CN104350107A - 纤维反应性染料、它们的制备和用途 - Google Patents
纤维反应性染料、它们的制备和用途 Download PDFInfo
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- CN104350107A CN104350107A CN201380030832.1A CN201380030832A CN104350107A CN 104350107 A CN104350107 A CN 104350107A CN 201380030832 A CN201380030832 A CN 201380030832A CN 104350107 A CN104350107 A CN 104350107A
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- alkyl
- chemically
- amino
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- 239000000985 reactive dye Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 9
- -1 polyazo Polymers 0.000 claims abstract description 70
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000007639 printing Methods 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 238000004043 dyeing Methods 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 claims abstract description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 3
- 239000000975 dye Substances 0.000 claims description 85
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 51
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 41
- 150000002367 halogens Chemical group 0.000 claims description 35
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 239000000460 chlorine Chemical group 0.000 claims description 22
- 229910052801 chlorine Chemical group 0.000 claims description 22
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 22
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 21
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- 239000011737 fluorine Substances 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229920000742 Cotton Polymers 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 6
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- OLCKRGCUQOKQCM-UHFFFAOYSA-N 2-fluoro-1,3,5-triazine Chemical compound FC1=NC=NC=N1 OLCKRGCUQOKQCM-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 4
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 125000003368 amide group Chemical group 0.000 abstract 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 abstract 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 41
- 239000000243 solution Substances 0.000 description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000004744 fabric Substances 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000344 soap Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 230000008719 thickening Effects 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 5
- 238000007641 inkjet printing Methods 0.000 description 5
- 150000002790 naphthalenes Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical group 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000009992 mercerising Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 3
- HSPSCWZIJWKZKD-UHFFFAOYSA-N n-chloroacetamide Chemical compound CC(=O)NCl HSPSCWZIJWKZKD-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000005184 naphthylamino group Chemical group C1(=CC=CC2=CC=CC=C12)N* 0.000 description 3
- PPSSQRUPSRPZON-UHFFFAOYSA-N nitrobenzene;sodium Chemical compound [Na].[O-][N+](=O)C1=CC=CC=C1 PPSSQRUPSRPZON-UHFFFAOYSA-N 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 C*C(N=C*)=*C(*)=NC Chemical compound C*C(N=C*)=*C(*)=NC 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XVTUILQTJLXDEI-UHFFFAOYSA-N acetamidourea Chemical group CC(=O)NNC(N)=O XVTUILQTJLXDEI-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000009980 pad dyeing Methods 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- YAIKCRUPEVOINQ-UHFFFAOYSA-N 2-aminonaphthalene-1,5-disulfonic acid Chemical class OS(=O)(=O)C1=CC=CC2=C(S(O)(=O)=O)C(N)=CC=C21 YAIKCRUPEVOINQ-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- NCVKFSRROIAVKB-GQCTYLIASA-N CC1(/C=C/C)C=C(C)C=C1 Chemical compound CC1(/C=C/C)C=C(C)C=C1 NCVKFSRROIAVKB-GQCTYLIASA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 240000008886 Ceratonia siliqua Species 0.000 description 1
- 235000013912 Ceratonia siliqua Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
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Classifications
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- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
- C09B62/80—Anthracene dyes
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- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
- C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
- C09B62/4405—Dioxazine dyes
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- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
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- C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
- C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
- C09B62/4407—Formazane dyes
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- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
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- C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
- C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
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- C09B62/4413—Non-metallized monoazo dyes
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- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
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- C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
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- C09B62/4415—Disazo or polyazo dyes
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- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
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- C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
- C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
- C09B62/4411—Azo dyes
- C09B62/4416—Metal complex azo dyes
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- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
- C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
- C09B62/4418—Porphines; Azoporphines
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- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
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- C09B62/825—Monoazo dyes
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
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- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
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- C09B62/835—Metal complex azo dyes
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
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Abstract
式(1)的反应性染料适用于染色和印刷纤维素纤维材料或含酰胺基团的纤维材料,其中Q1和Q2彼此独立地为氢,或者未取代或被取代的C1-C4烷基,A为单偶氮、多偶氮、金属络合物偶氮、蒽醌、酞菁、甲或二噁嗪发色团的基团,X为卤素、3-或4-羧基吡啶-1-基、或3-或4-氨基甲酰基吡啶-1-基,Y为乙烯基或基团-CH2-CH2-U,U为在碱性条件下可除去的基团,且q为数字1或2。
Description
本发明涉及纤维反应性染料、它们的制备方法以及它们在染色或印刷纺织品纤维材料中的用途。
使用反应性染料进行染色和印刷的实践近来已导致对印刷物品质以及染色和印刷方法收益性的更高的要求。结果是,仍需要具有改进的性质的新的反应性染料,尤其是关于它们的应用。
当今,需要具有足够直接性并且同时具有洗去未固定的染料的良好便利性的反应性染料。它们还应具有良好的得色量和高反应性,目标尤其是提供具有高固定度的染色物和印刷物。已知的染料不能在所有性质上都满足这些要求。
因此,本发明潜在的问题是,对于纤维材料的染色或印刷,寻求具有高程度的以上表明的品质的新的改进的反应性染料。新的染料的特征应尤其在于良好的提升率(build-up)性能、高固定产出(fixing yield)和高纤维-染料结合稳定性;对于不固定于纤维而容易被洗掉的染料也应是可能的。所述染料还应得到具有良好的全面的牢度性质(例如光牢度和湿牢度性质)的染色物和印刷物。
已显示,通过以下定义的新的染料,大大解决造成的问题。
因此,本发明涉及式(1)的反应性染料
其中
Q1和Q2彼此独立地为氢,或者未取代或被取代的C1-C4烷基,
A为单偶氮、多偶氮、金属络合物偶氮、蒽醌、酞菁、甲或二噁嗪发色团的基团,
X为卤素、3-或4-羧基吡啶-1-基、或3-或4-氨基甲酰基吡啶-1-基,
Y为乙烯基或基团-CH2-CH2-U,U为在碱性条件下可除去的基团,且q为数字1或2。
C1-C4烷基Q1和Q2为直链或支化的。烷基可例如被羟基、磺基、硫酸根合、氰基或被羧基进一步取代。可提及以下基团作为实例:甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基,以及被羟基、磺基、硫酸根合、氰基或被羧基取代的相应的基团。优选羟基、磺基、硫酸根合或羧基作为取代基。尤其优选羟基或硫酸根合作为取代基。
优选,Q1和Q2彼此独立地为氢或C1-C4烷基,尤其是氢、甲基或乙基,烷基未取代或被羟基、磺基、硫酸根合或被羧基取代;更尤其是,Q1为氢,并且Q2为氢、甲基或乙基。
非常尤其是,Q1和Q2为氢。
作为卤素的X为例如氟、氯或溴,尤其是氯或氟。
优选,X为卤素,尤其是氯或氟。
作为在碱性条件下可除去的基团,U可为例如-Cl、-Br、-F、-OSO3H、-SSO3H、-OCO-CH3、-OPO3H2、-OCO-C6H5、-OSO2-C1-C4烷基或-OSO2-N(C1-C4烷基)2。U优选为式-Cl、-OSO3H、-SSO3H、-OCO-CH3、-OCO-C6H5或-OPO3H的基团2,尤其是-Cl或-OSO3H,更尤其是-OSO3H。
因此,合适的基团Y的实例为乙烯基、β-溴-或β-氯-乙基、β-乙酰氧基-乙基、β-苯甲酰氧基乙基、β-磷酸根合乙基、β-硫酸根合乙基和β-硫代硫酸根合乙基。本发明的式(1)的染料中的Y优选为乙烯基、β-氯乙基或β-硫酸根合乙基,尤其是乙烯基或β-硫酸根合乙基。
优选,q为数字1。
A例如为以下染料基团之一:
a) 苯或萘系列的1:1铜络合物偶氮染料的染料基团,其中铜原子与能在偶氮桥的邻位的任一侧上被金属化的基团结合;
b) 式(2)或(3)的单偶氮或双偶氮染料的染料基团或由其衍生的金属络合物,
或
其中
P1为苯或萘系列的重氮或偶联组分的基团,M为苯或萘系列的中心组分的基团,K1为苯、萘、吡唑啉酮、6-羟基吡啶-2-酮或乙酰乙酸芳基酰胺系列的偶联组分的基团,u为数字0或1,其中P1、D1、M和K1可携带偶氮染料常规的取代基;
c) 式(4)的双偶氮染料的染料基团
-D2-N=N-K2-N=N-D3 (4),
其中D2和D3彼此独立地为苯或萘系列的重氮组分的不同基团,和K2为萘系列的偶联组分的基团,其中D2、D3和K2可携带偶氮染料常规的取代基;
d) 式(5)的甲染料的染料基团
其中苯环不含其它取代基或被C1-C4烷基、C1-C4烷氧基、C1-C4烷基磺酰基、卤素或被羧基进一步取代;
e) 式(6)的蒽醌染料的染料基团
其中G为未取代或被C1-C4烷基、C1-C4烷氧基、卤素、羧基或被磺基取代的亚苯基或为亚环己基、亚苯基亚甲基或C2-C6亚烷基;
f) 式(7)的酞菁染料的染料基团
其中Pc为金属酞菁的基团,尤其是铜或镍酞菁的基团,J为-OH和/或-NQ4Q5,Q4和Q5彼此独立地为氢或未取代或被羟基或被磺基取代的C1-C4烷基,Q3为氢或C1-C4烷基,E为未取代或被C1-C4烷基、卤素、羧基或被磺基取代的亚苯基或为C2-C6亚烷基,且k为1-3;
g) 式(8a)、(8b)或(8c)的二噁嗪染料的染料基团
其中E'为未取代或被C1-C4烷基、卤素、羧基或被磺基取代的亚苯基或为C2-C6亚烷基,v为数字1,v'为数字0或1,且式(8a)、(8b)和(8c)中的外部苯环可被C1-C4烷基、C1-C4烷氧基、乙酰基氨基、硝基、卤素、羧基、磺基或被式-SO2-Y的纤维反应性基团进一步取代,Y如上定义并且具有以上给出的优选含义。
表述"偶氮染料常规的取代基"旨在包括纤维反应性和非纤维反应性取代基二者。
可作为例子提及以下非纤维反应性取代基:C1-C4烷基,其应理解为甲基、乙基、正丙基或异丙基以及正丁基、异丁基、仲丁基或叔丁基;C1-C4烷氧基、其应理解为甲氧基、乙氧基、正丙氧基或异丙氧基以及正丁氧基、异丁氧基、仲丁氧基或叔丁氧基;羟基-C1-C4烷氧基;苯氧基;未取代或在烷基部分中被羟基或被C1-C4烷氧基取代的C2-C6烷酰基氨基,例如乙酰基氨基、羟基乙酰基氨基、甲氧基乙酰基氨基或丙酰基氨基;未取代或苯基部分中被羟基、磺基、卤素、C1-C4烷基或被C1-C4烷氧基取代的苯甲酰基氨基;未取代或在烷基部分中被羟基、C1-C4烷基或被C1-C4烷氧基取代的C1-C6烷氧基羰基氨基;未取代或在苯基部分中被羟基、C1-C4烷基或被C1-C4烷氧基取代的苯氧基羰基氨基;氨基;未取代或在烷基部分中被羟基、C1-C4烷氧基、羧基、氰基、卤素、磺基、硫酸根合、苯基或被磺基苯基取代的N-C1-C4烷基-氨基或N,N-二-C1-C4烷基-氨基,例如甲基氨基、乙基氨基、N,N-二甲基氨基、N,N-二乙基氨基、β-氰基乙基氨基、β-羟乙基氨基、N,N-二-β-羟乙基氨基、β-磺基乙基氨基、γ-磺基-正丙基氨基、β-硫酸根合乙基氨基、N-乙基-N-(3-磺基苄基)-氨基、N-(β-磺基乙基)-N-苄基氨基;环己基氨基;未取代或在苯基部分中被硝基、C1-C4烷基、C1-C4烷氧基、羧基、卤素或被磺基取代的N-苯基氨基或N-C1-C4烷基-N-苯基氨基;C1-C4烷氧基羰基,例如甲氧基-羰基或乙氧基-羰基;三氟甲基;硝基;氰基;卤素,其通常应理解为例如氟、溴或尤其是氯;脲基;羟基;羧基;磺基;磺基甲基;氨基甲酰基;脲基;氨磺酰基;未取代或在苯基部分中被磺基或被羧基取代的N-苯基氨磺酰基或N-C1-C4烷基-N-苯基氨磺酰基;甲基-磺酰基或乙基-磺酰基。
纤维反应性基团应理解为能与纤维素的羟基、与羊毛和丝中的氨基、羧基、羟基和硫醇基团或与合成聚酰胺的氨基和可能的羧基反应以形成共价化学键的那些基团。纤维反应性基团通常与染料基团直接结合或经由桥连成员结合。合适的纤维反应性基团为例如在脂族、芳族或杂环基团处具有至少一个可除去的取代基的那些基团,或其中提及的基团含有适用于与纤维材料反应的基团(例如乙烯基)的那些基团。
在A中存在的纤维反应性取代基例如相应于式(9a)、(9b)、(9c)、(9d)、(9e)、(9f)或(9g)
-SO2-Y (9a),
-NH-CO-(CH2)l-SO2-Y (9b),
-CONR2-(CH2)m-SO2-Y (9c),
-NH-CO-CH(Hal)-CH2-Ha (9d),
-NH-CO-C(Hal)=CH2 (9e),
其中
Hal为氯或溴,
X1为卤素、3-或4-羧基吡啶-1-基、或3-或4-氨基甲酰基吡啶-1-基,
T1独立地具有与X1相同的定义或为式(10a)、(10b)、(10c)、(10d)、(10e)或(10f)的非纤维反应性取代基或纤维反应性基团
其中
R1、R1a和R1b彼此独立地为氢或C1-C4烷基,
R2为氢、未取代或被羟基、磺基、硫酸根合、羧基或被氰基取代的C1-C4烷基,或基团,
R3为氢、羟基、磺基、硫酸根合、羧基、氰基、卤素、C1-C4烷氧基羰基、C1-C4烷酰氧基、氨基甲酰基或基团-SO2-Y,
alk和alk1彼此独立地为直链或支化C1-C6亚烷基,
亚芳基为未取代或被磺基、羧基、C1-C4烷基、C1-C4烷氧基或被卤素取代的亚苯基或亚萘基,
Q为基团-O-或-NR1-,其中R1如上定义,
W为基团-SO2-NR2-、-CONR2-或-NR2CO-,其中R2如上定义,
Y如上定义并且具有以上给出的优选含义,
Y1为基团-CH(Hal)-CH2-Hal或-C(Hal)=CH2,Hal为氯或溴,且
l和m彼此独立地为1-6的整数,n为数字0或1,和
X2为卤素或C1-C4烷基磺酰基,
X3为卤素或C1-C4烷基,和
T2为氢、氰基或卤素。
R1、R1a和R1b优选彼此独立地为氢、甲基或乙基,尤其是氢。
R2优选为氢或C1-C4烷基,例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基或叔丁基,尤其是氢、甲基或乙基。R2更尤其是氢。
R3优选为氢。
在式(9a)和(9c)的取代基的情况下,Y优选为乙烯基或β-硫酸根合乙基。在式(9b) )的取代基的情况下,Y优选为β-氯乙基。
l和m优选彼此独立地为数字2、3或4,尤其是数字2或3。
更尤其是,l为数字3,m为数字2。
对于非纤维反应性取代基T1,考虑例如羟基或未取代或在烷基部分中被取代的C1-C4烷氧基、未取代或在苯基部分中被取代的苯氧基、未取代或在烷基部分中被取代的C1-C4烷硫基、未取代或被取代的氨基或可含有或可不含其它杂原子的N-杂环。
T1作为非纤维反应性基团优选为C1-C4烷氧基、C1-C4烷硫基、羟基、氨基;未取代或在烷基部分中被羟基、硫酸根合或被磺基取代的N-单-C1-C4烷基氨基或N,N-二-C1-C4烷基氨基;吗啉代;或各自未取代或在苯环中被磺基、羧基、乙酰基氨基、氯、甲基或被甲氧基取代的苯基氨基或N-C1-C4烷基-N-苯基氨基(其中烷基未取代或被羟基、磺基或被硫酸根合取代);或未取代或被1-3个磺基取代的萘基氨基。
尤其优选的非纤维反应性基团T1为氨基、N-甲基氨基、N-乙基氨基、Ν-β-羟乙基氨基、N-甲基-N-β-羟乙基氨基、N-乙基-N-β-羟乙基氨基、N,N-二-β-羟乙基氨基、吗啉代、2-、3-或4-羧基苯基氨基、2-、3-或4-磺基-苯基氨基或N-C1-C4烷基-N-苯基氨基。
X1优选为卤素,例如氟、氯或溴,尤其是氯或氟。
T2、X2和X3作为卤素为例如氟、氯或溴、尤其是氯或氟。
X2作为C1-C4烷基磺酰基为例如乙基磺酰基或甲基磺酰基,尤其是甲基磺酰基。
X3作为C1-C4烷基为例如甲基、乙基、正丙基或异丙基、正丁基、异丁基或叔丁基,尤其是甲基。
X2和X3优选彼此独立地为氯或氟。
T2优选为氰基或氯。
Hal优选为溴。
alk和alk1彼此独立地为例如亚甲基、亚乙基、1,3-亚丙基、1,4-亚丁基、1,5-亚戊基或1,6-亚己基或它们的支化异构体。
alk和alk1彼此独立地优选为C1-C4亚烷基,尤其是亚乙基或亚丙基。
亚芳基优选为未取代或例如被磺基、甲基、甲氧基或被羧基取代的1,3-或1,4-亚苯基,尤其是未取代的1,3-或1,4-亚苯基。
Q优选为-NH-或-O-,尤其是-O-。
W优选为式-CONH-或-NHCO-的基团,尤其是式-CONH-的基团。
n优选为数字0。
式(10a)至(10f)的反应性基团优选为这些基团:其中W为式-CONH-的基团,R1、R2和R3各自为氢,Q为基团-O-或-NH-,alk和alk1彼此独立地为亚乙基或亚丙基,亚芳基为未取代的或被甲基、甲氧基、羧基或被磺基取代的亚苯基,Y为乙烯基或β-硫酸根合乙基,Y1为-CHBr-CH2Br或-CBr=CH2,n为数字0。
在A中存在的纤维反应性基团优选相应于式(9a)、(9b)、(9c)、(9d)、(9e)或(9f)的基团,尤其是(9a)、(9b)或(9f),尤其优选(9a)或(9b),其中
Y为乙烯基、β-氯乙基或β-硫酸根合乙基,
Hal为溴,
R2和R1a为氢,
m和l为数字2或3,
X1为氯或氟,
T1为C1-C4烷氧基、C1-C4烷硫基、羟基、氨基;未取代或在烷基部分中被羟基、硫酸根合或被磺基取代的N-单-C1-C4烷基氨基或N,N-二-C1-C4烷基氨基;吗啉代;或各自未取代或在苯环中被磺基、羧基、乙酰基氨基、氯、甲基或被甲氧基取代的苯基氨基或N-C1-C4烷基-N-苯基氨基(其中烷基未取代或被羟基、磺基或被硫酸根合取代);或未取代或被1-3个磺基取代的萘基氨基,或为式(10a')、(10b')、(10c')、(10d')或(10f)的纤维反应性基团
-NH-(CH2)2-3-SO2Y (10a'),
-NH-(CH2)2-3-O-(CH2)2-3-SO2Y (10b'),
优选式(10b')或(10c')的纤维反应性基团,其中
Y如上定义,
Y1为基团-CH(Br)-CH2-Br或-C(Br)=CH2,
Me为甲基,Et为乙基,且式(10c')中的氮原子被氢、甲基或乙基(优选氢或乙基)取代。
在式(10a')和(10b')的基团的情况下,Y优选为β-氯乙基。在式(10c')和(10d')的基团的情况下,Y优选为乙烯基或β-硫酸根合乙基。
在本发明的一个实施方案中,A为式(2a)、(2b)、(2c)、(2d)、(2e)、(2f)、(2g)、(2h)、(2i)或(2j)的单偶氮染料的基团
其中(R4)0-3表示选自以下基团的0-3个相同或不同的取代基:C1-C4烷基、C1-C4烷氧基、卤素、羧基和磺基,和
Z1为式(9a)、(9b)、(9c)、(9d)、(9e)或(9f)的纤维反应性基团,优选(9a)、(9b)或(9f),尤其是(9a)或(9b),提及的纤维反应性基团具有以上给出的定义和优选的含义,
其中(R4)0-3如上定义,
(R5)0-3表示选自以下基团的0-3个相同或不同的取代基:卤素、硝基、氰基、三氟甲基、氨磺酰基、氨基甲酰基、C1-C4烷基;未取代或被羟基、硫酸根合或被C1-C4烷氧基取代的C1-C4烷氧基;氨基、C2-C4烷酰基氨基、脲基、羟基、羧基、磺基甲基、C1-C4烷基磺酰基氨基、磺基和式(9b)和(9f)的纤维反应性基团,其中基团R1a、Y、T1、X1和l如上定义并且具有以上给出的优选含义,和
Z1如上定义并且具有以上给出的优选含义。
在式(2a)、(2b)、(2e)和(2f)的基团的萘基环上的数字指示可能的键合位置。
在本发明的另一个实施方案中,A为式(2k)、(2l)、(2m)、(2n)、(2o)、(2p)、(2q)、(2r)、(2s)、(2t)、(2u)、(3a)、(3b)、(3c)、(3d)、(3e)、(3f)、(4a)、(4b)、(4c)或(4d)的单偶氮或双偶氮染料的基团,
其中(R4)0-3和(R5)0-3如上定义,
(R6)0-3和(R8)0-3彼此独立地表示选自以下基团的0-3个相同或不同的取代基:C1-C4烷基、C1-C4烷氧基、卤素、羧基和磺基,
(R7)0-3表示选自以下基团的0-3个相同或不同的取代基:C1-C4烷基、C1-C4烷氧基、卤素、羧基和磺基,和
Z1如上定义并且具有以上给出的优选含义,
其中R9为磺基苯基、C2-C4烷酰基、苯甲酰基或以上指示的式(9b)或(9f)的基团,其中基团如上定义并且具有以上给出的优选含义,优选C2-C4烷酰基或苯甲酰基,
其中(R7)0-3如上定义,
其中R10和R12彼此独立地为氢、C1-C4烷基或苯基,和R11为氢、氰基、氨基甲酰基或磺基甲基,
其中(R4)0-3和Z1在每一种情况下如上定义并且具有以上给出的优选含义。
在式(2k)、(2l)、(2m)、(2n)、(2t)、(3a)、(3b)、(3c)、(4a)、(4b)、(4c)和(4d)的基团的萘基环上的数字指示可能的键合位置。
式(2r)和(2s)的双偶氮染料基团的中心组分为用虚线指示的苯或萘基团。
在本发明的反应性染料中,合适的染料基团A的实例在US-A-5
484 899 (第13-40栏)和EP-A-0 623 655 (第11-27页)中给出。
在本发明的染料的尤其优选的实施方案中,A为式(2a)、(2b)、(2c)、(2d)、(2e)、(2f)、(2g)、(2h)、(2i)、(2j)或(6)的染料基团,尤其是(2b)、(2f)、(2i)、(2j)或(6),其中
(R4)0-3、(R5)0-3、G和Z1在每一种情况下如上定义,和
(R4)0-3优选表示选自以下基团的0-3个相同或不同的取代基:甲基、甲氧基和磺基,
(R5)0-3优选表示0-3个,尤其是0-2个选自以下基团的相同或不同的取代基:甲基、甲氧基、β-羟基乙氧基、β-硫酸根合乙氧基、磺基、乙酰基氨基、脲基和式(9b)的纤维反应性基团,
G优选为未取代或被C1-C4烷基、C1-C4烷氧基或被磺基取代的亚苯基,
如果期望,Z1优选可为式(9a)或(9b)的纤维反应性基团,其中Y和l如上定义并且具有以上给出的优选含义。
在本发明的反应性染料的另一尤其优选的实施方案中,A为以上指示的式(2k)、(2l)、(2m)、(4a)、(4b)、(4c)或(4d)的染料基团,其中
(R4)0-3、(R5)0-3和Z1在每一种情况下如上定义并且具有以上给出的优选含义。
本发明的一个优选的实施方案涉及式(1)的反应性染料,其中
Q1和Q2为氢,
q为数字1,
X为氯或氟,
Y为乙烯基、β-氯乙基或β-硫酸根合乙基,和
A为式(2b)、(2f)、(2i)、(2j)或(6)的染料基团,其中
(R4)0-3表示选自以下基团的0-3个相同或不同的取代基:C1-C4烷基、C1-C4烷氧基、卤素、羧基和磺基,优选甲基、甲氧基和磺基,
(R5)0-3表示选自以下基团的0-3个相同或不同的取代基:卤素、硝基、氰基、三氟甲基、氨磺酰基、氨基甲酰基、C1-C4烷基;未取代或被羟基、硫酸根合或被C1-C4烷氧基取代的C1-C4烷氧基;氨基、C2-C4烷酰基氨基、脲基、羟基、羧基、磺基甲基、C1-C4烷基磺酰基氨基、磺基和式(9b)和(9f)的纤维反应性基团,优选表示选自以下基团的0-2个相同或不同的取代基:甲基、甲氧基、β-羟基乙氧基、β-硫酸根合乙氧基、磺基、乙酰基氨基、脲基和式(9b)的纤维反应性基团,
G为未取代或被C1-C4烷基、C1-C4烷氧基或被磺基取代的亚苯基,Z1为式(9a)、(9b)或(9f)的纤维反应性基团,尤其是(9a)或(9b),其中
Y如上定义,
R1a为氢,
l为数字3,
X1为氯或氟,
T1为C1-C4烷氧基、C1-C4烷硫基、羟基、氨基;未取代或在烷基部分中被羟基、硫酸根合或被磺基取代的N-单-C1-C4烷基氨基或N,N-二-C1-C4烷基氨基;吗啉代;或各自未取代或在苯环中被磺基、羧基、乙酰基氨基、氯、甲基或被甲氧基取代的苯基氨基或N-C1-C4烷基-N-苯基氨基(其中烷基未取代或被羟基、磺基或被硫酸根合取代);或未取代或被1-3个磺基取代的萘基氨基,或为式(10a')、(10b')、(10c')、(10d')或(10f')的纤维反应性基团,优选式(10b')或(10c')的纤维反应性基团,其中
Y如上定义,
Y1为基团-CH(Br)-CH2-Br或-C(Br)=CH2,
Me为甲基,Et为乙基,且式(10c')中的氮原子被氢、甲基或乙基(优选氢或乙基)取代。
本发明还涉及一种用于制备其中q为数字1的式(1)的反应性染料的方法,所述方法包括按任何顺序使以下彼此反应:约1摩尔当量的式(11a)的氨基染料化合物或式(11a)的化合物的合适的前体,
约1摩尔当量的式(12)的化合物
和约1摩尔当量的卤代三嗪,优选2,4,6-三氯-或2,4,6-三氟-均三嗪;和
用于制备其中q为数字2的式(1)的反应性染料的方法,所述方法包括按任何顺序使以下彼此反应:约2摩尔当量的式(11b)的氨基染料化合物或式(11b)的化合物的合适前体,
约2摩尔当量的以上给出的式(12)的化合物,和约2摩尔当量的以上给出的卤代三嗪,或者,如果使用式(11a)或(11b)的化合物的前体,将得到的中间体转化为期望的染料,并按需继续进行进一步的转化反应,例如用于将三嗪上的卤素原子转化为任何期望的基团X;Q1、Q2、A、X和Y在每一种情况下如上定义并且具有以上给出的优选含义。
将由使用式(11a)或(11b)的氨基染料的前体得到的中间体转化为最终的染料尤其是包括得到偶氮染料的偶联反应。根据本领域通常已知的方法进行与常规重氮化化合物的偶联,例如在中性至稍微酸性pH下和在例如0-20℃的温度下。采用常规的方式实现重氮化,例如使用亚硝酸盐,例如碱金属亚硝酸盐,例如亚硝酸钠,在酸介质中,例如含有盐酸的介质,在例如-5至40℃,优选-5至10℃,尤其是0至5℃的温度下。
可通过其中X为卤素(优选氟或氯)的得到的式(1)化合物与化合物X*-H缩合,可替代三嗪上的卤素原子X,其中X*具有以上对于X给出的含义,卤素除外。
这样的缩合反应为已知的,并且描述于例如EP-A-0 260 227和US-A-4 841 049。
终产物可任选经历另外的转化反应。这样的转化反应例如为通过用稀氢氧化钠溶液处理,将具有含义-CH2CH2-U(其中U如上定义)的基团Y和在A中存在并且能转化为乙烯基的反应性基团转化为乙烯基形式,例如将β-硫酸根合乙基磺酰基或β-氯乙基磺酰基转化为乙烯基磺酰基。这样的反应本身为已知的。
由于以上提及的各单独方法步骤可采用不同的顺序进行,以及在某些情况下适当地同时进行,不同的方法变体是可能的。反应通常逐步连续进行,各单独反应组分之间的本身已知的简单反应的顺序由具体的条件决定。
制备本发明的染料的优选的变体包括使1摩尔当量的2,4,6-三氯-或2,4,6-三氟-均三嗪首先与1摩尔当量的式(12)的化合物反应(如果q为数字1)或使2摩尔当量的2,4,6-三氯-或2,4,6-三氟-均三嗪首先与2摩尔当量的式(12)的化合物反应(如果q为数字2),在约中性pH,例如pH 5-7下,和在低温下,例如0至5℃,随后使得到的式(13)的反应产物
与1摩尔当量的式(11a) (如果q为数字1)或(11b) (如果q为数字2)的氨基染料反应,在稍微酸性至中性pH,例如pH 4.5-6下,和在例如0至30℃的温度下,以形成式(1)的染料,其中Q1,Q2、A、X和Y在每一种情况下如上定义并且具有以上给出的优选含义,并且X为氯或氟。
式(11a)、(11b)和(12)的化合物为本身已知的,它们可采用与已知的化合物类似的方式制备或者市售可得。
本发明的反应性染料以它们的游离酸形式或优选以它们的盐形式存在。合适的盐为例如有机胺的碱金属、碱土金属或铵盐。可提及的实例为钠、锂、钾或铵盐或单乙醇胺盐、二乙醇胺盐或三乙醇胺盐。
本发明的反应性染料适用于染色和印刷(特别是印刷)多种材料,尤其是含羟基或含氮纤维材料。实例包括纸、丝、皮革、羊毛、聚酰胺纤维和聚氨酯,尤其是所有种类的纤维素纤维材料。这样的纤维材料为例如天然纤维素纤维(例如棉、亚麻和大麻)以及纤维素和再生纤维素。本发明的染料还适用于染色或印刷存在于混纺织物(例如棉和聚酯纤维或聚酰胺纤维的混纺物)中的含羟基纤维。
因此,本发明还涉及本发明的反应性染料在染色或印刷含羟基或含氮(尤其是含棉)纤维材料中的用途。
本发明的反应性染料可采用多种方式施用于纤维材料和固定于纤维,尤其是含水染料溶液或染料印刷糊膏形式。它们适用于尽染方法和根据轧染方法染色二者;它们可在低染色温度下使用并且在浸轧汽蒸方法中仅需要短的汽蒸时间。固定度高,并且未固定的染料可容易洗掉,尽染度和固定度之间的差异显著小,也就是说皂洗损失非常小。本发明的反应性染料也适用于尤其是在棉上印刷,并且还适用于印刷含氮纤维,例如羊毛或丝或含有羊毛的混纺织物。
使用本发明的反应性染料产生的染色物和印刷物在酸性和碱性两种范围内均具有高着色强度和高纤维-染料结合稳定性,并且对光还具有良好的牢度和非常良好的湿牢度性质,例如对洗涤、水、海水、交叉染色和汗液的牢度。得到的染色物呈现纤维均染性和表面均染性。
本发明的式(1)的染料还适合作为着色剂用于记录系统。这样的记录系统为例如用于纸或纺织品印刷的市售可得的喷墨印刷机,或书写设备例如钢笔或圆珠笔,尤其是喷墨印刷机。出于该目的,本发明的染料首先成为适用于记录系统的形式。合适的形式为例如包含本发明的染料作为着色剂的水性油墨。通过在期望量的水中将各单独组分混合在一起,可采用常规的方式制备油墨。
作为基材,考虑以上提及的含羟基或含氮纤维材料,尤其是棉纤维材料。纤维材料优选为纺织品纤维材料。
还考虑的基材为纸和塑料膜。
可提及的纸的实例为市售可得的喷墨纸、相纸、光泽纸、塑料涂覆的纸,例如Epson喷墨纸、Epson相纸、Epson光泽纸、Epson光泽膜、HP专用喷墨纸、Encad相纸光泽纸和Ilford相纸。塑料膜例如为透明的或浑浊/不透明的。合适的塑料膜为例如3M透明膜。
取决于应用的性质,例如纺织品印刷或纸印刷,可能需要据此调节例如粘度或油墨的其它物理性质,尤其是对讨论的基材的亲和力有影响的性质。
用于水性油墨的染料应优选具有低盐含量,也就是说它们的总盐含量应小于0.5 %重量,基于染料的重量。例如通过膜分离程序,例如超滤、反渗透或渗析,使由于其制备和/或由于随后加入稀释剂而具有相对高盐含量的染料脱盐。
油墨优选具有染料总含量为1-35 %重量,尤其是1-30 %重量,优选1-20 %重量,基于油墨的总重量。在这种情况下,优选的下限为1.5 %重量的限度,优选2 %重量,尤其是3 %重量。
油墨可包含水混溶的有机溶剂,例如C1-C4醇,例如甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇或异丁醇;酰胺,例如二甲基甲酰胺或二甲基乙酰胺;酮或酮醇,例如丙酮或二丙酮醇;醚,例如四氢呋喃或二氧杂环己烷;含氮杂环化合物,例如N-甲基-2-吡咯烷酮或1,3-二甲基-2-咪唑烷酮;聚亚烷基二醇,例如聚乙二醇或聚丙二醇;C2-C6亚烷基二醇和硫甘醇,例如乙二醇、丙二醇、丁二醇、三甘醇、硫二甘醇、己二醇和二甘醇;其它多元醇,例如甘油或1,2,6-己三醇;和多元醇的C1-C4烷基醚,例如2-甲氧基-乙醇、2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、2-[2-(2-甲氧基-乙氧基)乙氧基]乙醇或2-[2-(2-乙氧基乙氧基)乙氧基]乙醇;优选N-甲基-2-吡咯烷酮、二甘醇、甘油或尤其是1,2-丙二醇,通常其量为2-30 %重量,尤其是5-30 %重量,优选10-25 %重量,基于油墨的总重量。
此外,油墨还可包含增溶剂,例如ε-己内酰胺。
油墨可包含天然或合成起源的增稠剂,特别是用于调节粘度的目的。
可提及的增稠剂的实例包括市售可得的藻酸盐增稠剂、淀粉醚或角豆面粉醚,尤其是藻酸钠自身或与改性纤维素的混合物,例如甲基纤维素、乙基纤维素、羧甲基纤维素、羟乙基纤维素、甲基羟乙基纤维素、羟丙基纤维素或羟丙基甲基纤维素,尤其是优选20-25 %重量羧甲基纤维素。还可提及的合成增稠剂为例如基于聚(甲基)丙烯酸或聚(甲基)丙烯酰胺的那些以及分子量为例如2000-20000的聚亚烷基二醇,例如像聚乙二醇或聚丙二醇或环氧乙烷和环氧丙烷的混合聚亚烷基二醇。
油墨含有这样的增稠剂,例如,其量为0.01-2 %重量,尤其是0.01-1%重量,优选0.01-0.5 %重量,基于油墨的总重量。
油墨还可包含缓冲物质,例如硼砂、硼酸盐、磷酸盐、聚磷酸盐或柠檬酸盐。可提及的实例包括硼砂、硼酸钠、四硼酸钠、磷酸二氢钠、磷酸氢二钠、三聚磷酸钠、五聚磷酸钠和柠檬酸钠。它们尤其是以0.1-3 %重量,优选0.1-1%重量的量使用,基于油墨的总重量,以确立例如4-9,尤其是5-8.5的pH值。
作为其它添加剂,油墨可包含表面活性剂或润湿剂。
合适的表面活性剂包括市售可得的阴离子或非离子表面活性剂。作为本发明的油墨中的润湿剂,考虑例如尿素或乳酸钠(有利地50
%-60 %水溶液形式)和甘油和/或丙二醇的混合物,其量优选为0.1-30 %重量,尤其是2-30 %重量。
优选油墨的粘度为1-40 mPa·s,尤其是1-20 mPa·s,更尤其是1-10 mPa·s。
此外,油墨可另外包含常规的添加剂,例如消泡剂或尤其是抑制真菌和/或细菌生长的防腐剂。这样的添加剂通常以0.01-1%重量的量使用,基于油墨的总重量。
作为防腐剂,考虑产生甲醛的剂例如仲甲醛和三噁烷(尤其是约30-40 %重量甲醛水溶液)、咪唑化合物例如2-(4-噻唑基)-苯并咪唑、噻唑化合物例如1,2-苯并异噻唑啉-3-酮或2-正辛基-异噻唑啉-3-酮、碘化合物、腈、苯酚、卤代烷硫基化合物或吡啶衍生物,尤其是1,2-苯并异噻唑啉-3-酮或2-正辛基-异噻唑啉-3-酮。合适的防腐剂为例如1,2-苯并异噻唑啉-3-酮在一缩二丙二醇中的20 %重量溶液(Proxel® GXL)。
油墨可另外包含其它添加剂,例如氟化的聚合物或调聚物,例如聚乙氧基全氟醇(Forafac®或Zonyl®产品),其量为例如0.01-1%重量,基于油墨的总重量。
在喷墨印刷方法的情况下,以受控的方式从喷嘴将单独的油墨液滴喷在基材上。主要是连续喷墨方法和按需滴墨方法用于该目的。在连续喷墨方法的情况下,连续产生液滴,对于印刷操作,液滴不需要排放至接收器并再循环。另一方面,在按需滴墨方法的情况下,如期望地产生液滴并且用于印刷;也就是说,仅当需要印刷操作时才产生液滴。例如,借助压电喷墨头或借助热能(泡压喷墨),可实现产生液滴。优选借助压电喷墨头印刷和根据连续喷墨方法印刷。
由此,本发明还涉及包含本发明的式(1)染料的水性油墨和所述油墨在用于印刷多种基材(尤其是纺织品纤维材料)的喷墨印刷方法中的用途,以上指示的定义和优选项适用于染料、油墨和基材。
本发明的染料显示非常良好的提升率性能、高最终提升率和高固定度,尤其是在纤维素纤维材料上的印刷应用中。
以下实施例用于说明本发明。除非另外指示,否则温度以摄氏度给出,份数为重量份,百分数涉及重量百分数。重量份数按千克与升的比率与体积份数关联。
实施例1:
(a) 将3.76 g (0.0204 mol)氰尿酰氯悬浮于40 ml水和40 g冰中。随后使用外部冰水浴将所得到的悬浮液冷却至0-5℃。随后将5 ml 10 %磷酸氢二钠水溶液和0.5 ml常规的分散剂(Sandozin NE,得自Clariant)加入到悬浮液中。将所得到的悬浮液在0-5℃下搅拌,直至进一步使用。
(b) 将7.55 g (0.02 mol) 2-(2-氨基-6-磺基-苯酚-4-磺酰基)乙基硫酸酯在80 ml水和60 g冰中混合。使用外部冰水浴调节和保持0-5℃的温度。通过加入氢氧化钠水溶液(30%),将pH调节至6.0。随后将所得到的黄褐色溶液在0-5℃下搅拌30分钟。
(c) 在pH 5.0-6.0和0-5℃温度下,经30分钟,将根据步骤(b)得到的溶液加入到根据步骤(a)得到的氰尿酰氯溶液中。通过加入碳酸钠水溶液(20%),pH保持在约5.0-6.0。45分钟后,完成第一缩合步骤。通过加入盐酸(32%),pH降低至4.5,随后溶液经历在步骤(e)中描述的程序。
(d) 在20℃下和在pH 4.5下,将12.0 g (0.02 mol)下式的氨基甲染料溶解于150 ml水中,搅拌,直至进一步使用。
e) 在20℃下,和在pH 4.5下,经30分钟,将根据步骤(c)得到的溶液加入到根据步骤(d)得到的甲溶液。通过加入盐酸(32%),pH保持恒定。加入完成后,将所得到的溶液加热至40℃,在该温度下搅拌3.5小时,同时借助碳酸钠水溶液(20%),使pH保持恒定。反应完成后,将反应混合物冷却至20℃,通过加入碳酸钠水溶液(20%),将pH调节至7.0。溶液经历反渗透12 小时,随后干燥,提供25.6 g蓝色粉末状的染料,其为λmax为610 nm的对应于下式的游离酸形式。
。
实施例2:
(a) 在20℃下,将6.1g (0.019 mol) 1-氨基-8-羟基-3,6-二磺基萘 (H-Acid)悬浮于100 ml水中。通过加入氢氧化钠水溶液(30%),将pH调节至6.0-7.0,随后将混合物搅拌,直至H-Acid完全溶解。
(b) 在pH 2.0和5-10℃温度下,将根据该实施例2的步骤(a)得到的溶液加入到根据实施例1(c)制备的溶液中。通过加入碳酸钠水溶液(20%),pH随后缓慢升高至pH 4.0。一旦达到pH 4,将温度升高至25-30℃,将混合物在该温度下搅拌6 小时,同时通过加入碳酸钠水溶液(20%),pH保持恒定。反应完成后,溶液原样保持,直至进一步使用。通过加入碳酸钠水溶液(20%),pH升高至7.0-7.5,随后溶液经历在步骤(d)中描述的程序。
(c) 将6.1g (0.02 mol) 1,5-二磺基-2-氨基萘悬浮于100 ml水中,在pH 2.0下,通过加入氢氧化钠水溶液(30%)溶解。一旦溶解,通过加入盐酸(32%),将pH降低至低于1.0,加入30 g冰,以将混合物冷却至0-5℃。通过使用外部冰-水浴,温度保持恒定。加入5.25ml 4 N亚硝酸钠,将混合物搅拌30分钟。重氮化反应完成后,用氨基磺酸破坏过量的亚硝酸钠。
(d) 借助外部冰-水浴冷却根据该实施例2的步骤(b)得到的溶液,并且将pH调节至7.0-7.5。移除冰-水浴,在约10℃下,经20分钟,加入根据该实施例2的步骤(c)的重氮盐溶液,同时通过加入碳酸钠水溶液(20%),pH保持在7.5-8.0。温度随后提高至20℃。反应完成后,通过加入盐酸(32%),将pH调节至7.0。溶液经历反渗透12小时,随后干燥,提供25.5g红色粉末状的染料,其为λmax为542/524 nm的对应于下式的游离酸形式。
。
实施例3:
(a) 在20℃下,将11.1 g (0.02 mol)下式的氨基单偶氮染料溶解于100 ml水中。
通过加入氢氧化钠水溶液(30%),将pH调节至4.0-4.5。随后将橙色溶液搅拌,直至进一步使用。
(b) 在pH 4.0-4.5和5-10℃温度下,经15分钟,将根据该实施例3的步骤(a)得到的溶液加入到根据实施例1(c)制备的溶液中。加入完成后,将温度升高至35-40℃,将混合物在该温度下搅拌5小时,同时通过加入碳酸钠水溶液(20%),pH保持恒定。反应完成后,将溶液冷却至20℃,通过加入碳酸钠水溶液(20%),将pH调节至7.0。溶液经历反渗透12小时,随后干燥,提供27.3 g橙色粉末状的染料,其为λmax为486 nm的对应于下式的游离酸形式。
。
实施例4至53:
可与在实施例1、2和3中描述的程序类似地制备在表1中指示的染料。
表1
染色说明 I:将2份根据实施例1得到的染料溶解于400份水中;加入1500份每升包含53 g氯化钠的溶液。在40℃下,将100份棉织物引入到该染料浴中。45分钟后,加入100份每升包含16 g氢氧化钠和20 g煅烧碳酸钠的溶液。染料浴的温度保持在40℃经另外45分钟。随后,将经染色的物品漂洗,在沸腾下用非离子洗涤剂皂洗一刻钟,再次漂洗,干燥。
染色说明 II:将2份根据实施例1得到的反应性染料溶解于400份水中;加入1500份每升包含53 g氯化钠的溶液。在35℃下,将100份棉织物引入到该染料浴中。20分钟后,加入100份每升包含16 g氢氧化钠和20 g煅烧碳酸钠的溶液。染料浴的温度保持在35℃经另外15分钟。随后,在20分钟过程中将温度升高至60℃。温度保持在60℃经另外35分钟。随后,将物品漂洗,在沸腾下用非离子洗涤剂皂洗一刻钟,再次漂洗,干燥。
染色说明 III:将8份根据实施例1得到的反应性染料溶解于400份水中;加入1400份每升包含100 g硫酸钠的溶液。在25℃下,将100份棉织物引入到该染料浴中。10分钟后,加入200份每升包含150 g磷酸三钠的溶液。随后,在10分钟过程中将染料浴的温度升高至60℃。温度保持在60℃经另外90分钟。随后,将物品漂洗,在沸腾下用非离子洗涤剂皂洗一刻钟,再次漂洗,干燥。
染色说明 IV:将4份根据实施例1得到的反应性染料溶解于50份水中。加入50份每升包含5g氢氧化钠和20 g煅烧碳酸钠的溶液。棉织物用所得到的溶液浸轧,使其提高70%重量,随后在辊上缠绕。将棉织物采用这种方式在室温下储存3小时。随后将经染色的物品漂洗,沸腾下用非离子洗涤剂浸泡一刻钟,再次漂洗,干燥。
染色说明 V:将6份根据实施例1得到的反应性染料溶解于50份水中。加入50份每升包含16 g氢氧化钠和0.04升水玻璃(38° bé)的溶液。棉织物用所得到的溶液浸轧,使其提高70%重量,随后在辊上缠绕。将棉织物采用这种方式在室温下储存10小时。随后将经染色的物品漂洗,在沸腾下用非离子洗涤剂皂洗一刻钟,再次漂洗,干燥。
染色说明 VI:将2份根据实施例1得到的反应性染料溶解于100份水中,加入0.5份间硝基苯磺酸钠。将棉织物用所得到的溶液浸渍,使其提高75%重量,随后干燥。织物随后用每升包含4 g氢氧化钠和300氯化钠的温热至20℃的溶液浸渍,挤出,至75%的重量提高,随后将染色物在100-102℃下汽蒸30秒,漂洗,在0.3%非离子洗涤剂的沸腾溶液中皂洗一刻钟,漂洗,干燥。
印刷说明 I:将3份根据实施例1得到的反应性染料在高速搅拌下洒在100份原料增稠剂中,该增稠剂包含50份5%藻酸钠增稠剂、27.8份水、20份尿素、1份间硝基苯磺酸钠和1.2份碳酸氢钠。棉织物用这样得到的印刷糊膏印刷,干燥,将得到的印刷材料在102℃的饱和蒸汽中汽蒸2分钟。随后将印刷的织物漂洗,在沸腾下皂洗,在适当情况下再次漂洗,随后干燥。
印刷说明 II:将5份根据实施例51得到的反应性染料在高速搅拌下洒在100份原料增稠剂中,该增稠剂包含50份5%藻酸钠增稠剂、36.5份水、10份尿素、1份间硝基苯磺酸钠和2.5份碳酸氢钠。丝光棉缎织物用这样得到的印刷糊膏印刷,其稳定性满足技术要求,将所得到的印刷材料在102℃的饱和蒸汽中汽蒸8分钟。随后将印刷织物漂洗,在沸腾下皂洗,在适当情况下再次漂洗,随后干燥。
根据以上印刷说明II,通过制备和施用含有不同染料浓度的印刷糊膏,根据本领域的常用实践,研究本发明的染料和具有类似结构的现有技术染料的提升率。使用制备的糊膏印刷丝光棉缎织物。通过光谱法测量印刷织物的参比色深。制作提升率图,采用常规的方式测定最大提升率。此外,通过切割限定尺寸的印刷织物的样品和在沸腾下用磷酸盐缓冲的水溶液(pH 7)溶解/萃取未固定的染料,采用常规的方式测定固定度。通过印刷而不在饱和蒸汽中汽蒸,制备参比织物。得到以下结果:
*E25指在λmax/c=25mg/l下的消光度
**RD指参比色深
比起现有技术的染料,本发明的染料显示优越的提升率和较高的固定度。
印刷说明 III:
(a) 用含有30 g/l碳酸钠和50 g/l尿素(70%吸液率)的液体轧染丝光棉缎并干燥。
(b) 使用按需滴墨喷墨头(泡压喷墨),根据步骤(a)预处理的棉缎用含有以下物质的水性油墨印刷
-15%重量根据实施例1的反应性染料,
-15%重量1,2-丙二醇,和
-70%重量水。
将印刷物完全干燥,在102℃的饱和蒸汽中固定8分钟,冷漂洗,在沸腾下洗掉,再次漂洗并干燥。
Claims (11)
1.一种式(1)的反应性染料
其中
Q1和Q2彼此独立地为氢,或者未取代或被取代的C1-C4烷基,
A为单偶氮、多偶氮、金属络合物偶氮、蒽醌、酞菁、甲
或二噁嗪发色团的基团,
X为卤素、3-或4-羧基吡啶-1-基、或3-或4-氨基甲酰基吡啶-1-基,
Y为乙烯基或基团-CH2-CH2-U,U为在碱性条件下可除去的基团,且q为数字1或2。
2.权利要求1的反应性染料,其中
Q1和Q2为氢。
3.权利要求1或权利要求2的反应性染料,其中
X为氟或氯。
4.权利要求1-3中任一项的反应性染料,其中
U为-Cl、-Br、-F、-OSO3H、-SSO3H、-OCO-CH3、-OPO3H2、-OCO-C6H5、-OSO2-C1-C4烷基或-OSO2-N(C1-C4烷基)2。
5.权利要求1-4中任一项的反应性染料,其中
q为数字1。
6.权利要求1-5中任一项的反应性染料,其中
A为式(2a)、(2b)、(2c)、(2d)、(2e)、(2f)、(2g)、(2h)、(2i)或(2j)或(6)的单偶氮染料的基团
其中
(R4)0-3表示选自以下基团的0-3个相同或不同的取代基:C1-C4烷基、C1-C4烷氧基、卤素、羧基和磺基,和
Z1为式(9a)、(9b)或(9f)的纤维反应性基团
-SO2-Y (9a),
-NH-CO-(CH2)l-SO2-Y (9b)或
(9f)
其中
Y为乙烯基或基团-CH2-CH2-U,且U为-Cl或-OSO3H,
R1a为氢,
l为数字3,
X1为氯或氟,
T1为式(10b')或(10c')的纤维反应性基团
-NH-(CH2)2-3-O-(CH2)2-3-SO2Y (10b')或
其中
Me为甲基,Et为乙基,和式(10c')中的氮原子被氢、甲基或乙基取代,
(R5)0-3表示选自以下基团的0-3个相同或不同的取代基:卤素、硝基、氰基、三氟甲基、氨磺酰基、氨基甲酰基、C1-C4烷基;未取代的或被羟基、硫酸根合取代或被C1-C4烷氧基取代的C1-C4烷氧基;氨基、C2-C4烷酰基氨基、脲基、羟基、羧基、磺基甲基、C1-C4烷基磺酰基氨基、磺基和式(9b)和(9f)的纤维反应性基团,其中所述基团R1a、Y、T1、X1和l如上定义,且G为未取代的或被C1-C4烷基、C1-C4烷氧基取代或被磺基取代的亚苯基。
7.权利要求1-5中任一项的反应性染料,其中
A为式(2k)、(2l)、(2m)、(4a)、(4b)、(4c)或(4d)的染料基团
其中
(R4)0-3表示选自以下基团的0-3个相同或不同的取代基:C1-C4烷基、C1-C4烷氧基、卤素、羧基和磺基,和
Z1为式(9a)、(9b)或(9f)的纤维反应性基团
-SO2-Y (9a),
-NH-CO-(CH2)l-SO2-Y (9b)或
其中
Y为乙烯基或基团-CH2-CH2-U,且U为-Cl或-OSO3H,
R1a为氢、
l为数字3,
X1为氯或氟,
T1为式(10b')或(10c')的纤维反应性基团
-NH-(CH2)2-3-O-(CH2)2-3-SO2Y (10b')或
其中
Me为甲基,Et为乙基,和式(10c')中的氮原子被氢、甲基或乙基取代,
(R5)0-3表示选自以下基团的0-3个相同或不同的取代基:卤素、硝基、氰基、三氟甲基、氨磺酰基、氨基甲酰基、C1-C4烷基;未取代的或被羟基、硫酸根合取代或被C1-C4烷氧基取代的C1-C4烷氧基;氨基、C2-C4烷酰基氨基、脲基、羟基、羧基、磺基甲基、C1-C4烷基磺酰基氨基、磺基和式(9b)和(9f)的纤维反应性基团,其中所述基团R1a、Y、T1、X1和l如上定义。
8.权利要求1-6中任一项的反应性染料,其中
Q1和Q2为氢,
q为数字1,
X为氯或氟,
Y为乙烯基、β-氯乙基或β-硫酸根合乙基,和
A为式(2b)、(2f)、(2i)、(2j)或(6)的染料基团,
其中
(R4)0-3表示选自以下基团的0-3个相同或不同的取代基:C1-C4烷基、C1-C4烷氧基、卤素、羧基和磺基,和
Z1为式(9a)、(9b)或(9f)的纤维反应性基团
-SO2-Y (9a),
-NH-CO-(CH2)l-SO2-Y (9b)或
其中
Y为乙烯基或基团-CH2-CH2-U,且U为-Cl或-OSO3H,
R1a为氢,
l为数字3,
X1为氯或氟,
T1为式(10b')或(10c')的纤维反应性基团
-NH-(CH2)2-3-O-(CH2)2-3-SO2Y (10b')或
其中
Me为甲基,Et为乙基,和式(10c')中的氮原子被氢、甲基或乙基取代,
(R5)0-3表示得选以下基团的0-3个相同或不同的取代基:卤素、硝基、氰基、三氟甲基、氨磺酰基、氨基甲酰基、C1-C4烷基;未取代的或被羟基、硫酸根合取代或被C1-C4烷氧基取代的C1-C4烷氧基;氨基、C2-C4烷酰基氨基、脲基、羟基、羧基、磺基甲基、C1-C4烷基磺酰基氨基、磺基和式(9b)和(9f)的纤维反应性基团,其中所述基团R1a、Y、T1、X1和l如上定义,且G为未取代或被C1-C4烷基、C1-C4烷氧基取代或被磺基取代的亚苯基。
9.一种用于制备其中q为数字1的式(1)的反应性染料的方法,所述方法包括按任何顺序使以下彼此反应:约1摩尔当量的式(11a)的氨基染料化合物或式(11a)的化合物的合适前体,
约1摩尔当量的式(12)的化合物
和约1摩尔当量的卤代三嗪,优选2,4,6-三氯-或2,4,6-三氟-均三嗪;和
用于制备其中q为数字2的式(1)的反应性染料的方法,所述方法包括按任何顺序使以下彼此反应:约2摩尔当量的式(11b)的氨基染料化合物或式(11b)的化合物的合适前体,
约2摩尔当量的以上给出的式(12)的化合物,和约2摩尔当量的以上给出的卤代三嗪,或者,如果使用式(11a)或(11b)的化合物的前体,将得到的中间体转化为期望的染料,并按需继续进行进一步的转化反应;Q1、Q2、A、X和Y在每一种情况下如在权利要求1中所定义。
10.权利要求1-8中任一项的反应性染料或根据权利要求9得到的反应性染料在染色或印刷含羟基或含氮纤维材料中的用途。
11.权利要求10的用途,其中将纤维素纤维材料尤其是含棉的纤维材料染色或印刷。
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CN108250794A (zh) * | 2018-02-01 | 2018-07-06 | 浙江劲光实业股份有限公司 | 一种红色活性染料原浆的制备方法 |
CN109776440A (zh) * | 2019-03-06 | 2019-05-21 | 上海工程技术大学 | 一种蓝色活性染料及其在非水介质中染棉纤维的方法 |
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CN106893352B (zh) * | 2015-12-17 | 2018-10-09 | 上海安诺其集团股份有限公司 | 一种单偶氮类化合物 |
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