や物性評価は、紫外可視吸収スペクトル分析（ＵＶ－Ｖｉｓ）、熱重量測定－示差熱分析（ＴＧ－ＤＴＡ）、ガスクロマトグラフィー分析（ＧＣ）、薄層クロマトグラフィー分析（ＴＬＣ）、ガスクロマトグラフィー－質量分析（ＧＣ／ＭＳ）、核磁気共鳴分析（ＮＭＲ）分析などを行うことができる。 The dye (1) of the present invention, its intermediates, or the various products obtained in step 1 or step 2 can be identified and their physical properties evaluated by ultraviolet-visible absorption spectroscopy (UV-Vis), thermogravimetry-differential thermal analysis (TG-DTA), gas chromatography analysis (GC), thin layer chromatography analysis (TLC), gas chromatography-mass spectrometry (GC/MS), nuclear magnetic resonance analysis (NMR) and the like.
本発明における、一般式（１）で表されるキサンテン系色素（色素（１））は、アルミニウム、アルミニウム酸化物またはアルミニウム合金の表面に、クロムなどの重金属を含まない、かつ、単色で紫色系を呈する陽極酸化皮膜を形成することができる。更に、色素（１）は、充分な耐熱性及び／又は耐光性を有することができる。したがって、色素（１）は、染料組成物の成分として用いることができる。色素（１）は、１種類単独で用いることによっても、アルミニウム、アルミニウム酸化物、繊維などを着色することができる。つまり、色素（１）は、１種類の単色の染料を単独で用いて、アルミニウム、アルミニウム酸化物、繊維などを着色するための色素化合物として好適に用いることができる。色素（１）は、混色により多様な色彩を得るために２種以上を併用してもよい。染料組成物は、最適な染色（染料を用いた着色）のために、その他の成分を混合してもよい。具体的には、水、アルコール、溶剤などの液体（溶媒）；界面活性剤などの添加剤；などがあげられる。溶媒としては、水が好ましい。色素（１）は、他の色素を併用して、染料組成物の成分に用いてもよい。他の色素は、色素（１）以外の他の化合物、顔料、染料などであり、具体的に、ルテニウム錯体、クマリン系色素、シアニン系色素、メロシアニン系色素、ロダシアニン系色素、フタロシアニン系色素、ポルフィリン系色素、他のキサンテン系色素などがあげられる。色素（１）と、他の成分とを組み合わせて用いる場合、色素（１）に対する他の成分の使用量を１０～２００質量％とするのが好ましく、２０～１００質量％とするのがより好ましい。アルミニウム酸化物とは、アルミニウムが酸化された、主としてアルミニウムと酸素を含む組成物であり、その組成比は任意でよく、酸化アルミニウムを含み、結晶系は、単結晶でも多結晶もしくは非晶質であってもよく、それらの混合であってもよい。 In the present invention, the xanthene dye (dye (1)) represented by the general formula (1) can form an anodized film on the surface of aluminum, aluminum oxide, or aluminum alloy, which does not contain heavy metals such as chromium and has a monochromatic purple color. Furthermore, the dye (1) can have sufficient heat resistance and/or light resistance. Therefore, the dye (1) can be used as a component of a dye composition. The dye (1) can be used alone to color aluminum, aluminum oxide, fibers, etc. In other words, the dye (1) can be suitably used as a dye compound for coloring aluminum, aluminum oxide, fibers, etc. by using one type of monochromatic dye alone. The dye (1) may be used in combination with two or more types to obtain a variety of colors by mixing colors. The dye composition may be mixed with other components for optimal dyeing (coloring using a dye). Specifically, liquids (solvents) such as water, alcohol, and solvents; additives such as surfactants; and the like. Water is preferable as the solvent. The dye (1) may be used in combination with other dyes as components of the dye composition. The other dyes are compounds, pigments, dyes, etc. other than the dye (1), and specifically include ruthenium complexes, coumarin dyes, cyanine dyes, merocyanine dyes, rhodacyanine dyes, phthalocyanine dyes, porphyrin dyes, other xanthene dyes, etc. When the dye (1) is used in combination with other components, the amount of the other components used relative to the dye (1) is preferably 10 to 200% by mass, more preferably 20 to 100% by mass. The aluminum oxide is a composition containing mainly aluminum and oxygen in which aluminum is oxidized, and the composition ratio may be arbitrary, and the crystal system may be single crystal, polycrystalline, or amorphous, or a mixture thereof.
本発明の染料組成物は、陽極酸化アルミニウム用の着色剤として応用できる。上述した染料組成物は、陽極酸化アルミニウム合金に用いられる着色剤に用いることもできる。すなわち、本発明の一実施形態として、陽極酸化アルミニウム、または陽極酸化アルミニウム合金を着色するための一般式（１）で表されるキサンテン系色素または該色素を含有する染料組成物の使用（応用）が提供される。また、本発明の一実施形態として、陽極酸化アルミニウム、または陽極酸化アルミニウム合金用の着色剤の製造のための一般式（１）で表されるキサンテン系色素または該色素を含有する染料組成物の使用が提供される。 The dye composition of the present invention can be applied as a colorant for anodized aluminum. The dye composition described above can also be used as a colorant for anodized aluminum alloys. That is, as one embodiment of the present invention, the use (application) of a xanthene dye represented by general formula (1) or a dye composition containing the dye for coloring anodized aluminum or anodized aluminum alloys is provided. Also, as one embodiment of the present invention, the use of a xanthene dye represented by general formula (1) or a dye composition containing the dye for producing a colorant for anodized aluminum or anodized aluminum alloys is provided.
色素（１）を陽極酸化アルミニウムなどの着色剤として用いる際、その着色（染色）方法において、色素（１）を含有する染料組成物における色素（１）の濃度は、染料組成物の全量を基準として、０．０２～１０質量％であることが好ましく、０．０５～３質量％であることがより好ましい。色素（１）の濃度が低いほど淡色の着色を行うことができ、濃度が高いほど中間色～濃色の着色を行うことができる。 When dye (1) is used as a colorant for anodized aluminum or the like, in the coloring (dyeing) method, the concentration of dye (1) in the dye composition containing dye (1) is preferably 0.02 to 10 mass % based on the total amount of the dye composition, and more preferably 0.05 to 3 mass %. The lower the concentration of dye (1), the lighter the coloring can be, and the higher the concentration, the medium to darker the coloring can be.
ここで、陽極酸化アルミニウムとは、酸水溶液などの電解液中で、電解処理したアルミニウム表面に、細孔を有する酸化物層を形成する処理を行ったアルミニウムを意味する。陽極酸化アルミニウム用着色剤は、この細孔を有するアルミニウム表面に、色素（１）を細孔内に吸着させることにより、着色（染色）させることのできるものを意味する。通常、着色されたアルミニウム表面の耐久性、耐光性を向上させるために、着色後に細孔を塞ぐための封孔処理が行われる。 Here, anodized aluminum refers to aluminum that has been electrolytically treated in an electrolyte such as an acidic aqueous solution, and has been treated to form an oxide layer with fine pores on the surface. A colorant for anodized aluminum refers to an agent that can color (dye) this aluminum surface with fine pores by adsorbing dye (1) into the pores. Usually, a sealing treatment is performed to close the pores after coloring in order to improve the durability and light resistance of the colored aluminum surface.
陽極酸化アルミニウムにおけるアルミニウムとしては、アルミニウム、酸化アルミニウム、または他の金属とのアルミニウム合金など、アルミニウムを含有する金属または金属化合物などがあげられる。 The aluminum in anodized aluminum can be aluminum, aluminum oxide, or a metal or metal compound containing aluminum, such as an aluminum alloy with another metal.
ここで、陽極酸化アルミニウム合金とは、アルミニウム合金の表面に陽極酸化処理を行った合金を意味する。陽極酸化アルミニウム合金におけるアルミニウム合金は、アルミニウムを主成分とする合金を意味しており、銅、マンガン、ケイ素、マグネシウム、亜鉛、ニッケル、などの金属との合金を意味する。アルミニウムと他の金属との組成比は特に限定されない。 Here, anodized aluminum alloy refers to an alloy in which the surface of an aluminum alloy has been anodized. The aluminum alloy in anodized aluminum alloy refers to an alloy containing aluminum as the main component, and refers to an alloy with metals such as copper, manganese, silicon, magnesium, zinc, and nickel. There are no particular limitations on the composition ratio of aluminum to other metals.
陽極酸化アルミニウム用着色剤を用いたアルミニウムの着色方法は、アルマイト染色法として公知の方法を用いることができる。例えば、日本産業規格（ＪＩＳ Ｈ ８６０１：１９９９「アルミニウム及びアルミニウム合金の陽極酸化皮膜」）、特許文献１などに記載の方法を用いることができる。アルミニウムの着色方法は、特に限定されないが、以下に一例を示す。 The method of coloring aluminum using a colorant for anodized aluminum can be a method known as anodized dyeing. For example, the method described in Japanese Industrial Standards (JIS H 8601: 1999 "Anodized Films of Aluminum and Aluminum Alloys") and Patent Document 1 can be used. The method of coloring aluminum is not particularly limited, but an example is shown below.
最初に、アルミニウム板を硫酸、シュウ酸、クロム酸、スルホン酸などの酸水溶液を用いて脱脂処理し水洗する。次に、脱脂処理したアルミニウム板を陽極として、電解液として酸水溶液を用いて電解し、アルミニウム陽極表面上に、多くの細孔を形成する陽極酸化皮膜（アルマイト皮膜）を形成させ（陽極酸化処理）、水洗する。続いて、適宜、表面調整、水洗などを施した後、本発明の化合物を含有する染料組成物を含有する陽極酸化アルミニウム用着色剤水溶液などに浸漬し、細孔内に染料を吸着（染色、電解着色）させ、表面の細孔をアルミニウム酸化物水和物などで封孔し封孔物質を形成することによって、着色することができる。
本発明の染料組成物を２種以上併用する場合、あるいは本発明の染料組成物を他の色素と併用する場合、使用するすべての色素の混合溶液を調製して陽極酸化アルミニウムを浸漬してもよく、また、各色素溶液を別々に調製し、各溶液に陽極酸化アルミニウムを順に浸漬してもよい。
First, the aluminum plate is degreased using an aqueous acid solution such as sulfuric acid, oxalic acid, chromic acid, or sulfonic acid, and washed with water. Next, the degreased aluminum plate is used as the anode and electrolyzed using an aqueous acid solution as the electrolyte to form an anodized film (alumite film) that forms many pores on the aluminum anode surface (anodizing treatment), and washed with water. Then, after performing surface conditioning, washing with water, etc. as appropriate, the plate is immersed in an aqueous colorant solution for anodized aluminum containing a dye composition containing the compound of the present invention, and the dye is adsorbed into the pores (dyeing, electrolytic coloring), and the pores on the surface are sealed with aluminum oxide hydrate or the like to form a sealing material, thereby coloring the plate.
When two or more types of the dye composition of the present invention are used in combination, or when the dye composition of the present invention is used in combination with other dyes, a mixed solution of all the dyes to be used may be prepared and the anodized aluminum may be immersed in the mixed solution, or each dye solution may be prepared separately and the anodized aluminum may be immersed in each solution in turn.
本発明の着色時における電解条件は、直流電解でも交流電解でもよく、直流電解が好ましい。電流密度は、０．１～１０Ａ／ｄｍ２が好ましく、０．５～３Ａ／ｄｍ２がより好ましい。通電時間は、１０秒～６０分が好ましい。陽極酸化皮膜の厚さは２～２０μｍが好ましい。これらの陽極酸化条件は、通電時間が長く陽極酸化皮膜が厚いほど濃色の着色となるため、これらの条件を調整することで、淡色～中間色～濃色の調整が行える。 The electrolysis conditions during coloring in the present invention may be DC electrolysis or AC electrolysis, with DC electrolysis being preferred. The current density is preferably 0.1 to 10 A/ dm2 , more preferably 0.5 to 3 A/ dm2 . The current application time is preferably 10 seconds to 60 minutes. The thickness of the anodized film is preferably 2 to 20 μm. With regard to these anodizing conditions, the longer the current application time and the thicker the anodized film, the darker the coloring will be, and therefore, by adjusting these conditions, it is possible to adjust the color from light to medium to dark.
上記の各工程の処理温度は、それぞれ適した温度が好ましく、陽極酸化時の温度は０～８０℃が好ましい。染色時の温度は１０℃～７０℃が好ましい。その他の処理温度は、１０～８０℃が好ましい。 The processing temperature for each of the above steps is preferably an appropriate temperature. The temperature for anodizing is preferably 0 to 80°C. The temperature for dyeing is preferably 10 to 70°C. The other processing temperatures are preferably 10 to 80°C.
本実施形態における染料組成物は、アルミニウム以外の金属を用いた陽極酸化物についても同様に使用することができる。たとえば、マグネシウム、亜鉛、チタン、ジルコニウムなど、陽極酸化した細孔に染料を吸着することができるものあれば、導電性プラスチックなどの非金属にも応用可能である。 The dye composition of this embodiment can be used in the same way for anodized oxides using metals other than aluminum. For example, it can be applied to nonmetals such as conductive plastics, as long as the anodized pores can adsorb the dye, such as magnesium, zinc, titanium, and zirconium.
本実施形態の陽極酸化アルミニウム用着色剤は、アルミニウムに着色した試料の特性を、色相、耐光性、耐熱性などを測定することによって評価することができる。色相は、目視で色味や均一性を評価することもでき、色差計により濃度（Ｋ／Ｓｄ）、色味（Ｌ*、ａ*、ｂ*）および色差（ΔＥ*）として測定してもよい。 The colorant for anodized aluminum of this embodiment can be evaluated by measuring the characteristics of a sample colored on aluminum, such as hue, light resistance, heat resistance, etc. The hue can be evaluated visually in terms of color tone and uniformity, or it may be measured using a color difference meter in terms of density (K/Sd), color tone (L * , a * , b * ) and color difference (ΔE * ).
本実施形態の陽極酸化アルミニウム用着色剤を用いて表すことのできる色は、紫、青紫、赤紫などの紫色系を表すことができる。これらの淡色（薄紫など）や濃色（濃紫など）など濃淡の異なるものを表すことができる。本実施形態の陽極酸化アルミニウム用着色剤は、上述した化合物と、他の色素を併用することにより、混色したもの（中間色）を表すこともできる。 The colors that can be expressed using the colorant for anodized aluminum of this embodiment include purple colors such as purple, blue-purple, and red-purple. These colors can also be expressed in different shades, such as light colors (such as light purple) and dark colors (such as dark purple). The colorant for anodized aluminum of this embodiment can also express mixed colors (intermediate colors) by using the above-mentioned compound in combination with other pigments.
本実施形態の陽極酸化アルミニウム用着色剤を用いて着色したアルミニウムの耐光性試験は、紫外光を含む太陽光を模した試験機などを用いて、一定時間、試料に光照射し、試験前後の着色アルミニウムの色相の変化を測定することで行ってもよい。具体的には、色差計などを用い、ＣＩＥ Ｌ*ａ*ｂ*表色系で色味を測定して得られた光照射試験前後の色差ΔＥ* ａｂ（またはΔＥ*）により評価してもよい。耐光性の判定には、着色アルミニウムの色相を、日本産業規格（ＪＩＳ Ｌ ０８０４「変退色用グレースケール」）にて定める方法に従って、グレースケールを用いた目視による染色堅牢度判定を行ってもよい。 The light fastness test of the aluminum colored with the coloring agent for anodized aluminum of this embodiment may be performed by irradiating the sample with light for a certain period of time using a tester that simulates sunlight including ultraviolet light, and measuring the change in the hue of the colored aluminum before and after the test. Specifically, the test may be evaluated based on the color difference ΔE * ab (or ΔE * ) before and after the light irradiation test obtained by measuring the color tone using the CIE L * a * b * color system using a color difference meter or the like. To judge the light fastness, the color fastness of the colored aluminum may be judged visually using a gray scale according to the method specified in the Japanese Industrial Standards (JIS L 0804 "Gray scale for discoloration").
本実施形態の陽極酸化アルミニウム用着色剤を用いて着色したアルミニウムの耐熱性試験は、例えば５０～３００℃の温度範囲の恒温器や熱風乾燥機内で、３０分～５０時間などの範囲で、適当な一定時間加熱する方法など、耐光性試験と同様に試験前後の色相の変化を評価する方法があげられる。 The heat resistance test for aluminum colored using the colorant for anodized aluminum of this embodiment can be performed by heating the aluminum for an appropriate fixed period of time, such as 30 minutes to 50 hours, in an incubator or hot air dryer at a temperature range of 50 to 300°C, and evaluating the change in hue before and after the test in the same manner as the light resistance test.
本実施形態の陽極酸化アルミニウム用着色剤を用いた着色アルミニウムは、多様多種のアルミ板材料、アルミニウム製外装を使用した製品に用いられる。 Colored aluminum produced using the colorant for anodized aluminum of this embodiment is used in a wide variety of aluminum sheet materials and products that use aluminum exteriors.
以下、本発明を実施例により具体的に説明するが、以下の実施例に限定されない。なお、実施例中に、化合物（色素）の水溶液の紫外可視吸収スペクトル分析（ＵＶ－Ｖｉｓ）にり測定した極大吸収波長（λｍａｘ）（ｎｍ）を示す。 The present invention will be described in detail below with reference to examples, but is not limited to these examples. In the examples, the maximum absorption wavelength (λmax) (nm) measured by ultraviolet-visible absorption spectroscopy (UV-Vis) of an aqueous solution of the compound (dye) is shown.
［合成実施例１］ 色素（１－１）の合成
反応容器に、３，６－ジクロロ－９－（２－スルホナトフェニル）キサンチリウム（またはジクロロスルホフルオラン、製品名：ＤＣＳＦ、太陽ファインケミカル株式会社製）４０ｇ、５－アミノ－２－ナフタレンスルホン酸７３．２ｇ、Ｎ－メチルピロリドン（ＮＭＰ）２４０ｍＬを入れ、１４０℃で２０時間撹拌した。反応液を１２０℃－減圧で溶媒除去し、濃縮した。残渣に３０％塩酸３００ｍＬを加え、室温で３０分間撹拌し、析出した固体をろ取し、乾燥し、目的の色素（１－１）を黒紫色粉末として得た（３６．８ｇ）（λｍａｘ：５３９ｎｍ）。
Synthesis Example 1 Synthesis of dye (1-1) 40 g of 3,6-dichloro-9-(2-sulfonatophenyl)xanthylium (or dichlorosulfofluoran, product name: DCSF, manufactured by Taiyo Fine Chemical Co., Ltd.), 73.2 g of 5-amino-2-naphthalenesulfonic acid, and 240 mL of N-methylpyrrolidone (NMP) were placed in a reaction vessel and stirred at 140° C. for 20 hours. The reaction liquid was concentrated by removing the solvent at 120° C. under reduced pressure. 300 mL of 30% hydrochloric acid was added to the residue and stirred at room temperature for 30 minutes. The precipitated solid was filtered and dried to obtain the target dye (1-1) as a black purple powder (36.8 g) (λmax: 539 nm).
［合成実施例２］ 色素（１－２）の合成
反応容器に、ＤＣＳＦ ８．５ｇ、６－アミノ－２－ナフタレンスルホン酸２２．５ｇ、ＮＭＰ４０ｍＬを入れ、１６０℃で２１時間撹拌した。反応液を３０℃以下に放冷後、アセトニトリル５０ｍＬを加え、３０分間撹拌後、析出した固体をろ過した。１７．５％塩酸６０ｍＬを加え、室温で３０分間撹拌した後、析出した結晶をろ過し、乾燥することにより、目的の色素（１－２）を黒紫色粉末として得た（１８．１ｇ）（λｍａｘ：５６７ｎｍ）。
Synthesis Example 2 Synthesis of dye (1-2) 8.5 g of DCSF, 22.5 g of 6-amino-2-naphthalenesulfonic acid, and 40 mL of NMP were placed in a reaction vessel and stirred at 160° C. for 21 hours. After the reaction solution was allowed to cool to 30° C. or less, 50 mL of acetonitrile was added, and the mixture was stirred for 30 minutes, after which the precipitated solid was filtered. 60 mL of 17.5% hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were filtered and dried to obtain the target dye (1-2) as a black-purple powder (18.1 g) (λmax: 567 nm).
［合成実施例３］ 色素（１－３）の合成
反応容器に、ＤＣＳＦ ８．０ｇ、７－アミノ－２－ナフタレンスルホン酸９．７ｇ、ＮＭＰ３０ｍＬ、を入れ、６０℃で３時間撹拌した。反応液を３０℃以下に放冷し、析出した固体をろ過し、乾燥することにより、中間体６．６ｇを得た。続いて、別の反応容器に、前記中間体５．０ｇ、２－アミノ－５－（ジエチルアミノ）トルエン６．８ｇ、ＮＭＰ２０ｍＬを入れ、１２０℃で４時間撹拌した。反応液を５％塩酸２００ｍＬに入れ、室温で３０分間撹拌した。析出した固体をろ取し、水５０ｍＬに入れ、４８％水酸化ナトリウム水溶液を加え中性にし、この水溶液を８０℃で２４時間以上減圧乾燥し、目的の色素（１－３）を黒紫色粉末として得た（５．５ｇ）（λｍａｘ：５５２ｎｍ）。
Synthesis Example 3 Synthesis of dye (1-3) 8.0 g of DCSF, 9.7 g of 7-amino-2-naphthalenesulfonic acid, and 30 mL of NMP were placed in a reaction vessel and stirred at 60° C. for 3 hours. The reaction solution was allowed to cool to 30° C. or lower, and the precipitated solid was filtered and dried to obtain 6.6 g of an intermediate. Next, 5.0 g of the intermediate, 6.8 g of 2-amino-5-(diethylamino)toluene, and 20 mL of NMP were placed in another reaction vessel and stirred at 120° C. for 4 hours. The reaction solution was placed in 200 mL of 5% hydrochloric acid and stirred at room temperature for 30 minutes. The precipitated solid was collected by filtration, placed in 50 mL of water, neutralized by adding a 48% aqueous sodium hydroxide solution, and the aqueous solution was dried under reduced pressure at 80° C. for 24 hours or more to obtain the target dye (1-3) as a black purple powder (5.5 g) (λmax: 552 nm).
［合成実施例４］ 色素（１－４）の合成
反応容器に、ＤＣＳＦ ６．９ｇ、６－アミノ－１－ナフトール－３－スルホン酸９．０９ｇ、ＮＭＰ５０ｍＬ、を入れ、１４０℃で２１時間撹拌した。反応液を２００ｍＬの水に入れ、更に３５％塩酸１００ｍＬを添加し、色素を析出させた。ろ過により固体を取り出し、乾燥後、目的の色素（１－４）を青紫色粉末として得た（１４．３ｇ）（λｍａｘ：５６３ｎｍ）。
Synthesis Example 4 Synthesis of dye (1-4) 6.9 g of DCSF, 9.09 g of 6-amino-1-naphthol-3-sulfonic acid, and 50 mL of NMP were placed in a reaction vessel and stirred at 140° C. for 21 hours. The reaction solution was placed in 200 mL of water, and 100 mL of 35% hydrochloric acid was added to precipitate the dye. The solid was removed by filtration and dried, and the target dye (1-4) was obtained as a blue-purple powder (14.3 g) (λmax: 563 nm).
［実施例１］
＜着色アルミニウムの作製＞
以下の手順でアルミニウム基板上に、陽極酸化処理して、着色アルミニウムを作製した。なお、陽極酸化および染色の工程で、処理時間と染料化合物濃度を設定した。
（脱脂） 容器に、脱脂剤（奥野製薬工業株式会社製、トップＡＤＤ－１００）１５０ｍＬ、９８％硫酸７０ｍＬ、水１０００ｍＬを混合したものを脱脂液として調製し、適当な寸法に裁断した染色用アルミニウム基板を浸漬し、６０℃で３分間脱脂処理を行い、処理後水洗した。
（陽極酸化） ９８％硫酸を用いて１８０ｇ／Ｌの電解液を調製し、電解装置の電極にアルミニウム基板を接続し、電解液槽に浸漬し、温度１９～２１℃、電流密度１．０Ａ／ｄｍ２の以下の通電時間の条件で陽極酸化を行い、以下の厚さの陽極酸化皮膜を得た。酸化後、水洗した。
陽極酸化条件：通電１５分間 陽極酸化皮膜厚：５μｍ
（表面調整） 表面調整剤（奥野製薬工業株式会社製、ＴＡＣソマール１２１）および水を用いて、濃度５０ｍＬ／Ｌの表面調整液を調製し、４５℃で１分間、アルミニウム基板を浸漬した。浸漬後アルミニウム基板を水洗した。
（染色） 合成実施例１で得られた色素（１－１）を用い、本発明の染料組成物としてそれぞれ下記の濃度の色素を含有する染色用水溶液を調製し、以下の染色時間で浸漬し、ともに温度（建浴温度）５５℃で染色した。染色後アルミニウム基板を水洗した。
染色条件：色素濃度２．０重量％ 染色時間：３０秒間
（封孔） 封孔剤（奥野製薬工業株式会社製、トップシールＨ－２９８）および水を用いて４０ｍＬ／Ｌの封孔液を調製し、約９０℃で１５分間封孔処理を行った。封孔処理後、温風で乾燥した。
[Example 1]
<Preparation of colored aluminum>
Colored aluminum was produced by anodizing an aluminum substrate in the following manner: In the anodizing and dyeing steps, the treatment time and the dye compound concentration were set.
(Degreasing) A degreasing solution was prepared by mixing 150 mL of a degreasing agent (TOP ADD-100, manufactured by Okuno Chemical Industries Co., Ltd.), 70 mL of 98% sulfuric acid, and 1000 mL of water in a container. An aluminum substrate for dyeing cut to an appropriate size was immersed in the solution and subjected to a degreasing treatment at 60° C. for 3 minutes, and then washed with water.
Anodization was performed at a temperature of 19 to 21° C., a current density of 1.0 A/ dm2 , and the following current application time conditions to obtain an anodized film with the following thickness. After oxidation, the substrate was washed with water.
Anodizing conditions: Electric current for 15 minutes Anodizing film thickness: 5 μm
(Surface Conditioning) A surface conditioner (TAC Somar 121, manufactured by Okuno Chemical Industries Co., Ltd.) and water were used to prepare a surface conditioner solution with a concentration of 50 mL/L, and the aluminum substrate was immersed in the solution for 1 minute at 45° C. After immersion, the aluminum substrate was washed with water.
(Dyeing) Using the dye (1-1) obtained in Synthesis Example 1, dyeing aqueous solutions containing the dye at the following concentrations were prepared as the dye compositions of the present invention, and the aluminum substrates were immersed for the following dyeing times and dyed at a temperature (make-up bath temperature) of 55° C. After dyeing, the aluminum substrates were washed with water.
Dyeing conditions: dye concentration 2.0% by weight Dyeing time: 30 seconds (sealing) A 40 mL/L sealing solution was prepared using a sealant (Topseal H-298, manufactured by Okuno Chemical Industries Co., Ltd.) and water, and sealing treatment was carried out for 15 minutes at about 90° C. After sealing treatment, the sample was dried with hot air.
＜色相の評価＞
色素（１－１）を用いて着色した着色アルミニウム板の色相を目視と色差計（装置名：コニカミノルタ製分光色差計 型式：ＣＭ－３７００Ａ）でＣＩＥ Ｌ*ａ*ｂ*表色系により評価した。評価した色相の結果を表１に示す。
<Evaluation of Hue>
The hue of the colored aluminum plate colored with the dye (1-1) was evaluated visually and with a colorimeter (apparatus name: Konica Minolta spectrophotometer, model: CM-3700A) according to the CIE L * a * b * color system. The results of the evaluated hues are shown in Table 1.
［実施例２～実施例４］
色素（１－１）の代わりに、色素（１－２）、（１－３）、または（１－４）を用いたこと以外は、実施例１と同様の方法で、着色アルミニウム板を作製し、色相を評価した。結果を表１にまとめて示す。
[Examples 2 to 4]
Colored aluminum plates were produced in the same manner as in Example 1, except that the dye (1-1) was replaced with the dye (1-2), (1-3), or (1-4), and the hues were evaluated. The results are shown in Table 1.
［参考例１～参考例４］
色素（１－１）の代わりに、本発明に属さない、下記式で表される次の色素（水溶液の極大吸収波長（λｍａｘ）（ｎｍ）も示す。）：
（Ｄ－１）Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ２８９ （λｍａｘ：５２６ｎｍ）、
（Ｄ－２）Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ １０２ （λｍａｘ：５３３ｎｍ）、
（Ｄ－３）Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ ９ （λｍａｘ：５２９ｎｍ）、
（Ｄ－４）Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ９２ （λｍａｘ：５３８ｎｍ）
について、実施例１と同様の作製条件で着色アルミニウムを作製し、色相を評価した結果を表１にまとめて示す。
[Reference example 1 to reference example 4]
Instead of the dye (1-1), the following dye not belonging to the present invention and represented by the following formula (the maximum absorption wavelength (λmax) (nm) of the aqueous solution is also shown):
(D-1)C. I. Acid Red 289 (λmax: 526 nm),
(D-2)C. I. Acid Violet 102 (λmax: 533nm),
(D-3)C. I. Acid Violet 9 (λmax: 529nm),
(D-4)C. I. Acid Red 92 (λmax: 538nm)
Colored aluminum was prepared under the same preparation conditions as in Example 1, and the hue was evaluated. The results are shown in Table 1.
［実施例５］
＜耐光性の評価＞
色素（１－３）を用いて着色した着色アルミニウム板について、次の方法で耐光性試験を行った。キセノンフェードメーター／ＡＴＬＡＳ Ｃｉ３０００＋Ｘｅｎｏｎ Ｗｅａｔｈｅｒ Ｏｍｅｔｅｒ（アトラス社製）を用いて、放射照度：３００～４００ｎｍ、６０Ｗ／ｍ２、試験槽内温度：３８℃、湿度：５０％、ブラックパネル（ＢＰ）温度：６３℃ の条件で、着色アルミニウム板に５０時間、１００時間および２００時間照射したものについて、色差計による色相および光照射前後の色差ΔＥ*の測定を行い、また、グレースケールの級数による染色堅牢度の目視判定（ＪＩＳ Ｌ ０８０４「変退色用グレースケール」）により耐光性の判定を行った。級数は、５級が最高で、１級が最低であり、級数が高いものほど色が濃く（色差ΔＥ*が小さく）照射前の色相を保っていることを示す。本発明の評価方法では、級数の判定結果を３段階に分け、以下の判定基準で評価し、結果を表２に示す。
グレースケール判定基準：級数と本発明における評価との対応
５級～４級：Ａ（特に良好な耐光性）
３級：Ｂ（通常レベルの耐光性）
２級以下：Ｃ（耐光性低い）
[Example 5]
<Evaluation of Light Fastness>
A lightfastness test was carried out on the colored aluminum plate colored with the dye (1-3) by the following method. Using a xenon fade meter/ATLAS Ci3000+Xenon Weather Ometer (manufactured by Atlas Co., Ltd.), the colored aluminum plate was irradiated for 50, 100 and 200 hours under the conditions of irradiance: 300-400 nm, 60 W/m 2 , temperature in test chamber: 38° C., humidity: 50%, black panel (BP) temperature: 63° C., and the hue and color difference ΔE * before and after light irradiation were measured by a color difference meter. In addition, the lightfastness was judged by visual judgment of the color fastness according to the grayscale series (JIS L 0804 "grayscale for discoloration"). The series is highest at 5 and lowest at 1, and the higher the series, the darker the color (smaller color difference ΔE * ) and the more the hue before irradiation is maintained. In the evaluation method of the present invention, the results of the series are divided into three stages and evaluated according to the following criteria. The results are shown in Table 2.
Grayscale criterion: Correspondence between the grade and the evaluation in the present invention Grade 5 to Grade 4: A (particularly good light resistance)
Grade 3: B (normal level of light resistance)
Grade 2 or below: C (low light resistance)
［参考例５～参考例７］
色素（１－３）の代わりに、前記色素（Ｄ－２）～（Ｄ－４）を用いて作製した着色アルミニウムについて、実施例４と同様に耐光性を評価した結果を表２にまとめて示す。
[Reference example 5 to reference example 7]
The colored aluminum films were prepared by using the dyes (D-2) to (D-4) instead of the dye (1-3). The light resistance of the colored aluminum films was evaluated in the same manner as in Example 4. The results are shown in Table 2. show.
表１および表２の結果から、本発明の色素を含有する染料組成物からなる陽極酸化アルミニウム着色剤を用いることにより、アルミニウム上に、紫色系で、従来品に対して遜色のない耐光性を有する皮膜を形成することができた。 The results in Tables 1 and 2 show that by using an anodized aluminum colorant made of a dye composition containing the dye of the present invention, it is possible to form a purple-colored coating on aluminum that has light resistance comparable to that of conventional products.
（耐熱性試験）
［実施例６～実施例８］
色素（１－１）、（１－２）および（１－４）について、上記実施例１において、陽極酸化皮膜厚および染色時間を淡色（７μｍ・３０秒間）、中間色（１１μｍ・２分間）、濃色（１５μｍ・５分間） の３条件で染色したこと以外は、実施例１と同様に着色したアルミニウム板について、次の方法で耐熱性試験を行った。定温乾燥機（アズワン株式会社製、型式：８７Ｌ ＥＯＰ－４５０Ｖ）を用いて、下記の暴露条件で試料を加熱した。
乾燥機内温度および加熱時間：２００℃－５時間、または２５０℃－３時間
本発明の耐熱性の評価方法は、加熱前後の着色アルミニウム試料の色差を下記の色差計で測定し、かつ、目視により、以下の判定基準で評価した。結果を表２に示す。
装置：色差計（コニカミノルタ株式会社製分光色差計、型式：ＣＭ－３７００Ａ）
色差計算式：ΔＥ＊
ａｂ（Ｌ＊ａ＊ｂ＊、ＣＩＥ １９７６）
およびΔＥ＊
００（ＣＩＥ ＤＥ２０００）
視野角：１０°
耐熱性判定基準：色差Ｅ＊
ａｂが小さいものほど良好な耐熱性であることを意味する。
Ａ：良好な耐熱性 ΔＥ＊≦２．０
Ｂ：通常レベルの耐熱性 ２．０＜ΔＥ＊≦５．０
Ｃ：耐熱性低い ΔＥ＊＞５．０
(Heat resistance test)
[Examples 6 to 8]
For the dyes (1-1), (1-2) and (1-4), heat resistance tests were carried out on aluminum plates dyed in the same manner as in Example 1, except that the anodized film thickness and dyeing time were changed to three conditions, light color (7 μm, 30 seconds), medium color (11 μm, 2 minutes) and dark color (15 μm, 5 minutes). The samples were heated under the following exposure conditions using a constant temperature dryer (model: 87L EOP-450V, manufactured by AS ONE Corporation).
Dryer temperature and heating time: 200°C-5 hours, or 250°C-3 hours. The heat resistance of the present invention was evaluated by measuring the color difference of the colored aluminum sample before and after heating with a color difference meter described below, and visually evaluating the color difference according to the following criteria. The results are shown in Table 2.
Equipment: Colorimeter (Konica Minolta spectrophotometer, model: CM-3700A)
Color difference calculation formula: ΔE * ab (L * a * b * , CIE 1976)
and ΔE * 00 (CIE DE2000)
Viewing angle: 10°
Heat resistance evaluation standard: the smaller the color difference E * ab , the better the heat resistance.
A: Good heat resistance ΔE * ≦2.0
B: Normal level of heat resistance 2.0<ΔE * ≦5.0
C: Low heat resistance ΔE * >5.0
［参考例８～参考例１１］
参考例１～参考例２の化合物（Ｄ－１）～（Ｄ－４）について同様に着色した試料について、実施例６～実施例９と同様に耐熱性を評価した結果を表３にまとめて示す。
[Reference example 8 to reference example 11]
The heat resistance of the samples colored in the same manner as in Examples 6 to 9 using the compounds (D-1) to (D-4) of Reference Examples 1 and 2 is evaluated. The results are summarized in Table 3. show.
表３の結果から、本発明の化合物を含有する染料組成物からなる陽極酸化アルミニウム着色剤を用いることにより、アルミニウム上に、紫色、青味の紫、青紫、青色系の皮膜を形成し、耐熱性の高い皮膜を形成することができた。従来の同系統色の紫～青色系のキサンテン色素と比較しても遜色ない耐熱性を有している。 The results in Table 3 show that by using an anodized aluminum colorant made of a dye composition containing the compound of the present invention, it is possible to form a film on aluminum that is purple, bluish purple, blue-purple, or blue, and that is highly heat-resistant. The heat resistance is comparable to that of conventional xanthene dyes of the same color family, purple to blue.
本発明に係るキサンテン系色素を含有する染料組成物によれば、耐光性や耐熱性に優れた、クロムなどの重金属を含まない着色剤として様々な材料に利用できる。特に、単色で紫色系の着色皮膜を形成する陽極酸化アルミニウム用着色剤を得ることができる。また、該着色剤を用いることにより、単色で紫色系に着色された、耐光性や耐熱性に優れた陽極酸化アルミニウム皮膜を得ることができる。
The dye composition containing the xanthene dye according to the present invention can be used for various materials as a colorant that is excellent in light fastness and heat resistance and does not contain heavy metals such as chromium. In particular, a colorant for anodized aluminum that forms a monochromatic purple-colored coating can be obtained. Furthermore, by using the colorant, an anodized aluminum coating that is monochromatically colored purple and has excellent light fastness and heat resistance can be obtained.
Claims (5)
［式（１）中、Ｒ１およびＲ２はそれぞれ独立に、
置換基を有していてもよい炭素原子数６～３０のナフチル基、または、
置換基を有していてもよい炭素原子数６～３０のフェニル基を表し、
ただし、Ｒ１およびＲ２のうち少なくとも１個は、
置換基を有していてもよい炭素原子数６～３０のナフチル基である。] A colorant for anodized aluminum, comprising a dye composition containing a xanthene colorant represented by the following general formula (1):
[In formula (1), R 1 and R 2 each independently represent
a naphthyl group having 6 to 30 carbon atoms which may have a substituent, or
represents a phenyl group having 6 to 30 carbon atoms which may have a substituent,
However, at least one of R 1 and R 2 is
and a naphthyl group having 6 to 30 carbon atoms which may have a substituent.]
［式（２）～（４）中、Ｒ３～Ｒ２１は、それぞれ独立に、―Ｈ、―ＯＨ、―ＣＯＯＭ、―ＮＯ２、―ＮＯ、―ＣＮ、―ＳＯ３Ｍ、―ＳＨ、
置換基を有していてもよい炭素原子数０～２０のアミノ基、
置換基を有していてもよい炭素原子数０～２０のスルホニル基、
置換基を有していてもよい炭素原子数１～２０の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数３～２０のシクロアルキル基、
置換基を有していてもよい炭素原子数１～２０の直鎖状もしくは分岐状のアルコキシ基、
置換基を有していてもよい炭素原子数３～２０のシクロアルコキシ基、
置換基を有していてもよい炭素原子数２～２０の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数１～２０のアシル基、
置換基を有していてもよい炭素原子数６～２０の芳香族炭化水素基、または
置換基を有していてもよい炭素原子数２～２０の複素環基を表し、
Ｍは、水素原子またはアルカリ金属原子を表す。］ 2. The colorant for anodized aluminum according to claim 1, wherein in the general formula (1), R 1 or R 2 is any one of monovalent groups represented by the following general formulas (2) to (4):
[In formulas (2) to (4), R 3 to R 21 each independently represent —H, —OH, —COOM, —NO 2 , —NO, —CN, —SO 3 M, —SH,
an amino group having 0 to 20 carbon atoms which may have a substituent;
a sulfonyl group having 0 to 20 carbon atoms which may have a substituent;
a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent;
a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent;
a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent;
a cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent,
a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent;
an acyl group having 1 to 20 carbon atoms which may have a substituent;
represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
M represents a hydrogen atom or an alkali metal atom.
［式（１）中、Ｒ １ およびＲ ２ はそれぞれ独立に、
置換基を有していてもよい炭素原子数６～３０のナフチル基、または、
置換基を有していてもよい炭素原子数６～３０のフェニル基を表し、
ただし、Ｒ １ およびＲ ２ のうち少なくとも１個は、
置換基を有していてもよい炭素原子数６～３０のナフチル基である。] A method for coloring anodized aluminum, anodized aluminum oxide, or anodized aluminum alloy, comprising using a dye composition containing 0.02 to 10 mass % of a xanthene dye represented by the following general formula (1) :
[In formula (1), R 1 and R 2 each independently represent
a naphthyl group having 6 to 30 carbon atoms which may have a substituent, or
represents a phenyl group having 6 to 30 carbon atoms which may have a substituent,
However, at least one of R 1 and R 2 is
and a naphthyl group having 6 to 30 carbon atoms which may have a substituent.]
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2000064988A1 (en) | 1999-04-23 | 2000-11-02 | Molecular Probes, Inc. | Xanthene dyes and their application as luminescence quenching compounds |
| JP2013506053A (en) | 2009-09-30 | 2013-02-21 | クラリアント・ファイナンス・（ビーブイアイ）・リミテッド | Method for coloring anodized aluminum surface |
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| DE3514387C2 (en) | 1984-04-27 | 2003-12-24 | Clariant Finance Bvi Ltd | 1: 2 metal complex azo compounds, their production and use |
| DE3718849A1 (en) | 1987-06-05 | 1988-12-15 | Henkel Kgaa | ELECTROLYTIC COLORING OF ANODISED ALUMINUM |
| JPH09302256A (en) | 1996-05-10 | 1997-11-25 | Hodogaya Chem Co Ltd | Dye composition and method for coloring aluminum using the same |
| CA2321767C (en) | 1998-08-14 | 2008-07-29 | Clariant Finance (Bvi) Limited | 1:2 chromium complex dyes, their production and use |
| JP5946174B2 (en) * | 2012-06-07 | 2016-07-05 | 日本化薬株式会社 | Xanthene-based soluble precursor compounds and colorants |
| TWI674477B (en) * | 2014-12-25 | 2019-10-11 | 日商富士軟片股份有限公司 | Coloring curable composition, color filter, pattern forming method, method of manufacturing color filter, solid-state imaging element, and image display device |
| CN109608429A (en) * | 2018-12-03 | 2019-04-12 | 浙江工业大学 | A kind of synthesis technology of sulfonic group rhodamine compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000064988A1 (en) | 1999-04-23 | 2000-11-02 | Molecular Probes, Inc. | Xanthene dyes and their application as luminescence quenching compounds |
| JP2013506053A (en) | 2009-09-30 | 2013-02-21 | クラリアント・ファイナンス・（ビーブイアイ）・リミテッド | Method for coloring anodized aluminum surface |
Non-Patent Citations (5)
| Title |
|---|
| REGISTRY(STN)，2004.08.30 RN 736095-53-7 |
| REGISTRY(STN)，2004.09.24 RN 750529-84-1 |
| REGISTRY(STN)，2004.10.15 RN 763883-78-9 |
| REGISTRY(STN)，2004.11.04 RN 775243-76-0 |
| REGISTRY(STN)，2004.11.25 RN 788780-98-3 |
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