CA1249902A - Process for the continuous trichromatic dyeing of synthetic polyamide materials - Google Patents
Process for the continuous trichromatic dyeing of synthetic polyamide materialsInfo
- Publication number
- CA1249902A CA1249902A CA000494712A CA494712A CA1249902A CA 1249902 A CA1249902 A CA 1249902A CA 000494712 A CA000494712 A CA 000494712A CA 494712 A CA494712 A CA 494712A CA 1249902 A CA1249902 A CA 1249902A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- hydrogen
- dye
- methyl
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 57
- 230000008569 process Effects 0.000 claims abstract description 52
- 238000004043 dyeing Methods 0.000 claims abstract description 44
- 239000001000 anthraquinone dye Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 229920002647 polyamide Polymers 0.000 claims abstract description 15
- -1 chloroacetylaminomethyl Chemical group 0.000 claims description 290
- 239000000975 dye Substances 0.000 claims description 127
- 229910052739 hydrogen Inorganic materials 0.000 claims description 112
- 239000001257 hydrogen Substances 0.000 claims description 112
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 55
- 150000002431 hydrogen Chemical class 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 41
- 150000003254 radicals Chemical class 0.000 claims description 35
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 30
- 239000000460 chlorine Chemical group 0.000 claims description 29
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical group 0.000 claims description 24
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 239000001043 yellow dye Substances 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 20
- 239000001045 blue dye Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 16
- 239000001044 red dye Substances 0.000 claims description 14
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 13
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 239000001048 orange dye Substances 0.000 claims description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 12
- 150000005840 aryl radicals Chemical class 0.000 claims description 11
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 11
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 9
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 9
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 claims description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 5
- 239000004753 textile Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- 125000006705 (C5-C7) cycloalkyl group Chemical group 0.000 claims description 3
- 125000002668 chloroacetyl group Chemical group ClCC(=O)* 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 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 claims description 3
- 125000004760 (C1-C4) alkylsulfonylamino group Chemical group 0.000 claims description 2
- 125000000242 4-chlorobenzoyl group Chemical group ClC1=CC=C(C(=O)*)C=C1 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000005146 naphthylsulfonyl group Chemical group C1(=CC=CC2=CC=CC=C12)S(=O)(=O)* 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 1
- 229910006074 SO2NH2 Inorganic materials 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000987 azo dye Substances 0.000 abstract description 8
- 238000010014 continuous dyeing Methods 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 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
- 125000003277 amino group Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 125000005236 alkanoylamino group Chemical group 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002790 naphthalenes Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229960005419 nitrogen Drugs 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000001439 semicarbazido group Chemical group [H]N([H])C(=O)N([H])N([H])* 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QOOQLKSEGVNYLA-UHFFFAOYSA-N 1-$l^{1}-oxidanylbutane Chemical compound CCCC[O] QOOQLKSEGVNYLA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241001648782 Chrysanthemum stem necrosis virus Species 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- WZKSXHQDXQKIQJ-UHFFFAOYSA-N F[C](F)F Chemical compound F[C](F)F WZKSXHQDXQKIQJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001024304 Mino Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 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 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000001691 aryl alkyl amino group Chemical group 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JYZIHLWOWKMNNX-UHFFFAOYSA-N benzimidazole Chemical compound C1=C[CH]C2=NC=NC2=C1 JYZIHLWOWKMNNX-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000006310 cycloalkyl amino group Chemical group 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical class C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- RELBGBUMWDAJGE-UHFFFAOYSA-N fluorocyclobutane Chemical compound FC1[CH]CC1 RELBGBUMWDAJGE-UHFFFAOYSA-N 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 229910052744 lithium Inorganic materials 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid 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
- 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
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0041—Blends of pigments; Mixtured crystals; Solid solutions mixtures containing one azo dye
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/248—Polyamides; Polyurethanes using reactive dyes
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Abstract
Process for the continuous trichromatic dyeing of synthetic polyamide materials Abstract:
Process for the continuous trichromatic dyeing of synthetic polyamide materials which comprises using at least one blue-dyeing fibre-reactive sulfo-containing anthra-quinone dye together with at least one red-dyeing sulfo-containing azo dye and at least one yellow- or orange-dyeing sulfo-containing azo dye.
The process according to the invention is suitable for the continuous dyeing of synthetic polyamide materials from aqueous liquors, producing level dyeings having good fastness properties, in particular good ozone fastness.
Process for the continuous trichromatic dyeing of synthetic polyamide materials which comprises using at least one blue-dyeing fibre-reactive sulfo-containing anthra-quinone dye together with at least one red-dyeing sulfo-containing azo dye and at least one yellow- or orange-dyeing sulfo-containing azo dye.
The process according to the invention is suitable for the continuous dyeing of synthetic polyamide materials from aqueous liquors, producing level dyeings having good fastness properties, in particular good ozone fastness.
Description
~2~9~Z
-]- 21489-6833 Process for the continuous trichromatic dyeing of synthetic polyamide materials The present invention relates to a process for the continuous trichromatic dyeing of synthetic polyamide materials with at least one blue-dyeing fibre-reactive sulfo-containing anthraquinone dye, at least one red-dyeing sulfo-containing azo dye and at least one yellow or orange-dyeing sulfo-containing azo dye.
It is repeatedly found that trichromatic dyeings on synthetic polyamide materials do not meet present-day demands on the ozone fastness of dyeings.
It is the object of the present invention to provide a process for dyeing synthetic polyamide materials with dyes which are suitable for trichromatic combinations which produces dyeings of very good ozone fastness.
This object is achieved according to the invention with the process described hereinafter. The dyeings produced thereby meet the stated demands on ozGne fastness.
The present invention accordingly provides a process for the continuous trichromatic dyeing of synthetic polyamide materials which comprises using at least one blue-dyeing fibre-reactive sulfo-containing anthraquinone dye together with at least one red-dying sulfo-containing azo dye and at least one yellow-or orange-dyeing sulfo-containing azo dye.
More particularly, the invention provides a process for the continuous trichromatic dyeing of synthetic polyamide 9(~2 -la- 21489-6833 materials which comprises usi.ng at least one blue-dyeing dye of the formula `" ~ -SO3H
Gl\ /G2 (13) O NH-~ G3 in which Gl, G3 and G5 are each methyl, G4 is ~ -chloroacryloyl-aminomethyl or ~-bromoacryloylaminomethyl, ~, ~-dibromopropionyl-aminomethyl, ~ '-sulfatoethylsulfonyl)-propionylaminomethyl, dibromopropionylamino, -CH(COOH)-NH-CO-CHBrCH2Br or chloro-acetylaminomethyl and G2 is hydrogen, sulfo or chloroacetylamino-methyl or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which Gl is hydrogen or methoxy, G2, G3 and G5 are each hydrogen and G4 is sulfato-ethylsulfonyl chloroacetylamino,~ , ~-dibromopropionylamino, vinyl-sulfonyl, 2-methoxy-4-fluoro-s-triazinylamino or 2-ethylamino-4-fluoro-s-triazinylamino, or in which Gl, G2, G4, and G5 are each hydrogen and G3 is chloroacetylamino,~ , ~-dibromopropionylamino,
-]- 21489-6833 Process for the continuous trichromatic dyeing of synthetic polyamide materials The present invention relates to a process for the continuous trichromatic dyeing of synthetic polyamide materials with at least one blue-dyeing fibre-reactive sulfo-containing anthraquinone dye, at least one red-dyeing sulfo-containing azo dye and at least one yellow or orange-dyeing sulfo-containing azo dye.
It is repeatedly found that trichromatic dyeings on synthetic polyamide materials do not meet present-day demands on the ozone fastness of dyeings.
It is the object of the present invention to provide a process for dyeing synthetic polyamide materials with dyes which are suitable for trichromatic combinations which produces dyeings of very good ozone fastness.
This object is achieved according to the invention with the process described hereinafter. The dyeings produced thereby meet the stated demands on ozGne fastness.
The present invention accordingly provides a process for the continuous trichromatic dyeing of synthetic polyamide materials which comprises using at least one blue-dyeing fibre-reactive sulfo-containing anthraquinone dye together with at least one red-dying sulfo-containing azo dye and at least one yellow-or orange-dyeing sulfo-containing azo dye.
More particularly, the invention provides a process for the continuous trichromatic dyeing of synthetic polyamide 9(~2 -la- 21489-6833 materials which comprises usi.ng at least one blue-dyeing dye of the formula `" ~ -SO3H
Gl\ /G2 (13) O NH-~ G3 in which Gl, G3 and G5 are each methyl, G4 is ~ -chloroacryloyl-aminomethyl or ~-bromoacryloylaminomethyl, ~, ~-dibromopropionyl-aminomethyl, ~ '-sulfatoethylsulfonyl)-propionylaminomethyl, dibromopropionylamino, -CH(COOH)-NH-CO-CHBrCH2Br or chloro-acetylaminomethyl and G2 is hydrogen, sulfo or chloroacetylamino-methyl or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which Gl is hydrogen or methoxy, G2, G3 and G5 are each hydrogen and G4 is sulfato-ethylsulfonyl chloroacetylamino,~ , ~-dibromopropionylamino, vinyl-sulfonyl, 2-methoxy-4-fluoro-s-triazinylamino or 2-ethylamino-4-fluoro-s-triazinylamino, or in which Gl, G2, G4, and G5 are each hydrogen and G3 is chloroacetylamino,~ , ~-dibromopropionylamino,
2,6-difluoro-5-chloropyrimidin-4-ylamino or 2-chloro-4-amino-or 4-N,N-dimethylamino-s-triazinylamino, or in which Gl is methyl, G2 is ~ -sulfatoethylsulfonyl and G3, G4 and G5 are each hydrogen, or in which Gl or G2 is sulfo, G3 is ~ -bromoacryloylamino or N-methyl-N-[3-( ~-chloroethylsulfonyl)-benzoyl]-amino and G2 or G
3 Z~90~
-lb- 21489-6833 and G4 and G5 are each hydrogen, or Gl, G2 and G5 are eaeh hydrogen, G3 is methyl and G4 is chloroacetylamino, or in which Gl is methyl and G2 is 2,6-dichloro-5-chloropyrimidinylamino, G4 is sulfo and G3 and G5 are each hydrogen, or at least one blue dye of the formula O NH-Yl ~ y ~ (S3 )1-2 (1) NHY3 ~r ~ T)1_2 in which Yl is eyelohexyl, Y2 is hydrogen, Y3 is 4-(4'-methylphenoxy)-phenyl and T is ehloroaeetylaminomethyl and the dye eontains a single sulfo group, or in whieh Yl is isopropyl, Y2 is hydrogen and Y3 is a phenyl-sec.-butyl radieal whieh is substituted in the phenyl ring by sulfo or chloroacetylaminomethyl or is a diphenyl ether radical whieh is substituted in the phenoxy radieal by sulfo and aeryloylaminomethyl, or in whieh Yl and Y3 both denote a phenyl-see.-butyl radieal whieh is substituted in the phenyl ring by sulfo and ehloroaeetylaminomethyl, and Y2 is hydrogen, or in whieh Yl and Y3 both denote a 4- ~-bromoaeryloylamino-3-sulfophenyl radieal and Y2 is hydrogen, together with at least one red dye of the formula A NH2 B- ~ -N=N- ~
~ ~ (2) -Ic- 21~89-6833 in which A is hydrogen, substituted or unsubstituted Cl_4-alkyl, Rl Rl 2 \ , -C0-N or -S02R3, where Rl is Cl_4 alkyl, R2 is substituted or unsubstituted C5 7-cycloalkyl or substituted or unsubstituted phenyl, and R3 is substituted or unsubstituted phenyl or substituted or unsubstituted phenoxy, and B is hydrogen, halogen, C2 4-alkanoylamino, C5_8-cycloalkoxycarbonylamino, Cl_4-alkoxycarbonylamino, Cl_4-alkylsulfonylamino or substituted or unsubstituted phenyl-sulfonylamino, and with at least one yellow or orange dye of the formulae ,~)-N=N- ~-N=N- ~
in which Bl, B2 and El are each hydrogen, Cl_4-alkyl or Cl_4-alkoxy and X is straight-chain or branched Cl 4-alkyl or straight-chain or branched C2 4-hydroxyalkyl, or ~-O-S02-~
Zl N = N - C-C -C~3 C ,N
~Z~902 -ld- 21489-6833 in which Zl' Z2 and Z3, independent:Ly of one another are each hydrogen, halogen, Cl_4-alkyl or Cl_4-alkoxy, or mixtures o:E dyes of the formulae(3) and (4), or a yellow dye of the formula W ~ I 503H ~5) in which Wl is hydrogen, Cl_4-alkyl, Cl_4-alkoxy, halogen, C2_4-alkanoylamino or a substituted or unsubstituted aryl-sulfonyl, aryloxy or arylcarbonyl radical, W2 is hydro-gen, halogen, a substituted or unsubstituted alkyl, aryloxy or aryloxysulfonyl radical or a radical of the formula w5 w5 S2N \ or -CON W3 is a substituted or unsubstitu-ted alkyl or aryl radical, W4 is hydrogen or alkyl and W5 and W6 independently of each other, are each hydrogen or substituted or unsubstituted alkyl, cycloalkyl or aryl radical.
Trichromatic dyeing is to be understood as meaning the additive colour mixture of suitably chosen yellow- or orange-, red-and blue-dyeing dyes with which every desired shade of the visible colour spectrum can be matched by a ~4~90;~
suitable choice of the mixing ratios of the dyes.
The process accord;ng to the invent;on produces dyeings of good to very good ozone fastness.
Suitable blue-dyeing fibre-reactive sulfo-containing anthraquinone dyes are for example the anthraquinone dyes given in the Colour Index as reactive blues.
Suitable red-, yellow- and orange-dyeing sulfo-containing azo dyes are for example the azo dyes given in the Colour Index as acid reds, acid yello~s and acid oranges respectively.
In a preferred embodiment of the process according to the nvention, at least one blue dye of the formula O NHYl I~ 1 2_ 3 )1-2 ~1 ) 11 l in which the ring L can be substituted by hydroxyl, halo-gen or sulfo, Y1 is hydrogen, C1_g-alkyl, Cs_7-cycloalkyl, phenyl or phenyl-c1-g-alkyl~ Y2 is hydrogen or halogen, such as chlorine or bromine, or is preferably a sulfo group, Y3 is unsubst;tuted or C1_4-alkyl-, C1_4-alkoxy-, phenoxy-, C1_4-alkylphenoxy or naphthoxy-substituted phenyl cr phenyl-C1_8~alkYl, and T is a fibre-reactive radical which is bonded either directly or via a bridge member, is used together with at least one red dye of the formula NH~, B-~ -N=N--~ ~-~ C--HO--~ ~-\S03H
in which A is hydrogen, substituted or unsubstituted C1_4-alkyl, z ~S02~ , -CO-~ or -S02R3, ~here R1 is C1_4 alkyl, R2 is subst;tuted or unsubstituted C5_7-cycloalkyl or substituted or unsubstituted phenyl, and R3 is substitu-ted or unsubstituted phenyl or substituted or unsubstituted phenoxy, and B is hydrogen, halogen, C2-4-alkanoylamin Cs_g-cycloalkoxycarbonylamino, c1_4-alkoxYcarbonylamin C1_4-alkylsulfonylamjno or substituted or unsubstituted phenylsulfonylamino, and with at least one yellow or orange dye of the formulae ~ 2 ~l (3) ;n which B1, B2 and E1 are each hydrogen, C1_4-alkyl or C1_4-alkoxy and X is straight-chain or branched C1_4-alkyl or straight-chain or branched C2_4-hydroxyalkyl, or ~< ~--O-S02--~ ~o Z ~ (4) C
H2 \1 Z~-/
in which Z1~ Z2 and Z3, independently of one another are each hydrogen, halogen~ C1_4-alkyl or C1_4-alkoxy, or mix-tures of dyes of the formulae (3) and (4), or a yellow dye of the formula C~2 2 ~ 3 ~ S03H
in which W1 is hydrogen, C1_4-alkyl, C1_4 alkoxy, haloge , C2-4-alkanoylamino or a substituted or unsubstituted arylsulfonyl, aryloxy or arylcarbonyl radical, W2 is hydro-gen, halogen, substituted or unsubstituted alkyl, aryloxy or aryloxysulfonyl radical or a radical of the formula -S2 ~ or -C0~ , W3 is a substituted or unsub-stituted alkyl or aryl radical, W4 ;s hydrogen or alkyl, and W5 and W6, independently of each other, are each hydrogen or a substituted or unsubstituted alkyl, cycloalkyl or aryl radical.
An alkyl radical Y1 in the formula (1) can be a straight-chain or branched alkyl radical, for example methyl, ethyl, propyl, isopropyL, butyl, sec.-butyl, iso-butyl, tert.-butyl, pentyl, hexyl, heptyl or octyl.
A C5_7-cycloalkyl radical Y1 in the formula (1) and a Cs_7-cycloalkyl radical R2 in the formula (Z3, independently of each other, can be for example an unsub-stituted cyclohexyl radical or a cyclohexyl radical which is substituted by alkyl, such as methyl.
A phenyl radical Y1 in the formula (1) can be a phenyl radical which can be substituted by C1_4-alkyl, C1_4-alkoxy or halo9en and be further substituted by a sulfo group and a fibre-reactive radical; the phenyl radi-cal is preferably substituted by a sulfo group and a fibre-reactive radical.
Phenyl-cl-8-alkyl radicals Y1 and Y3 in the formula (1), independently of each other, can each be for example a benzyl, phenethyl, phenylbutyl or phenyl-sec.-butyl radical which is preferably subst;tuted by a sulfo group and at least one fibre-reactive radical.
A phenyl radical Y3 in the formula (1) can be a phenyl radical which is substituted by C1_4-alkyl, in par-ticular methyl, C1_4-alkoxy, in particular methoxy, phenoxy, C1_4-alkylphenoxy, for example p-methylphenoxy, or naphthoxy and ~hich is further substituted by a sulfo group and preferably one or two fibre-reactive radicals.
Fibre-reactive radicals T are to be understood as mean;ng radicals which are capable of reacting w;th the hydroxyl groups of cellulose, w;th the amino, carboxyl, hydroxyl and thiol groups of wool and silk, or ~ith the amino and carboxyl groups of synthetic polyamides to form covalent chemical bonds~
Alkyl radicals A, B1, B2, E1, R1, X~ Z1~ Z2 and Z3 in the formulae (2), (3~ an~ (4), independently of one another, can be straight-chain or branched alkyl radi-cals, for example methyl, ethyl, propyl, isopropyl~ butyl, sec~-butyl, isobutyl or tert.-butyl.
An alkyl radical A can be substituted, for exa~ple, by halogen, such as chlorine or bromine or in particular fluorine, but preferably an alkyl radical A is a C1_4-perfluoro-alkyl radical, in particular a trifluoromethyl radical.
Substituted or unsubstituted phenyl radicals R2 and R3 can each be a phenyl radical which is substituted by C1_4-alkyl, C1_4-alkoxy or halogen; R2 or R3 is prefer-ably an unsubstituted phenyl radical.
A substituted or unsubstituted phenoxy radical R3 can be a phenoxy radical which is substituted by C1_4-alkyL, in particular methyl, C1_4-alkoxy or halogen, in particular chlorine; a phenoxy radical R3 is preferably a phenoxy radical which is unsubstituted or substituted by chlorine.
Halogens B, Z1~ Z2 and Z3 in the formulae (2) and
-lb- 21489-6833 and G4 and G5 are each hydrogen, or Gl, G2 and G5 are eaeh hydrogen, G3 is methyl and G4 is chloroacetylamino, or in which Gl is methyl and G2 is 2,6-dichloro-5-chloropyrimidinylamino, G4 is sulfo and G3 and G5 are each hydrogen, or at least one blue dye of the formula O NH-Yl ~ y ~ (S3 )1-2 (1) NHY3 ~r ~ T)1_2 in which Yl is eyelohexyl, Y2 is hydrogen, Y3 is 4-(4'-methylphenoxy)-phenyl and T is ehloroaeetylaminomethyl and the dye eontains a single sulfo group, or in whieh Yl is isopropyl, Y2 is hydrogen and Y3 is a phenyl-sec.-butyl radieal whieh is substituted in the phenyl ring by sulfo or chloroacetylaminomethyl or is a diphenyl ether radical whieh is substituted in the phenoxy radieal by sulfo and aeryloylaminomethyl, or in whieh Yl and Y3 both denote a phenyl-see.-butyl radieal whieh is substituted in the phenyl ring by sulfo and ehloroaeetylaminomethyl, and Y2 is hydrogen, or in whieh Yl and Y3 both denote a 4- ~-bromoaeryloylamino-3-sulfophenyl radieal and Y2 is hydrogen, together with at least one red dye of the formula A NH2 B- ~ -N=N- ~
~ ~ (2) -Ic- 21~89-6833 in which A is hydrogen, substituted or unsubstituted Cl_4-alkyl, Rl Rl 2 \ , -C0-N or -S02R3, where Rl is Cl_4 alkyl, R2 is substituted or unsubstituted C5 7-cycloalkyl or substituted or unsubstituted phenyl, and R3 is substituted or unsubstituted phenyl or substituted or unsubstituted phenoxy, and B is hydrogen, halogen, C2 4-alkanoylamino, C5_8-cycloalkoxycarbonylamino, Cl_4-alkoxycarbonylamino, Cl_4-alkylsulfonylamino or substituted or unsubstituted phenyl-sulfonylamino, and with at least one yellow or orange dye of the formulae ,~)-N=N- ~-N=N- ~
in which Bl, B2 and El are each hydrogen, Cl_4-alkyl or Cl_4-alkoxy and X is straight-chain or branched Cl 4-alkyl or straight-chain or branched C2 4-hydroxyalkyl, or ~-O-S02-~
Zl N = N - C-C -C~3 C ,N
~Z~902 -ld- 21489-6833 in which Zl' Z2 and Z3, independent:Ly of one another are each hydrogen, halogen, Cl_4-alkyl or Cl_4-alkoxy, or mixtures o:E dyes of the formulae(3) and (4), or a yellow dye of the formula W ~ I 503H ~5) in which Wl is hydrogen, Cl_4-alkyl, Cl_4-alkoxy, halogen, C2_4-alkanoylamino or a substituted or unsubstituted aryl-sulfonyl, aryloxy or arylcarbonyl radical, W2 is hydro-gen, halogen, a substituted or unsubstituted alkyl, aryloxy or aryloxysulfonyl radical or a radical of the formula w5 w5 S2N \ or -CON W3 is a substituted or unsubstitu-ted alkyl or aryl radical, W4 is hydrogen or alkyl and W5 and W6 independently of each other, are each hydrogen or substituted or unsubstituted alkyl, cycloalkyl or aryl radical.
Trichromatic dyeing is to be understood as meaning the additive colour mixture of suitably chosen yellow- or orange-, red-and blue-dyeing dyes with which every desired shade of the visible colour spectrum can be matched by a ~4~90;~
suitable choice of the mixing ratios of the dyes.
The process accord;ng to the invent;on produces dyeings of good to very good ozone fastness.
Suitable blue-dyeing fibre-reactive sulfo-containing anthraquinone dyes are for example the anthraquinone dyes given in the Colour Index as reactive blues.
Suitable red-, yellow- and orange-dyeing sulfo-containing azo dyes are for example the azo dyes given in the Colour Index as acid reds, acid yello~s and acid oranges respectively.
In a preferred embodiment of the process according to the nvention, at least one blue dye of the formula O NHYl I~ 1 2_ 3 )1-2 ~1 ) 11 l in which the ring L can be substituted by hydroxyl, halo-gen or sulfo, Y1 is hydrogen, C1_g-alkyl, Cs_7-cycloalkyl, phenyl or phenyl-c1-g-alkyl~ Y2 is hydrogen or halogen, such as chlorine or bromine, or is preferably a sulfo group, Y3 is unsubst;tuted or C1_4-alkyl-, C1_4-alkoxy-, phenoxy-, C1_4-alkylphenoxy or naphthoxy-substituted phenyl cr phenyl-C1_8~alkYl, and T is a fibre-reactive radical which is bonded either directly or via a bridge member, is used together with at least one red dye of the formula NH~, B-~ -N=N--~ ~-~ C--HO--~ ~-\S03H
in which A is hydrogen, substituted or unsubstituted C1_4-alkyl, z ~S02~ , -CO-~ or -S02R3, ~here R1 is C1_4 alkyl, R2 is subst;tuted or unsubstituted C5_7-cycloalkyl or substituted or unsubstituted phenyl, and R3 is substitu-ted or unsubstituted phenyl or substituted or unsubstituted phenoxy, and B is hydrogen, halogen, C2-4-alkanoylamin Cs_g-cycloalkoxycarbonylamino, c1_4-alkoxYcarbonylamin C1_4-alkylsulfonylamjno or substituted or unsubstituted phenylsulfonylamino, and with at least one yellow or orange dye of the formulae ~ 2 ~l (3) ;n which B1, B2 and E1 are each hydrogen, C1_4-alkyl or C1_4-alkoxy and X is straight-chain or branched C1_4-alkyl or straight-chain or branched C2_4-hydroxyalkyl, or ~< ~--O-S02--~ ~o Z ~ (4) C
H2 \1 Z~-/
in which Z1~ Z2 and Z3, independently of one another are each hydrogen, halogen~ C1_4-alkyl or C1_4-alkoxy, or mix-tures of dyes of the formulae (3) and (4), or a yellow dye of the formula C~2 2 ~ 3 ~ S03H
in which W1 is hydrogen, C1_4-alkyl, C1_4 alkoxy, haloge , C2-4-alkanoylamino or a substituted or unsubstituted arylsulfonyl, aryloxy or arylcarbonyl radical, W2 is hydro-gen, halogen, substituted or unsubstituted alkyl, aryloxy or aryloxysulfonyl radical or a radical of the formula -S2 ~ or -C0~ , W3 is a substituted or unsub-stituted alkyl or aryl radical, W4 ;s hydrogen or alkyl, and W5 and W6, independently of each other, are each hydrogen or a substituted or unsubstituted alkyl, cycloalkyl or aryl radical.
An alkyl radical Y1 in the formula (1) can be a straight-chain or branched alkyl radical, for example methyl, ethyl, propyl, isopropyL, butyl, sec.-butyl, iso-butyl, tert.-butyl, pentyl, hexyl, heptyl or octyl.
A C5_7-cycloalkyl radical Y1 in the formula (1) and a Cs_7-cycloalkyl radical R2 in the formula (Z3, independently of each other, can be for example an unsub-stituted cyclohexyl radical or a cyclohexyl radical which is substituted by alkyl, such as methyl.
A phenyl radical Y1 in the formula (1) can be a phenyl radical which can be substituted by C1_4-alkyl, C1_4-alkoxy or halo9en and be further substituted by a sulfo group and a fibre-reactive radical; the phenyl radi-cal is preferably substituted by a sulfo group and a fibre-reactive radical.
Phenyl-cl-8-alkyl radicals Y1 and Y3 in the formula (1), independently of each other, can each be for example a benzyl, phenethyl, phenylbutyl or phenyl-sec.-butyl radical which is preferably subst;tuted by a sulfo group and at least one fibre-reactive radical.
A phenyl radical Y3 in the formula (1) can be a phenyl radical which is substituted by C1_4-alkyl, in par-ticular methyl, C1_4-alkoxy, in particular methoxy, phenoxy, C1_4-alkylphenoxy, for example p-methylphenoxy, or naphthoxy and ~hich is further substituted by a sulfo group and preferably one or two fibre-reactive radicals.
Fibre-reactive radicals T are to be understood as mean;ng radicals which are capable of reacting w;th the hydroxyl groups of cellulose, w;th the amino, carboxyl, hydroxyl and thiol groups of wool and silk, or ~ith the amino and carboxyl groups of synthetic polyamides to form covalent chemical bonds~
Alkyl radicals A, B1, B2, E1, R1, X~ Z1~ Z2 and Z3 in the formulae (2), (3~ an~ (4), independently of one another, can be straight-chain or branched alkyl radi-cals, for example methyl, ethyl, propyl, isopropyl~ butyl, sec~-butyl, isobutyl or tert.-butyl.
An alkyl radical A can be substituted, for exa~ple, by halogen, such as chlorine or bromine or in particular fluorine, but preferably an alkyl radical A is a C1_4-perfluoro-alkyl radical, in particular a trifluoromethyl radical.
Substituted or unsubstituted phenyl radicals R2 and R3 can each be a phenyl radical which is substituted by C1_4-alkyl, C1_4-alkoxy or halogen; R2 or R3 is prefer-ably an unsubstituted phenyl radical.
A substituted or unsubstituted phenoxy radical R3 can be a phenoxy radical which is substituted by C1_4-alkyL, in particular methyl, C1_4-alkoxy or halogen, in particular chlorine; a phenoxy radical R3 is preferably a phenoxy radical which is unsubstituted or substituted by chlorine.
Halogens B, Z1~ Z2 and Z3 in the formulae (2) and
(4) can each be fluorine or bromine or in particular chlorine.
A C2_4 alkanoylamino ~ in the formula (2) can be 90;~ `
for example an acetylamino, propionylamino or butyrylamino rad;cal.
A Cs-C8-cycloalkoxycarbonylamino B can be in par-ticular a cyclohexyloxycarbonylamino radical.
A C1-4-alkylsulfonylamino ~ can be a methylsul-fonylamino, ethylsulfonylamino, propylsulfonYlamino, iso-propylsulfonylamino, butylsulfonylamino, tert.-butylsul-fonylamino, isobutylsulfonylamino or sec.-butylsulfonYl-amino radical.
A phenylsulfonyLamino radicaL can be a phenyLsuL-fonylamino radical which is substituted by C1_4-alkyl, C1_4-alkoxy or halogen; it preferably is a phenylsulfonyl-amino radical which is unsubstituted or substituted by methyl.
Alkoxy radicals ~ 2r E1~ Z1~ Z2 and Z3 in the formulae (3) and ~4) can each be for example a methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec.-butoxy, isobut-oxy or tert. butoxy radical.
A hydroxyalkyl radical X in the formula (3) can be a straight-chain or branched hydroxyalkyl radical, for example a ~-hydroxyethyl, ~-hydroxypropyl, ~-hydroxybutyl or ~-ethyl-~-hydroxyethyL radical.
A C1_4-alkyl W1 is methyL, ethyL, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl or tert.-butyl.
A C1_4-alkoxy W1 ;s methoxy, ethoxy, r,-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy or tert.-butoxy.
A C2_4-alkanoylamino W1 is for example acetylamino, propionylamino or butyrylamino.
In a substituted or unsubstituted arylsulfonyl, aryloxy or arylcarbonyl radical W1, aryl is preferably a radi-cal of the benzene or naphthalene series which can be further substituted, for example by C1_4-alkyl groups, such as methyl and ethyl, C1-4-alkoxy groups, such as methoxy and ethoxy, halogen, such as fluorine~ chlorine and bromine, alkanoylamino groups having 1 to 6 carbon atoms, such as acetylamino, and hydroxyl.
~Lg~O',~
Halosens W1 and/or W2 are fluorine, chlorine or brom;ne.
In a substituted or unsubstituted aryloxy or aryl-oxysulfonyl radical W2, aryl is a radical of the benzene or naphthalene series which can be further substituted, for example, by C1_4-alkyl groups, such as methyl and ethyl, C1_4-alkoxy groups, such as methoxy and ethoxy, halogen, such as fluorine, chlorine and bromine, alkanoyl-amino groups having 1 to 6 carbon atoms, such as acetyl-amino, and hydroxyl.
Substituted or unsubstituted alkyl radicals W2, W3, W5 and W6, independently of one another, are each pre-ferably a straight-chain or branched C1_12-alkyl, in parti-cular C1_4-alkyl, radical which can be further substi-tuted, for example by halogen, such as fluorine, chlorine or bromine, hydroxyl, cyano, C1_4-alkoxy, such as methoxy or ethoxy, and alkanoyl groups having 1 to 6 carbon atoms, such as the acetyl or propionyl group, and benzoyl group.
The alkyl radical W3 can also be substituted by sulfo.
Examples of alkyl radicals W2, W3, Ws and W6 are:
methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, iscbutyl and trifluoromethyl.
Substituted or unsubstituted aryl radicals W3, W5 and W6, independently of one another, are preferably mem-bers of the benzene or naphthalene series and can be fur-ther substituted, for example by C1_4-alkyl groups, such as methyl, C1_4-alkoxy groups, such as methoxy and eth-oxy, halogen, such as fluorine, chlorine or bromine, tri-fluoromethyl, alkanoylamino groups having 1 to 6 carbon atoms, such as acetylamino, hydroxyl and carboxyl. The aryl radical W3 can also be substituted by sulfo. In part;cular aryl radicals W3, W5 and W6 are each a phenyl radical which can be substituted by methyl, trifluoro-methyl and chlorine.
An alkyl radical W4 is preferably a straight-chain or branched C1_12-alkyl and in particular a c1_~-alkYl radical. Examples are~ methyl, ethyl, propyl, isopropyl, ~LZ~ 2 butyl, sec.-butyl, tert.-butyl, isobutyl, pent-1-yl, pent-3-yl, hept-1-Yl, hept-3-yl and oct-1-yl.
Subst;tuted or unsubstituted cycloalkyl rad;cals Ws and W6, ,ndependently of each other, are preferably cycloalkyl groups having 5- to 7-membered rings, which can be further substituted, for example by C1_4-alkYl, such as methyl. In part;cular the cyclohexyl group comes into consideration.
T ;n the formula (1) is preferabLy a fibre-reactive radical of the aliphat;c, aromat;c or heterocyclic series which ;s bonded to the radical Y1 and/or Y3 e;ther d;-rectly or v;a a bridge member.
T ;s preferably bonded to the rad;cal Y1 and/or Y3 either directly or v;a an amino group ~hich can be mono alkylated, for example via -NH-, -N(CH3)-, -N(C2H5)- or -N(C3H7)-, or via a bridge member containing an am;no group.
A fibre-react;ve radical T ;n the formula t1) can be for example one of the follow;ng al;phat;c or aromat;c radicals:
vinylsulfonyl, ~-chloroethylsulfonyl, ~-sulfato-ethylsulfonyl, ~-acetoxy-ethylsulfonyl, phosphonooxyethyl-sulfonyl, ~-thiosulfatoethylsulfonyl, N-methyl-N-(~-sulfatoethylsulfonyl)-am;no, acryloyl, monochloroacryloyl, d;chloroacryloyl or trichloroacryloyl such as CO-CCl=CH2, -CO-CH=CH-Cl, -CO-CCl=CH-CH3; monobromoacryloyl, di-bromoacryloyl or tribromoacryloyl such as -CO-CBr=CH2, -CO-CH=CH-Br, -CO-CBr=CH-CH3; and also -CO-CCl=CH-COOH, -CO-CH=CCl-COOH, -CO-CBr=CH-COOH, -CO-CH=CBr-COOH~ -CO-CCl=CCl-COOH, -CO-CBr=CBr-COOH; precursors of the acryloyl rad;cal and of the der;vat;ves of the acryloyl rad;cal, such as ~-chloroprop;onyl, ff-bromoprop;onyl, 3-phenyl-sulfonyLprop;onyl, 3-methylsulfonylprop;onyl, 3-chloro-3-phenylsulfonylpropionyl, 2,3-dichloroprop;onyl, 2,3-d;bromoprop;onyl; and also 2-fluoro-2-chloro-3,3-d;fluoro-cyclobutane 1-carbonyl, 2,2,3,3-tetrafluorocyclobutane-1-carbonyl or -1-sulfonyl, ~-(2,2,3,3-tetrafluorocyclobut-1-yl)-acryloyl, ~- or ~-alkylsulfonylacryloyl or arylsulfonylacryloyl groups such as ~- or ~-methylsulfonylacryloyl, propiolyl, chloroacetyl, bromoacetyl, 4-(~ chloroethylsulfonyl~-butyryl, 4-vinylsulfonyl-butyryl, 5-(~-chloroethylsulfonyl)-valeryl, 5-vinylsulfonYl-valerYl, 6-(~ chloroethylsulfonyL)-caproyl, 6-v;nylsulfonyl-caproyl; and also 4-fluoro-3-nitrobenzoyl, 4-fluoro-3-n;trophenylsulfonyl, 4-fluoro-3-methylsulfonylbenzoyl, 4-fluoro-3-cyanobenzoyl, 2-fluoro-
A C2_4 alkanoylamino ~ in the formula (2) can be 90;~ `
for example an acetylamino, propionylamino or butyrylamino rad;cal.
A Cs-C8-cycloalkoxycarbonylamino B can be in par-ticular a cyclohexyloxycarbonylamino radical.
A C1-4-alkylsulfonylamino ~ can be a methylsul-fonylamino, ethylsulfonylamino, propylsulfonYlamino, iso-propylsulfonylamino, butylsulfonylamino, tert.-butylsul-fonylamino, isobutylsulfonylamino or sec.-butylsulfonYl-amino radical.
A phenylsulfonyLamino radicaL can be a phenyLsuL-fonylamino radical which is substituted by C1_4-alkyl, C1_4-alkoxy or halogen; it preferably is a phenylsulfonyl-amino radical which is unsubstituted or substituted by methyl.
Alkoxy radicals ~ 2r E1~ Z1~ Z2 and Z3 in the formulae (3) and ~4) can each be for example a methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec.-butoxy, isobut-oxy or tert. butoxy radical.
A hydroxyalkyl radical X in the formula (3) can be a straight-chain or branched hydroxyalkyl radical, for example a ~-hydroxyethyl, ~-hydroxypropyl, ~-hydroxybutyl or ~-ethyl-~-hydroxyethyL radical.
A C1_4-alkyl W1 is methyL, ethyL, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl or tert.-butyl.
A C1_4-alkoxy W1 ;s methoxy, ethoxy, r,-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy or tert.-butoxy.
A C2_4-alkanoylamino W1 is for example acetylamino, propionylamino or butyrylamino.
In a substituted or unsubstituted arylsulfonyl, aryloxy or arylcarbonyl radical W1, aryl is preferably a radi-cal of the benzene or naphthalene series which can be further substituted, for example by C1_4-alkyl groups, such as methyl and ethyl, C1-4-alkoxy groups, such as methoxy and ethoxy, halogen, such as fluorine~ chlorine and bromine, alkanoylamino groups having 1 to 6 carbon atoms, such as acetylamino, and hydroxyl.
~Lg~O',~
Halosens W1 and/or W2 are fluorine, chlorine or brom;ne.
In a substituted or unsubstituted aryloxy or aryl-oxysulfonyl radical W2, aryl is a radical of the benzene or naphthalene series which can be further substituted, for example, by C1_4-alkyl groups, such as methyl and ethyl, C1_4-alkoxy groups, such as methoxy and ethoxy, halogen, such as fluorine, chlorine and bromine, alkanoyl-amino groups having 1 to 6 carbon atoms, such as acetyl-amino, and hydroxyl.
Substituted or unsubstituted alkyl radicals W2, W3, W5 and W6, independently of one another, are each pre-ferably a straight-chain or branched C1_12-alkyl, in parti-cular C1_4-alkyl, radical which can be further substi-tuted, for example by halogen, such as fluorine, chlorine or bromine, hydroxyl, cyano, C1_4-alkoxy, such as methoxy or ethoxy, and alkanoyl groups having 1 to 6 carbon atoms, such as the acetyl or propionyl group, and benzoyl group.
The alkyl radical W3 can also be substituted by sulfo.
Examples of alkyl radicals W2, W3, Ws and W6 are:
methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, iscbutyl and trifluoromethyl.
Substituted or unsubstituted aryl radicals W3, W5 and W6, independently of one another, are preferably mem-bers of the benzene or naphthalene series and can be fur-ther substituted, for example by C1_4-alkyl groups, such as methyl, C1_4-alkoxy groups, such as methoxy and eth-oxy, halogen, such as fluorine, chlorine or bromine, tri-fluoromethyl, alkanoylamino groups having 1 to 6 carbon atoms, such as acetylamino, hydroxyl and carboxyl. The aryl radical W3 can also be substituted by sulfo. In part;cular aryl radicals W3, W5 and W6 are each a phenyl radical which can be substituted by methyl, trifluoro-methyl and chlorine.
An alkyl radical W4 is preferably a straight-chain or branched C1_12-alkyl and in particular a c1_~-alkYl radical. Examples are~ methyl, ethyl, propyl, isopropyl, ~LZ~ 2 butyl, sec.-butyl, tert.-butyl, isobutyl, pent-1-yl, pent-3-yl, hept-1-Yl, hept-3-yl and oct-1-yl.
Subst;tuted or unsubstituted cycloalkyl rad;cals Ws and W6, ,ndependently of each other, are preferably cycloalkyl groups having 5- to 7-membered rings, which can be further substituted, for example by C1_4-alkYl, such as methyl. In part;cular the cyclohexyl group comes into consideration.
T ;n the formula (1) is preferabLy a fibre-reactive radical of the aliphat;c, aromat;c or heterocyclic series which ;s bonded to the radical Y1 and/or Y3 e;ther d;-rectly or v;a a bridge member.
T ;s preferably bonded to the rad;cal Y1 and/or Y3 either directly or v;a an amino group ~hich can be mono alkylated, for example via -NH-, -N(CH3)-, -N(C2H5)- or -N(C3H7)-, or via a bridge member containing an am;no group.
A fibre-react;ve radical T ;n the formula t1) can be for example one of the follow;ng al;phat;c or aromat;c radicals:
vinylsulfonyl, ~-chloroethylsulfonyl, ~-sulfato-ethylsulfonyl, ~-acetoxy-ethylsulfonyl, phosphonooxyethyl-sulfonyl, ~-thiosulfatoethylsulfonyl, N-methyl-N-(~-sulfatoethylsulfonyl)-am;no, acryloyl, monochloroacryloyl, d;chloroacryloyl or trichloroacryloyl such as CO-CCl=CH2, -CO-CH=CH-Cl, -CO-CCl=CH-CH3; monobromoacryloyl, di-bromoacryloyl or tribromoacryloyl such as -CO-CBr=CH2, -CO-CH=CH-Br, -CO-CBr=CH-CH3; and also -CO-CCl=CH-COOH, -CO-CH=CCl-COOH, -CO-CBr=CH-COOH, -CO-CH=CBr-COOH~ -CO-CCl=CCl-COOH, -CO-CBr=CBr-COOH; precursors of the acryloyl rad;cal and of the der;vat;ves of the acryloyl rad;cal, such as ~-chloroprop;onyl, ff-bromoprop;onyl, 3-phenyl-sulfonyLprop;onyl, 3-methylsulfonylprop;onyl, 3-chloro-3-phenylsulfonylpropionyl, 2,3-dichloroprop;onyl, 2,3-d;bromoprop;onyl; and also 2-fluoro-2-chloro-3,3-d;fluoro-cyclobutane 1-carbonyl, 2,2,3,3-tetrafluorocyclobutane-1-carbonyl or -1-sulfonyl, ~-(2,2,3,3-tetrafluorocyclobut-1-yl)-acryloyl, ~- or ~-alkylsulfonylacryloyl or arylsulfonylacryloyl groups such as ~- or ~-methylsulfonylacryloyl, propiolyl, chloroacetyl, bromoacetyl, 4-(~ chloroethylsulfonyl~-butyryl, 4-vinylsulfonyl-butyryl, 5-(~-chloroethylsulfonyl)-valeryl, 5-vinylsulfonYl-valerYl, 6-(~ chloroethylsulfonyL)-caproyl, 6-v;nylsulfonyl-caproyl; and also 4-fluoro-3-nitrobenzoyl, 4-fluoro-3-n;trophenylsulfonyl, 4-fluoro-3-methylsulfonylbenzoyl, 4-fluoro-3-cyanobenzoyl, 2-fluoro-
5-methylsulfonylbenzoyl.
The fibre-reactive radical T can also be a member of the he-terocyclic series, for example a 2~4-dichlorotri-azin-6-yl or monohalogenopyrimidinyl, dihalogenopyrimidinyl or trihalogenopyrimidinyl radical, such as 2,4-dichloro-pyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 2,4-dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy-or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-monochloro-methyl- or -5-dichloromethyl- or -5-trichloromethyl- or -5-methylsulfonyl-pyrimidin-6-yl, 2,5-dichloro-4-methyl-sulfonylpyrimidin-6-yl, 2-fluoro-4-pyrimidinyl, 2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyr;midinyl, 2,6-difluoro-5-methyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-
The fibre-reactive radical T can also be a member of the he-terocyclic series, for example a 2~4-dichlorotri-azin-6-yl or monohalogenopyrimidinyl, dihalogenopyrimidinyl or trihalogenopyrimidinyl radical, such as 2,4-dichloro-pyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 2,4-dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy-or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-monochloro-methyl- or -5-dichloromethyl- or -5-trichloromethyl- or -5-methylsulfonyl-pyrimidin-6-yl, 2,5-dichloro-4-methyl-sulfonylpyrimidin-6-yl, 2-fluoro-4-pyrimidinyl, 2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyr;midinyl, 2,6-difluoro-5-methyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-
6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 2,5,6-trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 2,6-difluoro-5-bromo-4-pyrimi-dinyl, 2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-chloromethyl 4-pyrimidinyl, 2,6-difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl, 6-tri-fluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoro-methyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimi-dinyl, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl- or -5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-carboxamido-4-pyrimidinyl, 2-fluoro-5-carbomethoxy-4-æ
pyrimidinyl, 2-fluoro-5-bromo-6-trjfluoromethyl-4-pyrim dinyl, 2-fluoro-6-carboxamido-4-pyrimidinyl, 2-fLuoro-6-carbomethoxy-4 pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimi-dinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluorc-5-sulfonaMido-4-pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimi-dinyl, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl; 2,4-bis-methylsulfonylpyrimidin-4-yl, 2~5-bis-methylsulfonyl-5-chloropyrimidin-4-yl, 2-methylsulfonyl-pyrimidin-4-yl, 2-phenylsulfonyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-methylpyrimidin-4-yl, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimi-din-4-yl, 2-methyLsulfonyl-5-chloro-methylpyrimidin-4-yl, 2-methylsulfonyl-5-nitro-6-methylpyrimidin-4-yl, 2,5,6-tris-methylsulfonyl-pyrimidin-4-yl, 2-methylsulfonyl-5,6-dimethylpyrimidin-4-yl, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-6-chloro-pyrimidin-4 yl, 2,6-bis-methylsulfonyl-5-chloropyrimidin-4-yl, 2-methyl-sulfonyl-6-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-5-sulfo-pyrimidin-4-yl, 2-methylsulfonyl-6-carbomethoxy-pyrimidin-4-yl, 2-methylsulfonyl-5-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-5-cyano-6-methoxy-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-pyrimidin-4-yl, 2-sulfoethyL-sulfonyl-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-5-bromo-pyrimidin-4-yl, 2-phenylsulfonyl-5-chloro-pyrimidin-4-yl, 2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2,4-dicnloropyrimidine-6-carbonyl or -6-sulfonyl, 2,4-dichloropyrimidine-5-carbonyl or -5-sulfonyl, 2-chloro-4-methylpyrimidine-5-carbonyl, 2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio-4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloropyrimidine-5-carbonyl, 2,4,6 tri-chloropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl, 2,4-dichloro-6-methylpyrimidine-5-carbonyl or -5-sulfonyl, 2-methylsulfonyl-6-chloropyrimidin-4-yl and -5-carbonyl, 2,6-bis-(methylsulfonyl)-pyrimidine-4- or -5-carbonyl, 2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl, 2,4-bis-lmethylsulfonyl)-pyrimidine-5-sulfonyl, 2-methyl-sulfo-nyl-4-chloro-6-methyl-pyrimidine-5-sulfonyl or -5-carbonyl;
2-chloroquinoxaline-3-carbonyl, 2- or 3-monochloroquinox-al;ne-6-carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5- or -6-carbonyl, 2,3-dichloroquin-oxaline-5- or 6-sulfonyl, 1,4-dichlorophthalazine-6-sul-fonyl or -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-sulfonyl or -carbonyl, 2,4,6-trichloroquinazoline-7- or -8-sulfonyl, 2- or 3- or 4-(4',5'-dichloropyridaz-6' on-1'-yl~-phenylsulfonyl or -carbonyl,~ -(4',5'-dichloropyri-dazin-6'-on-1'-yl)-propionyl, 3,6-d;chLoro-pyr;daz;n-4-carbonyl or -4-sulfonyl, 2-chlorobenzoth;azole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonylbenzoth;azole-or Z-alkyLsulfonylbenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, such as 2-methylsulfonylbenzothiazole- or 2-ethyl-sulfonylbenzothiazole-5- or -6-sulfonyl- or -carbonyl~ 2-phenylsulfonylbenzothiazole-5- or -6-sulfonyl or -carbonyl and the corresponding 2-sulfonylbenzothiazole-5- or -6-carbonyl or -sulfonyl der;vatives which contain sulfo groups in the fused-on benzene ring, 2-chlorobenzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chlorobenzim;dazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-1-methylbenz;midazole-5-or -6-carbonyl or -sulfonyl, 2-chloro-4-methyl-1,3-thiazole-5-carbonyl or -4- or -5-sulfonyl; ammonium-containing tri-az;ne rings, such as 2-trimethylammonium-4-phenylamino-or -4-(o-, m- or p-sulfophenyl)-amino-tr;azin-6-yl, 2-(1,1-dimethyl-hydrazinium)-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-aminotriazin-6-yl, 2-(2-isopropylidene-1,1-dimethyl)-hydrazinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-aminotriazin-6-yl, 2-N-aminopyrrolidinium-or 2-N-aminopiperidinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-aminotriazin-6-yl, and also 4-phenylamino-or 4-(sulfophenylamino)-triazin-6-yl radicals which, in the 2-position, contain 1,4-bis-azabicycloC2.2.2.]octane or 1,2-bis-azabicyclo~0.3.3.]-octane via a quaternary nitrogen bond, 2-pyridinium-4-phenylamino- or -4 (o-, m-or p-sulfophenyl)-amino-triazin-6-yl and corresponding 2-oniumtriazin-6-yl radicals wh;ch are substituted in the 5~
4-position by alkylamino, such as methylamino, ethylamino or ~-hydroxyethylamino, or alkoxy, such as methoxy or ethoxy, or aryloxy, such as phenoxy, or sulfophenoxy groups.
An interesting fibre-reactive radical can also be a chloro- or fluoro-1,3,5-triazine radical of the formula F, Cl V
where the substituent V on the triazine ring can be in particular:
halogen, for example chlorine or fluorine, C1_8-alkoxy, for example methoxy, cyclohexyloxy, phenoxy, C1_6-alkylmercapto, such as methylmercapto, phenylmer-capto, -NH2, alkylamino, N,N-dialkylamino, cycloalkyl-amino, N,N-dicycloalkylamino, aralkylamino, arylamino, mixed-substituted amino groups, such as N-alkyl-N-cyclo-hexylamino and N-alkyl-N-arylamino groups, and also amino groups wh;ch contain heterocyclic radicals which can have further fused-on carbocyclic rings, and amino groups in which the amino nitrogen atom is a member of an N-hetero-cyclic ring which can contain further hetero atoms, as well as hydrazino and semicarbazido. The abovementioned alkyl rad;cals can be straight-chain or branched and of low molecular weight or higher molecular weight and are preferably alkyl radicals having 1 to 6 carbon atoms, cycloalkyl, aralkyl and aryl radicals can be in particular cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radi-cals; heterocyclic radicals can be in particular furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, ben-zimidazole, benzothiazole and benzoxazole radicals; and amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring are preferably radicals of six-membered N-heterocyclic compounds which can contain nitro-gen, oxygen or sulfur as further hetero atoms. The above-mentioned alkyl, cycloalkyl, aralkyl and aryl radicals, O~
the heterocyclic radicals and the N-heterocyclic rings can be further substituted, for example by: halogen, such as fluorine, chlorine or bromine, nitro, cyano, trifluoro-methyl, sulfamoyl, carbamoyl, C1_~,-alkyl, C1_4-alkoxy, acylamino groups, such as acetylamino or benzoylamino, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo. Examples of such amino groups are: -NH2, methylamino, ethylamino, propylamino, isopropylamino, butylamino, hexylamino,~ -methoxyethylamino, ~-methoxypropylamino, ~-ethoxyethyl-amino, N,N-dimethylamino, N,N-diethylamino,~ -chLoroethyl-amino, ~cyanoethylamino, ~-cyanopropylamino, ~-carboxyethyl-amino, sulfomethylamino,~ -sulfoethylamino, ~-hydroxy-ethylamino, N,N-di-~-hydroxyethylamino,~-hydroxypropyl-amino, benzylamino, phenethylamino, cyclohexylamino, phenylamino, toluidino, xylidino, chloranilino, anisidino, phenetidino, N-methyl-N-phenylamino, N-ethyl-N-phenylam;no, N-~-hydroxyethyl-N-phenylamino, 2-, 3- or 4-sulfoanilino, 2,5-disulfoanilino, 4-sulfomethylanilino, N-sulfomethyl-anilino, 2-, 3- or 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfo-naphth-1-ylamino, 3,6-disulfonaphth-1-ylamino, 3,6,8-trisulfonaphth-1-ylamino, 4,6,8-trisulfonaphth-1-ylamino, 1-sulfonaphth-2-yl-amino, 1,5-disulfonaphth-2-yl-amino, 6-sulfonaphth-2-yl-amino, morpholino, piperidino, pipera-zino, hydrazino and semicarbazido.
In particularly preferred embodiments o-f the pro-cess accordin~ to the invention, a) a blue dye of the formula - SO H
~ ( )N)o-l (6), in ~hich T is as defined under the formula ~1) and the phenyl ring L1 can be monosubstituted, disubstituted, ~2~0~
trisubstituted or tetrasubstituted by C1_4-alkyl, C1_4-alkoxy or phenoxy, or a blue dye of the formuLa / \i/ ~- ~ (S3H)l 2 0 E~H--~ L2/- ~ (T)1-2 hich Y4 is a C1_6-alkyl or C5_7-cycloalkyl radical, T is as defined in the formula (1) and the phenyl ring L2 can be monosubstituted, disubstituted or trisubstituted by C1_4-alkyl, C1_4-alkoxy, phenoxy or C1_4-alkylphenoxy, or a blue dye of the formula 0 ~H-Y
o~ ,.,!,.,!~. _ - (S03H) 1-2 !~ ! 1 - (T)l-2 (8~
~ O E`IH-(Cl 8-alkylene~-\ L3/~ ,_ in which Y4 is as defined under the formula (7), T is as defined in the formula (1) and the phenyl ring L3 can be monosubstituted or disubstituted by C1_4-alkyl or C1_4-alkoxy, or a blue dye of the formula o ~H-(Cl_6-alk'~l~ne)o_l \ >~
.~ \./ \./
~ ! ! ( 9), / \./ \.~ T
Il I ~o-~O NE~-(Cl-6- alky1ene) ~ -in which T ;s as defined in the formula ~1), is used;
~z~ o;~
b) at least one red dye of the formula (2) in which A ishydrogen, methyl, trifluoromethyl, ~ ~
-CON~ , -SO2N~ or -S02R3 where R~ is methyl or ethyl, R2 is cyclohexyl or phenyl, and R3 is phenyl, methylphenyl, phenoxy or chlorophenoxy, and B is hydrogen, chlorine, acetylamino, propionylamino, cyclohexyloxycarbonylamino, phenylsulfonylamino or methyl-phenylsulfonylamino, A and B not both being hydrogen at the same time, is used; and c) at least one yellow or orange dye of the formula ~CH3 ~l N=N-~ -N N--~ O-X1 ~10), Al in which A1 is hydrogen or methyl, F1 is hydrogen or methyl and X1 is methyl, ethyl, ~-hydroxyethyl,~ -hydroxy-propyl, ~-hydroxybutyl or ~-ethyl-~-hydroxyethyl or a mix-ture of at least one dye of the formula (10) and a yello~
dye of the formula ~ ~--O-S02--~ ~-Z
N
.~ ~. ( 1 1 ), Z + 1I SO H
6 ~ /- 3 in which Zs and Z6~ independently of each other, are each hydrogen, methyl or chlorine, or a yello~ dye of the formula w~ I ~so3H
n~
in which W1 ;s hydrogen, methyl, chlorine, methoxy, ethoxy, o-methylphenoxy, phenoxy, acetylamino, phenylsul-fonyl, p-methylphenylsulfonyl, p-chlorophenylsulfonyl, naphthylsulfonyl, p-methylbenzoyl or p-chlorobenzoyl, W2 is hydrogen, chlorine, methyl, tr;fluoromethyl, o-methyl-phenoxy, o-chlorophenoxy, o-chlorophenoxysulfonyl, -S02NHz, N-C1_2-alkylaminosulfonyl, N,N-dimethylaminosulfonyl, N-methyl-N-~-hydroxyethylaminosulfonyl, N-methyl-N-cyclo-hexylaminosulfonyl, N-phenylaminosulfonyl, N-o-methyl-phenylaminosulfonyl, N-o-chlorophenyLaminosu~fonyl, N-m-trifluoromethylphenylaminosulfonyl, N-ethyl-N-pheny'amino-sulfonyl~ CONH2 or -CON(CH3)2, W3 is methyl or phenyl and W4 is hydrogen~ methyl, ethyl or octyl, is used.
In particularly interesting embodiments of the process according to the invention d) a dye of the formula (6) or (7) is used:
e) use is made of anthraquinone dyes of the formulae (6) to (9), in particular of the formulae (6) or ~7) in which T is a fibre-reactive radical of the aliphatic, aromatic or heterocyclic series which can be bonded via a bridge member of the formula ~ ~ o l ~ ~ 3 o--1 or via -CH2-N- or -CH~-~(R4), and R4 is hydrogen or C1 4-alkyl;
f) use is made of anthraquinone dyes of the formulae (6) to (9) in which T is a chloroacetyl, bromoacetyl, acryloyl, ~,~-dichloropropionyl, ~-~-dibromopropionyl, ~-bromoacryl-oyl or ~-chloroacryloyl radical which is bonded via -NH, -CH-NH- or -CH2-NH- or is a radical for the formulae COOH
~2~
-NH ~ Cl ~! ,F, Cl N~ ~ or N~ ~
R5 F, C1 in ~hich R5 is C1_6-alkoxy, c1_6-alkYlmercapto or a radical of the formula _N~6 where R6 and R7, ~ 7 independently of each other, are each hydrogen, C1_6-alkyl or substituted or unsubstituted phenyl or naphthyl, or is a vinylsulfonyl, ~-sulfatoethylsulfonyl, ~-acetoxyethyl-sulfonyl, ~-chloroethylsulfonyl or g-~'-sulfatoethylsul-fonyL)-propionylaminomethyl radical;
g) use is made of preferably a blue anthraquinone dye of the formula o NH
SO ~1 / \ / \ ~
I\._./ 2 tl3), \.=./ 3 G/ \G
in which G1, G3 and Gs are each methyl, G4 is q-chloro-acryloylaminomethyl or d-bromoacryloylaminomethyl, d,~-dibromopropionylaminomethyl, ~-(g'-sulfatoethylsulfonyl)-propionylaminomethyl, ~,~-dibromopropionylamino -CH ( COOH) -.~'H-CO-~H
H2Br or chloroacetylaminoethyl and G2 is hydrogen, sulfo or chloro-acetylaminomethyl or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which G1 is hydrogen or methoxy, G2, G3 and Gs are each hydro-gen and G4 is sulfatoethylsulfonYl, chloroacetylamino, ~g-dibromopropionylamino, vinylsulfonyl, 2-methoxy-4-fluoro-s-triazinylamino or 2-ethylamino-4-fluoro-s-triazinylamino, or in ~hich G1, G2, G4 and GS are each hydrogen and G3 is g~oz chloroacetylamino, ~p,-dibromopropionylamino~ 2,6-difluoro-5-chloropyrimidin-4-yl-amino or 2-chloro-4-amino- or 4-N,N-di-methylamino-s-triazinylamino, or in which G1 is methyl, G2 is ~-sulfatoethylsulfonyl and G3, G4 and G5 are each hydrogen, or in which G1 or G2 is sulfo~ G3 is ~- bromo-acryloylamino or N-methyl-N-[3-(~-chloroethylsulfonyl~-ben-Y mino and G2 or G1 and G4 and G5 are each hydro-gen, or G1, G2 and G5 are each hydrogen, G3 is methyl and G4 is chloroacetylamino, or in which G1 is methyL, G2 is 2,6-difluoro 5-chloropyrimidinylamino, G4 is sulfo and G3 and Gs are each hydrogen; and h) in particular a dye of the formula (13) in which G1, G2, G4 and Gs are each hydrogen and G3 is chloroacetyl-amino or ~v~-dibromoprop;onylamino, or in which G1, G2, G3 and G5 are each hydrogen and G4 is vinylsulfonyl, chloro-acetylamino, 2-methoxy- or 2-ethylamino-4-fluoro-s-triazinyl-amino, or in which G1, G3 and Gs are each methyl, G2 is hydrogen and G4 is chloroacetylaminomethyl, ~
dibromopropionylaminomethyl or -CHtCOOH)-NH-CO-CHBr-CH2Br, or in which G1 is methoxy, G2, G3 and G5 are each hydrogen and G4 is ~-sulfatoethylsulfonyl, or in which G1, G3 and Gs are each hydrogen and G2 and G4 are each chloroacetylaminomethyl or -CH(COOH)-NH-CO-CHBr-CH2sr, or in which G1, G3 and Gs are each methyl, G2 is ~v~~
dibromopropionylamino and G4 is sulfo, or in which G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~-bromoacryloylamino, or in which G1 is methyl, G2 is 2,6-difluoro-5-chloropyrimidylamino, G3 and G5 are each hydro-gen and G4 is sulfo; or i) use is made of a blue dye of the formula (1) in which Y1 is cyclohexyl, Y2 is hydrogen, Y3 is 4-(4'-methyl-phenoxy)-phenyl and T is chloroacetylaminomethyl and the dye contains a single sulfo group, or in which Y1 is isopropyl, Y2 is hydrogen and Y3 is a phenyl-sec.-butyl radical which is subst;tuted in the phenyl ring by sulfo and chloroacetylaminomethyl or is a diphenyl ether radical which is substituted in the phenoxy radical by sulfo and acryLoylaminomethyl~ or in which Y1 and Y3 both denote a phenyl-sec.-butyl radical which is substituted in the phenyl ring by sulfo and chloroacetylamino methyl, and Y2 is hydrogen, or in which Y1 and Y3 both denote a 4-~-bromo-acryloylamino-3-sulfophenyl radical and Y2 is hydrogen.
Of the dyes given in i), preference is gi~en to the dye of the formula (1) in which Y1 is cyclohexYl, Y2 is hydrogen and Y3 is 4-(4'-methylphenoxy)-phenyl, the phenyl ring of the phenoxy group being substituted by sulfo and chloroacetylaminomethyl.
In a particular~y important embodiment of the pro-cess according to the invention, a blue dye of the formula (13) in which G1, Gz, G4 and Gs are each hydrogen and G~
is ~ dibromopropionylamino, or in which G1, G3, G4 and G5 are each hydrogen and G2 is vinylsulfonyl, chloro-acetylamino, 2-methoxy-4-fluoro-s-triazinylamino or Z-ethylamino-4-fLuoro-s-triazinylamino, or in which G1 is methyl, G2 is 2,6-difluoro-5-chloropyrimidinylamino~ G3 and G5 are each hydrogen and G4 is sulfo, or in which G1 is methoxy, G2, G3 and G5 are each hydrogen and G4 is ~-sulfato-ethylsulfonyl, or in which G1, G3 and G5 are each methyl, G2 is hydrogen or -CH(COOH)-NH-CO-CHBr-CH29r and G4 is ~,g-dibromopropionylaminomethyl or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which G1, G3 and Gs are each methyl, G2 is ~
dibromopropionyLamino and G4 is sulfo, or in which G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~ -bromoacryloylamino, is used together with a red dye of the formula (2) and the yellow or orange dyes of the for-mulae (3) and/or (4) or ~5)~
In very particularly important embodiments of the process according to the invention, the blue dye of the formula R ~H2 S O ~{
Cl .=./ 3 (14), c~3 1;~4~90~
or the dye of the forMula I i1 i1 i C~3 ~CH2~1cOcH2Cl \.=./ 3 (15), CH3 CH2~HCOCH2Cl or the dye of the formu~a ~ ~R ~2~So3H
!~ ,ii, i!, ~! (16), ~H--~ NH-C0-CH2Cl =--or the dye of the formula _ --~H- ~ H ~-.~ \o/ \ /
- ~./ \ / \ ,~ ,CH2-'.~H-CO-CH2Cl (17), O ~H - ~ CH3 ;s used.
In the process according to the invention, it is also possible to use mixtures of two or more anthraquinone dyes of the type defined. In particular, use is made of a mixture of two anthraquinone dyes whose individual components each contain one or two fibre-reactive groups and one or two sulfo groups.
Preferably, each ;ndividual component of the mix-ture corresponds to one of the anthraquinone dyes specified above under the formula (1).
It is very particularly preferred to use in the process according to the invention mixtures of anthraquinone ~J~ 2 dyes of the formulae (6), (7), (8) or (9), i~e. mixtures ;n which one component corresponds to a dye of the formula ~6), (7), (~) or (9) and the other component corresponds to a dye of the formula (6), (7)~ (~) or (9)~ In parti-cular, use is made of a mixture of two anthraquinone dyes in which one component corresponds to a dye of the formula (6) and the other component corresponds to a dye of the formula (6) or (7).
In an important mixture of anthraquinone dyes wh;ch can be used in the process according to the inven-t;on, one component corresponds to a dye of the formula (14), (~15~ or a dye of the formula t7) in which Y4 is cyclohexyl, L2 is substituted by p-methylphenoxy and T is chloroacetylaminomethyl, and the dye of the formula ~7) contains only one sulfo group, and the other component corresponds to a dye of the formula (13) in which G1, G2, G4 and Gs are each hydrogen and G3 is ~,~-dibromo-propionylamino, or in which G1, G3, G4 and G5 are each hydrogen and G2 is vinylsulfonyl, chloroacetylamino, 2-methoxy-4-fluoro-s-triazinylam;no or 2-ethylamino-4-fluoro-s-triazinylamino, or ;n wh;ch G1 is methyl, and G2 is 2,6-difluoro-5-chloro-pyrimidinylamino, G3 and G5 are both hydrogen and G4 is sulfo, or in which G1 is sulfo, G2, G4 and G5 are each hydrogen and G3 is ~-bromoacryl-oylamino, or in which G1, G3 and G5 are each methyl, and G2 is ~,~- dibromopropionylaminomethyl, -CH(COOH)-NH-CO-CHBr-CH2Br or ~,~-dibromopropionylamino and G4 is hydrogen, -CH(COOH)-NH-CO-CHBr-CH2Br or sulfo, or in which G1 is methoxy, G2, G3 and Gs are each hydrogen and G4 is ~-sulfatoethylsulfonyl.
In a particularly important mixture of anthraqui-none dyes which can be used in the process according to ~he ;nvention, one component corresponds to the dye of the formula (14) or (15) and the other component corres-ponds ~o the dye of the formula ~7) in which Y4 is cyclo-hexyl, L2 is substituted by p-methylphenoxy and T ;s chloroacetylaminomethyl and the dye of the formuia (7) contains only one sulfo group.
In a further particularly important mixture of anthraquinone dyes which can be used in the process accord-ing to the invention, one component corresponds to the dye of the formula (14) or (15) and the other component corresponds to the dye of the formula (13) in which G1, G2, G4 and G5 are each hydrogen and G3 is chloroacetylamino.
In a very particularly important mixture of anthra-quinone dyes which can be used in the process according to the invention, one component corresponds to the dye of the formula (15) and the other component corresponds to the dye of the formula (17). Preferably the weight ratio of the dyes of the formulae (15) to (17) is 90:10 to 70:30, in particular 80:20.
In general the weight ratio of the anthraquinone dyes in the mixtures used according to the invention can vary ~ithin ~ide limits. A weight ratio of 90:10 to 10:90 and in particular of 70:30 to 30:70, has been found to be advantageous.
The anthraquinone dyes of the formula (1) or the components of the mixtures of the anthraquinone dyes used in the process according to the invention preferably con-tain only one sulfo group.
In the process according to the invention, the red dye used is preferably j) a red dye of the formula (Z) in ~hich A is hydrogen, N-methyl-N-cyclohexylsulfamoyl, phenylsulfonyl, N-ethyl-N-phenylsulfamoyl, phenoxysulfonyl or trifluoromethyl and B
is hydrogen, acetylamino or cyclohexyloxycarbonylamino;
and in particular k) a red dye of the formula (2) in which A is hydrogen and B is acetylamino or cyclohexyloxycarbonylamino or A
is trifluoromethyl and B is acetylamino or A is phenylsul-fonyl, N-methyl-N-cyclohexylsulfamoyl, N-ethyl-N-phenyl-sulfamoyl or phenoxysulfonyl and B is hydrogen; and the yellow or orange dye of the formulae (3) to (5~ is l) the yellow dye of the formula ~5~102 ~OCH3 \. ./ \ / \ / 3 (18) S~3H
or the orange dye of the formula OCH
HO S--~ ~-N=N--~ N=N~ -OCH t19 C~3 or a mixture of the yeLlow dye of the formula (18) with the orange dye of the formula (19), or a mixture of the dyes of the formulae (18) andlor (19) w;th the dye of the formula ~ ~.-n-so2-.~ ~.
\Cl ~=N-~ -~C~-CH3 ,~ ~ (20) H2N' ~
~ Cl i '!
HO3S ~-/
are used, in weight ratios of the dyes of formulae (18) and (19) of 60:40 to 40:60 and in particular 1:1 and weight ratios of the dyes of the formulae (18) or (19) and (20) of 80:20 to 20:80 and in particular 70:30 and weight ratios of the dyes of the formulae (18), t19) and t20) of 60:20:20, 20:60:20 to 20:20:60 and in particular 1:1:1, or the yel-low dye of the formula -- ---SO
N = N-- - ~ \ / 3 (21), ~./ H
o~
In a very part;cularly preferred embodiment of the process according to the invention, a blue dye of the formula (14), (15), (16) or t17) or a mixture of the dyes of the formulae (15~ and (17) is used in a weight rat;o of in particular 70:30 together with a red dye of the formulae H3C-N-~ /
il-N=N-~ (22), ~. o~
\SO3H
0- ~
SO =--N - N~ - (23) or / HO /
\S03H
ICF3 H2N~
C0 ~ ~- ~ ~ ( 2 4 ) and c~3 \S03H
the yellow dye of the formula (18), (19) or (21) or the mixture of the yellow dyes of the formulae (18) and (20) ;n a weight ratio of 70:30.
In a very particularly important embodiment of the process according to the invention, a dye of the formula (14) or (15) is used together with a dye of the formula (22) and ~he dye of the formula (19).
The dyes used for trichromatic dyeing in the pro-cess according to the invention are known or can be pre-pared analogously to a known method. For instance, the dyes of the formula (1) can be prepared as indicated in German Offenlegungsschriften 2,305,206 and 3,142,852, in lz~$~lo2 Sw;ss Patent 466,470 and ;n British Patent 903,590, the dyes of the formula (2) are indicated in German Patents 702,932 and 2,063,907 and in German Offenlegungsschrift 2,712,170 and the dyes of the formulae (3) and (4) as in-dicated in German Offenlegungsschrift 2,142~412 and German Auslegeschrift 1,100,~46.
Mixtures of dyes used in the process according to the invention can be prepared by mixing the individual dyes, for example in suitable mills, for example ball and pin mills, and in kneaders or mixers.
Mixtures of dyes can also be prepared by spray-drying the aqueous mixtures of dyes.
The dyes used in the process according to the invention are either in the form of their free sulfonic acid or preferably in the form of its salts.
Examples of suitable salts are the alkali metal, alkaline earth metal and ammonium salts and the salts of organic amines. Examples are the sodium, lithium, potas-sium and ammonium salts and the salt of triethanolamine.
The dyes used in the process according to the in-vention generally contain further additives, such as sodium chloride or dextrin.
The novel process for trichromatic dyeing can be applied to the customary continuous dyeing methods. The dyeing liquors, in addition to water and the dyes, can contain further additives, for example wetting agents, antifoams, levelling agents or agents which affect the nature of the textile material, for example softeners, fire retardants or soil-, water- or oil-repellent agents, and water-softening agents and natural or synthetic thick-eners, for example alginates or cellulose ethers.
The process according to the invention is parti-cularly suitable for dyeing from short liquors and employed for example in continuous dyeing methods or/and continuous foam-dyeing methods.
The dyes used in the process according to the invention are distinguished in trichromatic dyeing by ~2~ Z
uniform build-up, good exhaustion properties, good shade consistency even in different concentrations, good fastness properties, in particular very good ozone fastness, and good compatibility.
The process according to ~he invention is suitable for the continuous dyeing of synthetic polyamide materials, for example nylon or Perlon, in particular nylon 66 and preferably nylon 6 materials.
Said textile material can be dyed at various stages in processing, for example as fibre, yarn, woven fabric or knitted fabric and in particular as carpet~
The particularly noteworthy good ozone fastness of the dyeings obtained wi~h the process according to the invention is determined by American Association of Textile Chemists and Colorists test methods 109-1975 and 129-1975~
The amounts in which the dyes or mixtures are used in the dyebaths can vary ~ithin wide limits depending on the desired depth of shade; in general amounts of 0~001 to 6% by weight on weight of fibre have been found to be advantageous.
The liquor ratio can be chosen within a wide range, in particular from 1:1 to 1:5 in the case of continuous dyeing methods.
Dyeing takes place from an aqueous liquor at tempera-tures between 6û and 98C. Preferably the dyeing liquor is hot when padded or sprayed on the cloth.
The pH range of the dyeing liquor can vary within the range from 5 to 9. In general, a pH of 6 to 8.5 has been found to be advantageous.
In the following examples, parts are by weight.
The temperatures are given in degrees centigrade. Parts by weight relate to parts by volume as the gramme relates to the cub;c centimetre.
Example 1: An aqueous solution containing per litre 0.65 9 of the dye of the formula - ~L2~ )2 ~OCH3 H03S~ N=N~ -N=N-~ OCH3 (19), CH/
0.29 9 of the dye of the formuLa H C N / H \
lso2 NH2~
il-N = N--~ ~- (21) HO
\S03H
and 0.57 9 of the dye of the formula i il i S03H
./ \./ \.~ H3C~ ~C~2NHCOCH2Cl t15) \.=./ 3 H3C CH2NHcocH2cl as well as 3 9 of an anionic wetting agent is brought to pH 8.2 with Na3P04.
300X on weight of fibre of this liquor are applied to a non-prewetted nylon 6 grey state carpet at a liquor temperature of 22 and a carpet speed of 8 metres per minute. The impregnated carpet then passes into a steamer where it is treated with saturated steam at 98 to 100 for four minutes.
The result after a wash in an open-width washer is a carpet in a brown shade which is level in respect of the surface of the carpet and in respect of the individual fibre and has good ozone fastness.
The ozone fastness of the dyeing obtained is tested in accordance with AATCC CAmerican Association of Textile Chemists and Colorists] test method 129-1975, and the colour change is evaluated against the standard grey scale CSNV
(S~iss Standards Institute) stanclard 95805] where 1 is worst and 5 is best.
The dyeing obtained with the above dyes has a fastness level of 4.
The above example is repeated, except that a hot liquor at 90 is used in place of the cold liquor, afford-ing without the use of a steamer or with a residence time in saturated steam at 98 or 100 of one minute a carpet likewise dyed in a level brown of good ozone fastness 4.
Example 2: An aqueous solution containing per litre 0.15 9 -of the dye of the formula ~OCH3 HO3S~ --N=N--~ ~--N=N--~ ~--OCH3 (19), =. =-- .=--0.1 9 of the dye of the formula 3 1 \ /
1 2 ~H2\
i~ il-N=N--\ ~- (22), 0~125 9 of the dye of the formula 3~)2 Il l ;~ \i/ \j/ ~ SO H
./ \~/ \.~ H3C~ ~CH2NHCOCH2Cl (14), O NH~ -CH3 2.0 9 of the ammonium sulfate ester of ethoxylated nonyl-phenol and 0.5 9 of ethoxylated nonylphenoL is brought to pH 8.0 with a mixture of Na2HP04 and NaH2P04 and is heated to 96 to 9~. The hot solution is sprayed in a sealed chamber through a number of nozzles under a pressure of 3 atmospheres onto a nylon 66 carpet passing continu-ously through the chamber. The residence time of the carpet in the chamber is about 5 seconds. The liquor pick-up is about 500% on weight of fibre. The result is a nylon 66 carpet dyed a level brown of ozone fastness 3-4, the ozone fastness being assessed as indicated in Example 1.
Example 1 is repeated, except that instead of the combination of dyes of the formulae (19), (22) and (15) which is mentioned in Example 1 the combination of dyes which is indicated in the Table below in Examples 3 to 12 in column II is used in the amounts indicated there, like-wise affording carpets which have been dyed a level olive to brown shade and have good ozone fastness, the ozone fastness being assessed as in Example 1 and the fastness level being indicated in column III.
~$~
Table .... ~
Ex- Dyes Fast-ampLe ness Level 3 0.84 g/l of the dye of the formula 3~4 3 \ ~ \ ;, OCH3 1.78 g/l of the dye of the formula 3 ~ \ /
t 11 ` , û.98 g/L of the dye of the formula _ _ 4 0.92 g/l of the dye of the formula (19) 4 1.67 g/l of the dye of the formula (22) and 0.76 g/l of the dye of the formula .~ So3H
li ~ -W`CO-~
~zL~
Ex- Dyes Fast-ample ness level 0.90 g/l of the dye of the formula (19), 4 1.30 g/l of the dye of the formula ~22~ and 1.02 g/l of the dye of the formula !~ C~3 ~03H (26) \.=./ 3 G~3 ~'H-C0-CHBr-CH2Br _ , .
6 0.92 g/l of the dye of the formuLa (19), 3-4 1.33 g/l of the dye of the formula (22) and 1.89 g/l of the dye of the formula ~._ / 3 .
pyrimidinyl, 2-fluoro-5-bromo-6-trjfluoromethyl-4-pyrim dinyl, 2-fluoro-6-carboxamido-4-pyrimidinyl, 2-fLuoro-6-carbomethoxy-4 pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimi-dinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluorc-5-sulfonaMido-4-pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimi-dinyl, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl; 2,4-bis-methylsulfonylpyrimidin-4-yl, 2~5-bis-methylsulfonyl-5-chloropyrimidin-4-yl, 2-methylsulfonyl-pyrimidin-4-yl, 2-phenylsulfonyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-methylpyrimidin-4-yl, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimi-din-4-yl, 2-methyLsulfonyl-5-chloro-methylpyrimidin-4-yl, 2-methylsulfonyl-5-nitro-6-methylpyrimidin-4-yl, 2,5,6-tris-methylsulfonyl-pyrimidin-4-yl, 2-methylsulfonyl-5,6-dimethylpyrimidin-4-yl, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-6-chloro-pyrimidin-4 yl, 2,6-bis-methylsulfonyl-5-chloropyrimidin-4-yl, 2-methyl-sulfonyl-6-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-5-sulfo-pyrimidin-4-yl, 2-methylsulfonyl-6-carbomethoxy-pyrimidin-4-yl, 2-methylsulfonyl-5-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-5-cyano-6-methoxy-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-pyrimidin-4-yl, 2-sulfoethyL-sulfonyl-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-5-bromo-pyrimidin-4-yl, 2-phenylsulfonyl-5-chloro-pyrimidin-4-yl, 2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2,4-dicnloropyrimidine-6-carbonyl or -6-sulfonyl, 2,4-dichloropyrimidine-5-carbonyl or -5-sulfonyl, 2-chloro-4-methylpyrimidine-5-carbonyl, 2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio-4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloropyrimidine-5-carbonyl, 2,4,6 tri-chloropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl, 2,4-dichloro-6-methylpyrimidine-5-carbonyl or -5-sulfonyl, 2-methylsulfonyl-6-chloropyrimidin-4-yl and -5-carbonyl, 2,6-bis-(methylsulfonyl)-pyrimidine-4- or -5-carbonyl, 2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl, 2,4-bis-lmethylsulfonyl)-pyrimidine-5-sulfonyl, 2-methyl-sulfo-nyl-4-chloro-6-methyl-pyrimidine-5-sulfonyl or -5-carbonyl;
2-chloroquinoxaline-3-carbonyl, 2- or 3-monochloroquinox-al;ne-6-carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5- or -6-carbonyl, 2,3-dichloroquin-oxaline-5- or 6-sulfonyl, 1,4-dichlorophthalazine-6-sul-fonyl or -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-sulfonyl or -carbonyl, 2,4,6-trichloroquinazoline-7- or -8-sulfonyl, 2- or 3- or 4-(4',5'-dichloropyridaz-6' on-1'-yl~-phenylsulfonyl or -carbonyl,~ -(4',5'-dichloropyri-dazin-6'-on-1'-yl)-propionyl, 3,6-d;chLoro-pyr;daz;n-4-carbonyl or -4-sulfonyl, 2-chlorobenzoth;azole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonylbenzoth;azole-or Z-alkyLsulfonylbenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, such as 2-methylsulfonylbenzothiazole- or 2-ethyl-sulfonylbenzothiazole-5- or -6-sulfonyl- or -carbonyl~ 2-phenylsulfonylbenzothiazole-5- or -6-sulfonyl or -carbonyl and the corresponding 2-sulfonylbenzothiazole-5- or -6-carbonyl or -sulfonyl der;vatives which contain sulfo groups in the fused-on benzene ring, 2-chlorobenzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chlorobenzim;dazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-1-methylbenz;midazole-5-or -6-carbonyl or -sulfonyl, 2-chloro-4-methyl-1,3-thiazole-5-carbonyl or -4- or -5-sulfonyl; ammonium-containing tri-az;ne rings, such as 2-trimethylammonium-4-phenylamino-or -4-(o-, m- or p-sulfophenyl)-amino-tr;azin-6-yl, 2-(1,1-dimethyl-hydrazinium)-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-aminotriazin-6-yl, 2-(2-isopropylidene-1,1-dimethyl)-hydrazinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-aminotriazin-6-yl, 2-N-aminopyrrolidinium-or 2-N-aminopiperidinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-aminotriazin-6-yl, and also 4-phenylamino-or 4-(sulfophenylamino)-triazin-6-yl radicals which, in the 2-position, contain 1,4-bis-azabicycloC2.2.2.]octane or 1,2-bis-azabicyclo~0.3.3.]-octane via a quaternary nitrogen bond, 2-pyridinium-4-phenylamino- or -4 (o-, m-or p-sulfophenyl)-amino-triazin-6-yl and corresponding 2-oniumtriazin-6-yl radicals wh;ch are substituted in the 5~
4-position by alkylamino, such as methylamino, ethylamino or ~-hydroxyethylamino, or alkoxy, such as methoxy or ethoxy, or aryloxy, such as phenoxy, or sulfophenoxy groups.
An interesting fibre-reactive radical can also be a chloro- or fluoro-1,3,5-triazine radical of the formula F, Cl V
where the substituent V on the triazine ring can be in particular:
halogen, for example chlorine or fluorine, C1_8-alkoxy, for example methoxy, cyclohexyloxy, phenoxy, C1_6-alkylmercapto, such as methylmercapto, phenylmer-capto, -NH2, alkylamino, N,N-dialkylamino, cycloalkyl-amino, N,N-dicycloalkylamino, aralkylamino, arylamino, mixed-substituted amino groups, such as N-alkyl-N-cyclo-hexylamino and N-alkyl-N-arylamino groups, and also amino groups wh;ch contain heterocyclic radicals which can have further fused-on carbocyclic rings, and amino groups in which the amino nitrogen atom is a member of an N-hetero-cyclic ring which can contain further hetero atoms, as well as hydrazino and semicarbazido. The abovementioned alkyl rad;cals can be straight-chain or branched and of low molecular weight or higher molecular weight and are preferably alkyl radicals having 1 to 6 carbon atoms, cycloalkyl, aralkyl and aryl radicals can be in particular cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radi-cals; heterocyclic radicals can be in particular furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, ben-zimidazole, benzothiazole and benzoxazole radicals; and amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring are preferably radicals of six-membered N-heterocyclic compounds which can contain nitro-gen, oxygen or sulfur as further hetero atoms. The above-mentioned alkyl, cycloalkyl, aralkyl and aryl radicals, O~
the heterocyclic radicals and the N-heterocyclic rings can be further substituted, for example by: halogen, such as fluorine, chlorine or bromine, nitro, cyano, trifluoro-methyl, sulfamoyl, carbamoyl, C1_~,-alkyl, C1_4-alkoxy, acylamino groups, such as acetylamino or benzoylamino, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo. Examples of such amino groups are: -NH2, methylamino, ethylamino, propylamino, isopropylamino, butylamino, hexylamino,~ -methoxyethylamino, ~-methoxypropylamino, ~-ethoxyethyl-amino, N,N-dimethylamino, N,N-diethylamino,~ -chLoroethyl-amino, ~cyanoethylamino, ~-cyanopropylamino, ~-carboxyethyl-amino, sulfomethylamino,~ -sulfoethylamino, ~-hydroxy-ethylamino, N,N-di-~-hydroxyethylamino,~-hydroxypropyl-amino, benzylamino, phenethylamino, cyclohexylamino, phenylamino, toluidino, xylidino, chloranilino, anisidino, phenetidino, N-methyl-N-phenylamino, N-ethyl-N-phenylam;no, N-~-hydroxyethyl-N-phenylamino, 2-, 3- or 4-sulfoanilino, 2,5-disulfoanilino, 4-sulfomethylanilino, N-sulfomethyl-anilino, 2-, 3- or 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfo-naphth-1-ylamino, 3,6-disulfonaphth-1-ylamino, 3,6,8-trisulfonaphth-1-ylamino, 4,6,8-trisulfonaphth-1-ylamino, 1-sulfonaphth-2-yl-amino, 1,5-disulfonaphth-2-yl-amino, 6-sulfonaphth-2-yl-amino, morpholino, piperidino, pipera-zino, hydrazino and semicarbazido.
In particularly preferred embodiments o-f the pro-cess accordin~ to the invention, a) a blue dye of the formula - SO H
~ ( )N)o-l (6), in ~hich T is as defined under the formula ~1) and the phenyl ring L1 can be monosubstituted, disubstituted, ~2~0~
trisubstituted or tetrasubstituted by C1_4-alkyl, C1_4-alkoxy or phenoxy, or a blue dye of the formuLa / \i/ ~- ~ (S3H)l 2 0 E~H--~ L2/- ~ (T)1-2 hich Y4 is a C1_6-alkyl or C5_7-cycloalkyl radical, T is as defined in the formula (1) and the phenyl ring L2 can be monosubstituted, disubstituted or trisubstituted by C1_4-alkyl, C1_4-alkoxy, phenoxy or C1_4-alkylphenoxy, or a blue dye of the formula 0 ~H-Y
o~ ,.,!,.,!~. _ - (S03H) 1-2 !~ ! 1 - (T)l-2 (8~
~ O E`IH-(Cl 8-alkylene~-\ L3/~ ,_ in which Y4 is as defined under the formula (7), T is as defined in the formula (1) and the phenyl ring L3 can be monosubstituted or disubstituted by C1_4-alkyl or C1_4-alkoxy, or a blue dye of the formula o ~H-(Cl_6-alk'~l~ne)o_l \ >~
.~ \./ \./
~ ! ! ( 9), / \./ \.~ T
Il I ~o-~O NE~-(Cl-6- alky1ene) ~ -in which T ;s as defined in the formula ~1), is used;
~z~ o;~
b) at least one red dye of the formula (2) in which A ishydrogen, methyl, trifluoromethyl, ~ ~
-CON~ , -SO2N~ or -S02R3 where R~ is methyl or ethyl, R2 is cyclohexyl or phenyl, and R3 is phenyl, methylphenyl, phenoxy or chlorophenoxy, and B is hydrogen, chlorine, acetylamino, propionylamino, cyclohexyloxycarbonylamino, phenylsulfonylamino or methyl-phenylsulfonylamino, A and B not both being hydrogen at the same time, is used; and c) at least one yellow or orange dye of the formula ~CH3 ~l N=N-~ -N N--~ O-X1 ~10), Al in which A1 is hydrogen or methyl, F1 is hydrogen or methyl and X1 is methyl, ethyl, ~-hydroxyethyl,~ -hydroxy-propyl, ~-hydroxybutyl or ~-ethyl-~-hydroxyethyl or a mix-ture of at least one dye of the formula (10) and a yello~
dye of the formula ~ ~--O-S02--~ ~-Z
N
.~ ~. ( 1 1 ), Z + 1I SO H
6 ~ /- 3 in which Zs and Z6~ independently of each other, are each hydrogen, methyl or chlorine, or a yello~ dye of the formula w~ I ~so3H
n~
in which W1 ;s hydrogen, methyl, chlorine, methoxy, ethoxy, o-methylphenoxy, phenoxy, acetylamino, phenylsul-fonyl, p-methylphenylsulfonyl, p-chlorophenylsulfonyl, naphthylsulfonyl, p-methylbenzoyl or p-chlorobenzoyl, W2 is hydrogen, chlorine, methyl, tr;fluoromethyl, o-methyl-phenoxy, o-chlorophenoxy, o-chlorophenoxysulfonyl, -S02NHz, N-C1_2-alkylaminosulfonyl, N,N-dimethylaminosulfonyl, N-methyl-N-~-hydroxyethylaminosulfonyl, N-methyl-N-cyclo-hexylaminosulfonyl, N-phenylaminosulfonyl, N-o-methyl-phenylaminosulfonyl, N-o-chlorophenyLaminosu~fonyl, N-m-trifluoromethylphenylaminosulfonyl, N-ethyl-N-pheny'amino-sulfonyl~ CONH2 or -CON(CH3)2, W3 is methyl or phenyl and W4 is hydrogen~ methyl, ethyl or octyl, is used.
In particularly interesting embodiments of the process according to the invention d) a dye of the formula (6) or (7) is used:
e) use is made of anthraquinone dyes of the formulae (6) to (9), in particular of the formulae (6) or ~7) in which T is a fibre-reactive radical of the aliphatic, aromatic or heterocyclic series which can be bonded via a bridge member of the formula ~ ~ o l ~ ~ 3 o--1 or via -CH2-N- or -CH~-~(R4), and R4 is hydrogen or C1 4-alkyl;
f) use is made of anthraquinone dyes of the formulae (6) to (9) in which T is a chloroacetyl, bromoacetyl, acryloyl, ~,~-dichloropropionyl, ~-~-dibromopropionyl, ~-bromoacryl-oyl or ~-chloroacryloyl radical which is bonded via -NH, -CH-NH- or -CH2-NH- or is a radical for the formulae COOH
~2~
-NH ~ Cl ~! ,F, Cl N~ ~ or N~ ~
R5 F, C1 in ~hich R5 is C1_6-alkoxy, c1_6-alkYlmercapto or a radical of the formula _N~6 where R6 and R7, ~ 7 independently of each other, are each hydrogen, C1_6-alkyl or substituted or unsubstituted phenyl or naphthyl, or is a vinylsulfonyl, ~-sulfatoethylsulfonyl, ~-acetoxyethyl-sulfonyl, ~-chloroethylsulfonyl or g-~'-sulfatoethylsul-fonyL)-propionylaminomethyl radical;
g) use is made of preferably a blue anthraquinone dye of the formula o NH
SO ~1 / \ / \ ~
I\._./ 2 tl3), \.=./ 3 G/ \G
in which G1, G3 and Gs are each methyl, G4 is q-chloro-acryloylaminomethyl or d-bromoacryloylaminomethyl, d,~-dibromopropionylaminomethyl, ~-(g'-sulfatoethylsulfonyl)-propionylaminomethyl, ~,~-dibromopropionylamino -CH ( COOH) -.~'H-CO-~H
H2Br or chloroacetylaminoethyl and G2 is hydrogen, sulfo or chloro-acetylaminomethyl or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which G1 is hydrogen or methoxy, G2, G3 and Gs are each hydro-gen and G4 is sulfatoethylsulfonYl, chloroacetylamino, ~g-dibromopropionylamino, vinylsulfonyl, 2-methoxy-4-fluoro-s-triazinylamino or 2-ethylamino-4-fluoro-s-triazinylamino, or in ~hich G1, G2, G4 and GS are each hydrogen and G3 is g~oz chloroacetylamino, ~p,-dibromopropionylamino~ 2,6-difluoro-5-chloropyrimidin-4-yl-amino or 2-chloro-4-amino- or 4-N,N-di-methylamino-s-triazinylamino, or in which G1 is methyl, G2 is ~-sulfatoethylsulfonyl and G3, G4 and G5 are each hydrogen, or in which G1 or G2 is sulfo~ G3 is ~- bromo-acryloylamino or N-methyl-N-[3-(~-chloroethylsulfonyl~-ben-Y mino and G2 or G1 and G4 and G5 are each hydro-gen, or G1, G2 and G5 are each hydrogen, G3 is methyl and G4 is chloroacetylamino, or in which G1 is methyL, G2 is 2,6-difluoro 5-chloropyrimidinylamino, G4 is sulfo and G3 and Gs are each hydrogen; and h) in particular a dye of the formula (13) in which G1, G2, G4 and Gs are each hydrogen and G3 is chloroacetyl-amino or ~v~-dibromoprop;onylamino, or in which G1, G2, G3 and G5 are each hydrogen and G4 is vinylsulfonyl, chloro-acetylamino, 2-methoxy- or 2-ethylamino-4-fluoro-s-triazinyl-amino, or in which G1, G3 and Gs are each methyl, G2 is hydrogen and G4 is chloroacetylaminomethyl, ~
dibromopropionylaminomethyl or -CHtCOOH)-NH-CO-CHBr-CH2Br, or in which G1 is methoxy, G2, G3 and G5 are each hydrogen and G4 is ~-sulfatoethylsulfonyl, or in which G1, G3 and Gs are each hydrogen and G2 and G4 are each chloroacetylaminomethyl or -CH(COOH)-NH-CO-CHBr-CH2sr, or in which G1, G3 and Gs are each methyl, G2 is ~v~~
dibromopropionylamino and G4 is sulfo, or in which G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~-bromoacryloylamino, or in which G1 is methyl, G2 is 2,6-difluoro-5-chloropyrimidylamino, G3 and G5 are each hydro-gen and G4 is sulfo; or i) use is made of a blue dye of the formula (1) in which Y1 is cyclohexyl, Y2 is hydrogen, Y3 is 4-(4'-methyl-phenoxy)-phenyl and T is chloroacetylaminomethyl and the dye contains a single sulfo group, or in which Y1 is isopropyl, Y2 is hydrogen and Y3 is a phenyl-sec.-butyl radical which is subst;tuted in the phenyl ring by sulfo and chloroacetylaminomethyl or is a diphenyl ether radical which is substituted in the phenoxy radical by sulfo and acryLoylaminomethyl~ or in which Y1 and Y3 both denote a phenyl-sec.-butyl radical which is substituted in the phenyl ring by sulfo and chloroacetylamino methyl, and Y2 is hydrogen, or in which Y1 and Y3 both denote a 4-~-bromo-acryloylamino-3-sulfophenyl radical and Y2 is hydrogen.
Of the dyes given in i), preference is gi~en to the dye of the formula (1) in which Y1 is cyclohexYl, Y2 is hydrogen and Y3 is 4-(4'-methylphenoxy)-phenyl, the phenyl ring of the phenoxy group being substituted by sulfo and chloroacetylaminomethyl.
In a particular~y important embodiment of the pro-cess according to the invention, a blue dye of the formula (13) in which G1, Gz, G4 and Gs are each hydrogen and G~
is ~ dibromopropionylamino, or in which G1, G3, G4 and G5 are each hydrogen and G2 is vinylsulfonyl, chloro-acetylamino, 2-methoxy-4-fluoro-s-triazinylamino or Z-ethylamino-4-fLuoro-s-triazinylamino, or in which G1 is methyl, G2 is 2,6-difluoro-5-chloropyrimidinylamino~ G3 and G5 are each hydrogen and G4 is sulfo, or in which G1 is methoxy, G2, G3 and G5 are each hydrogen and G4 is ~-sulfato-ethylsulfonyl, or in which G1, G3 and G5 are each methyl, G2 is hydrogen or -CH(COOH)-NH-CO-CHBr-CH29r and G4 is ~,g-dibromopropionylaminomethyl or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which G1, G3 and Gs are each methyl, G2 is ~
dibromopropionyLamino and G4 is sulfo, or in which G1 is sulfo, G2, G4 and Gs are each hydrogen and G3 is ~ -bromoacryloylamino, is used together with a red dye of the formula (2) and the yellow or orange dyes of the for-mulae (3) and/or (4) or ~5)~
In very particularly important embodiments of the process according to the invention, the blue dye of the formula R ~H2 S O ~{
Cl .=./ 3 (14), c~3 1;~4~90~
or the dye of the forMula I i1 i1 i C~3 ~CH2~1cOcH2Cl \.=./ 3 (15), CH3 CH2~HCOCH2Cl or the dye of the formu~a ~ ~R ~2~So3H
!~ ,ii, i!, ~! (16), ~H--~ NH-C0-CH2Cl =--or the dye of the formula _ --~H- ~ H ~-.~ \o/ \ /
- ~./ \ / \ ,~ ,CH2-'.~H-CO-CH2Cl (17), O ~H - ~ CH3 ;s used.
In the process according to the invention, it is also possible to use mixtures of two or more anthraquinone dyes of the type defined. In particular, use is made of a mixture of two anthraquinone dyes whose individual components each contain one or two fibre-reactive groups and one or two sulfo groups.
Preferably, each ;ndividual component of the mix-ture corresponds to one of the anthraquinone dyes specified above under the formula (1).
It is very particularly preferred to use in the process according to the invention mixtures of anthraquinone ~J~ 2 dyes of the formulae (6), (7), (8) or (9), i~e. mixtures ;n which one component corresponds to a dye of the formula ~6), (7), (~) or (9) and the other component corresponds to a dye of the formula (6), (7)~ (~) or (9)~ In parti-cular, use is made of a mixture of two anthraquinone dyes in which one component corresponds to a dye of the formula (6) and the other component corresponds to a dye of the formula (6) or (7).
In an important mixture of anthraquinone dyes wh;ch can be used in the process according to the inven-t;on, one component corresponds to a dye of the formula (14), (~15~ or a dye of the formula t7) in which Y4 is cyclohexyl, L2 is substituted by p-methylphenoxy and T is chloroacetylaminomethyl, and the dye of the formula ~7) contains only one sulfo group, and the other component corresponds to a dye of the formula (13) in which G1, G2, G4 and Gs are each hydrogen and G3 is ~,~-dibromo-propionylamino, or in which G1, G3, G4 and G5 are each hydrogen and G2 is vinylsulfonyl, chloroacetylamino, 2-methoxy-4-fluoro-s-triazinylam;no or 2-ethylamino-4-fluoro-s-triazinylamino, or ;n wh;ch G1 is methyl, and G2 is 2,6-difluoro-5-chloro-pyrimidinylamino, G3 and G5 are both hydrogen and G4 is sulfo, or in which G1 is sulfo, G2, G4 and G5 are each hydrogen and G3 is ~-bromoacryl-oylamino, or in which G1, G3 and G5 are each methyl, and G2 is ~,~- dibromopropionylaminomethyl, -CH(COOH)-NH-CO-CHBr-CH2Br or ~,~-dibromopropionylamino and G4 is hydrogen, -CH(COOH)-NH-CO-CHBr-CH2Br or sulfo, or in which G1 is methoxy, G2, G3 and Gs are each hydrogen and G4 is ~-sulfatoethylsulfonyl.
In a particularly important mixture of anthraqui-none dyes which can be used in the process according to ~he ;nvention, one component corresponds to the dye of the formula (14) or (15) and the other component corres-ponds ~o the dye of the formula ~7) in which Y4 is cyclo-hexyl, L2 is substituted by p-methylphenoxy and T ;s chloroacetylaminomethyl and the dye of the formuia (7) contains only one sulfo group.
In a further particularly important mixture of anthraquinone dyes which can be used in the process accord-ing to the invention, one component corresponds to the dye of the formula (14) or (15) and the other component corresponds to the dye of the formula (13) in which G1, G2, G4 and G5 are each hydrogen and G3 is chloroacetylamino.
In a very particularly important mixture of anthra-quinone dyes which can be used in the process according to the invention, one component corresponds to the dye of the formula (15) and the other component corresponds to the dye of the formula (17). Preferably the weight ratio of the dyes of the formulae (15) to (17) is 90:10 to 70:30, in particular 80:20.
In general the weight ratio of the anthraquinone dyes in the mixtures used according to the invention can vary ~ithin ~ide limits. A weight ratio of 90:10 to 10:90 and in particular of 70:30 to 30:70, has been found to be advantageous.
The anthraquinone dyes of the formula (1) or the components of the mixtures of the anthraquinone dyes used in the process according to the invention preferably con-tain only one sulfo group.
In the process according to the invention, the red dye used is preferably j) a red dye of the formula (Z) in ~hich A is hydrogen, N-methyl-N-cyclohexylsulfamoyl, phenylsulfonyl, N-ethyl-N-phenylsulfamoyl, phenoxysulfonyl or trifluoromethyl and B
is hydrogen, acetylamino or cyclohexyloxycarbonylamino;
and in particular k) a red dye of the formula (2) in which A is hydrogen and B is acetylamino or cyclohexyloxycarbonylamino or A
is trifluoromethyl and B is acetylamino or A is phenylsul-fonyl, N-methyl-N-cyclohexylsulfamoyl, N-ethyl-N-phenyl-sulfamoyl or phenoxysulfonyl and B is hydrogen; and the yellow or orange dye of the formulae (3) to (5~ is l) the yellow dye of the formula ~5~102 ~OCH3 \. ./ \ / \ / 3 (18) S~3H
or the orange dye of the formula OCH
HO S--~ ~-N=N--~ N=N~ -OCH t19 C~3 or a mixture of the yeLlow dye of the formula (18) with the orange dye of the formula (19), or a mixture of the dyes of the formulae (18) andlor (19) w;th the dye of the formula ~ ~.-n-so2-.~ ~.
\Cl ~=N-~ -~C~-CH3 ,~ ~ (20) H2N' ~
~ Cl i '!
HO3S ~-/
are used, in weight ratios of the dyes of formulae (18) and (19) of 60:40 to 40:60 and in particular 1:1 and weight ratios of the dyes of the formulae (18) or (19) and (20) of 80:20 to 20:80 and in particular 70:30 and weight ratios of the dyes of the formulae (18), t19) and t20) of 60:20:20, 20:60:20 to 20:20:60 and in particular 1:1:1, or the yel-low dye of the formula -- ---SO
N = N-- - ~ \ / 3 (21), ~./ H
o~
In a very part;cularly preferred embodiment of the process according to the invention, a blue dye of the formula (14), (15), (16) or t17) or a mixture of the dyes of the formulae (15~ and (17) is used in a weight rat;o of in particular 70:30 together with a red dye of the formulae H3C-N-~ /
il-N=N-~ (22), ~. o~
\SO3H
0- ~
SO =--N - N~ - (23) or / HO /
\S03H
ICF3 H2N~
C0 ~ ~- ~ ~ ( 2 4 ) and c~3 \S03H
the yellow dye of the formula (18), (19) or (21) or the mixture of the yellow dyes of the formulae (18) and (20) ;n a weight ratio of 70:30.
In a very particularly important embodiment of the process according to the invention, a dye of the formula (14) or (15) is used together with a dye of the formula (22) and ~he dye of the formula (19).
The dyes used for trichromatic dyeing in the pro-cess according to the invention are known or can be pre-pared analogously to a known method. For instance, the dyes of the formula (1) can be prepared as indicated in German Offenlegungsschriften 2,305,206 and 3,142,852, in lz~$~lo2 Sw;ss Patent 466,470 and ;n British Patent 903,590, the dyes of the formula (2) are indicated in German Patents 702,932 and 2,063,907 and in German Offenlegungsschrift 2,712,170 and the dyes of the formulae (3) and (4) as in-dicated in German Offenlegungsschrift 2,142~412 and German Auslegeschrift 1,100,~46.
Mixtures of dyes used in the process according to the invention can be prepared by mixing the individual dyes, for example in suitable mills, for example ball and pin mills, and in kneaders or mixers.
Mixtures of dyes can also be prepared by spray-drying the aqueous mixtures of dyes.
The dyes used in the process according to the invention are either in the form of their free sulfonic acid or preferably in the form of its salts.
Examples of suitable salts are the alkali metal, alkaline earth metal and ammonium salts and the salts of organic amines. Examples are the sodium, lithium, potas-sium and ammonium salts and the salt of triethanolamine.
The dyes used in the process according to the in-vention generally contain further additives, such as sodium chloride or dextrin.
The novel process for trichromatic dyeing can be applied to the customary continuous dyeing methods. The dyeing liquors, in addition to water and the dyes, can contain further additives, for example wetting agents, antifoams, levelling agents or agents which affect the nature of the textile material, for example softeners, fire retardants or soil-, water- or oil-repellent agents, and water-softening agents and natural or synthetic thick-eners, for example alginates or cellulose ethers.
The process according to the invention is parti-cularly suitable for dyeing from short liquors and employed for example in continuous dyeing methods or/and continuous foam-dyeing methods.
The dyes used in the process according to the invention are distinguished in trichromatic dyeing by ~2~ Z
uniform build-up, good exhaustion properties, good shade consistency even in different concentrations, good fastness properties, in particular very good ozone fastness, and good compatibility.
The process according to ~he invention is suitable for the continuous dyeing of synthetic polyamide materials, for example nylon or Perlon, in particular nylon 66 and preferably nylon 6 materials.
Said textile material can be dyed at various stages in processing, for example as fibre, yarn, woven fabric or knitted fabric and in particular as carpet~
The particularly noteworthy good ozone fastness of the dyeings obtained wi~h the process according to the invention is determined by American Association of Textile Chemists and Colorists test methods 109-1975 and 129-1975~
The amounts in which the dyes or mixtures are used in the dyebaths can vary ~ithin wide limits depending on the desired depth of shade; in general amounts of 0~001 to 6% by weight on weight of fibre have been found to be advantageous.
The liquor ratio can be chosen within a wide range, in particular from 1:1 to 1:5 in the case of continuous dyeing methods.
Dyeing takes place from an aqueous liquor at tempera-tures between 6û and 98C. Preferably the dyeing liquor is hot when padded or sprayed on the cloth.
The pH range of the dyeing liquor can vary within the range from 5 to 9. In general, a pH of 6 to 8.5 has been found to be advantageous.
In the following examples, parts are by weight.
The temperatures are given in degrees centigrade. Parts by weight relate to parts by volume as the gramme relates to the cub;c centimetre.
Example 1: An aqueous solution containing per litre 0.65 9 of the dye of the formula - ~L2~ )2 ~OCH3 H03S~ N=N~ -N=N-~ OCH3 (19), CH/
0.29 9 of the dye of the formuLa H C N / H \
lso2 NH2~
il-N = N--~ ~- (21) HO
\S03H
and 0.57 9 of the dye of the formula i il i S03H
./ \./ \.~ H3C~ ~C~2NHCOCH2Cl t15) \.=./ 3 H3C CH2NHcocH2cl as well as 3 9 of an anionic wetting agent is brought to pH 8.2 with Na3P04.
300X on weight of fibre of this liquor are applied to a non-prewetted nylon 6 grey state carpet at a liquor temperature of 22 and a carpet speed of 8 metres per minute. The impregnated carpet then passes into a steamer where it is treated with saturated steam at 98 to 100 for four minutes.
The result after a wash in an open-width washer is a carpet in a brown shade which is level in respect of the surface of the carpet and in respect of the individual fibre and has good ozone fastness.
The ozone fastness of the dyeing obtained is tested in accordance with AATCC CAmerican Association of Textile Chemists and Colorists] test method 129-1975, and the colour change is evaluated against the standard grey scale CSNV
(S~iss Standards Institute) stanclard 95805] where 1 is worst and 5 is best.
The dyeing obtained with the above dyes has a fastness level of 4.
The above example is repeated, except that a hot liquor at 90 is used in place of the cold liquor, afford-ing without the use of a steamer or with a residence time in saturated steam at 98 or 100 of one minute a carpet likewise dyed in a level brown of good ozone fastness 4.
Example 2: An aqueous solution containing per litre 0.15 9 -of the dye of the formula ~OCH3 HO3S~ --N=N--~ ~--N=N--~ ~--OCH3 (19), =. =-- .=--0.1 9 of the dye of the formula 3 1 \ /
1 2 ~H2\
i~ il-N=N--\ ~- (22), 0~125 9 of the dye of the formula 3~)2 Il l ;~ \i/ \j/ ~ SO H
./ \~/ \.~ H3C~ ~CH2NHCOCH2Cl (14), O NH~ -CH3 2.0 9 of the ammonium sulfate ester of ethoxylated nonyl-phenol and 0.5 9 of ethoxylated nonylphenoL is brought to pH 8.0 with a mixture of Na2HP04 and NaH2P04 and is heated to 96 to 9~. The hot solution is sprayed in a sealed chamber through a number of nozzles under a pressure of 3 atmospheres onto a nylon 66 carpet passing continu-ously through the chamber. The residence time of the carpet in the chamber is about 5 seconds. The liquor pick-up is about 500% on weight of fibre. The result is a nylon 66 carpet dyed a level brown of ozone fastness 3-4, the ozone fastness being assessed as indicated in Example 1.
Example 1 is repeated, except that instead of the combination of dyes of the formulae (19), (22) and (15) which is mentioned in Example 1 the combination of dyes which is indicated in the Table below in Examples 3 to 12 in column II is used in the amounts indicated there, like-wise affording carpets which have been dyed a level olive to brown shade and have good ozone fastness, the ozone fastness being assessed as in Example 1 and the fastness level being indicated in column III.
~$~
Table .... ~
Ex- Dyes Fast-ampLe ness Level 3 0.84 g/l of the dye of the formula 3~4 3 \ ~ \ ;, OCH3 1.78 g/l of the dye of the formula 3 ~ \ /
t 11 ` , û.98 g/L of the dye of the formula _ _ 4 0.92 g/l of the dye of the formula (19) 4 1.67 g/l of the dye of the formula (22) and 0.76 g/l of the dye of the formula .~ So3H
li ~ -W`CO-~
~zL~
Ex- Dyes Fast-ample ness level 0.90 g/l of the dye of the formula (19), 4 1.30 g/l of the dye of the formula ~22~ and 1.02 g/l of the dye of the formula !~ C~3 ~03H (26) \.=./ 3 G~3 ~'H-C0-CHBr-CH2Br _ , .
6 0.92 g/l of the dye of the formuLa (19), 3-4 1.33 g/l of the dye of the formula (22) and 1.89 g/l of the dye of the formula ~._ / 3 .
7 0.86 g/l of the dye of the formula (19), 3-4 1.67 g/l of the dye of the formula (22) and 1.60 g/l of the dye of the formula ~,~ h~ U-CO-CU~CI
Ex- Dyes Fast-ampl ness _ level
Ex- Dyes Fast-ampl ness _ level
8 1.18 g/l of the dye of the formula (19), 4 1.99 g/l of the dye of the formula (22) and 1.14 g/l of the m;xture of the dyes of for-mulae (14) and (17), ~hich contains 80 per cent by weight of the dye of the formula (14) and 20 per cent by weight of the dye of the formula (17), based on 100X of the mixture.
9 1.97 g/l of the dye of the formula 4 ,._.~
1 li N - N~ \i/ 3H (21), 2.47 g/l of the dye of the formula (22) and 1.08 g/l of the mixture of the dyes of for-mulae (14) and (17), ~hich contains 80X by weight of the dye of the formula (14) and 20% by ~eight of the dye of the formula (17), based on 100X of the mixture.
.
1.89 g/l of the dye of the formula 4 ._ ~, . _ ./ 3 ~ N=N~ "-N=N- ~ -OCH3 ( ) 1.06 g/l of the dye of the formula _.~ ~.
~ ~ / N ~1 (23) ~ ¦
-- ~ -Ex- Dyes Fast-ample ness and 1.06 g/l of the dye of formula (14) 11 2~03 g/l of the mixture o-f the dyes of the 4 formula (18) and \ ~ /C ~ 2 ~ ~ ~H (20) , where, based on 100X by we;ght, the mixture contains 70X by weight of the dye of the formula (18) and 30%
by weight of the dye of the formula (20), 0.89 g/l of the dye of the formula I ~-/ dO-.' \ and 1.30 g/l of the mixture of the dyes of the formulae (15~ and (17), which conta ns 80X by weight of the dye of the formula (15) and 20X by weight of the dye of the formula (17), based on 100X of the m;xture.
_ - ~29~ 02 Ex- Dyes Fast-ample level _ _ 12 1.82 g/l of the dye of the formula (19), 4 2.32 g/l of the dye of the formula (22) and I CH3 \~H~
Comparative Example 1 Example 1 is repeated, except that the 0.57 g/l of the dye of the formula (15) is replace by 1.26 g/l of the non fibre-reactive dye of the formula !~ ,il, ,i!, ~i ~CH3 (28) \ _ / 3 \SO ~NHCH2CH20H
afford;ng a carpet of brown shade which, according to the test method for ozone fastness ~AATCC 129-1975] has a fast-ness level for the change of sha~e rSNV standard 95805 of only 2.
Comparative Example 2 Example 1 is repeated, except that the 0.57 g/l of the dye of the formula (15) is replaced by 1.D9 g/l of the non fibre-reactive dye of the formula - ~J~S~o;~
~'H2 .~ \~/ \ /-~ /S03~
C~3 /cl~2~ co-.~ ~. (29), \ -./ 3 c~3 affording a carpet dyed in a brown shade ~hich, according to the test method indicated in Comparative Example 1, has an ozone fastness level of 2.
1 li N - N~ \i/ 3H (21), 2.47 g/l of the dye of the formula (22) and 1.08 g/l of the mixture of the dyes of for-mulae (14) and (17), ~hich contains 80X by weight of the dye of the formula (14) and 20% by ~eight of the dye of the formula (17), based on 100X of the mixture.
.
1.89 g/l of the dye of the formula 4 ._ ~, . _ ./ 3 ~ N=N~ "-N=N- ~ -OCH3 ( ) 1.06 g/l of the dye of the formula _.~ ~.
~ ~ / N ~1 (23) ~ ¦
-- ~ -Ex- Dyes Fast-ample ness and 1.06 g/l of the dye of formula (14) 11 2~03 g/l of the mixture o-f the dyes of the 4 formula (18) and \ ~ /C ~ 2 ~ ~ ~H (20) , where, based on 100X by we;ght, the mixture contains 70X by weight of the dye of the formula (18) and 30%
by weight of the dye of the formula (20), 0.89 g/l of the dye of the formula I ~-/ dO-.' \ and 1.30 g/l of the mixture of the dyes of the formulae (15~ and (17), which conta ns 80X by weight of the dye of the formula (15) and 20X by weight of the dye of the formula (17), based on 100X of the m;xture.
_ - ~29~ 02 Ex- Dyes Fast-ample level _ _ 12 1.82 g/l of the dye of the formula (19), 4 2.32 g/l of the dye of the formula (22) and I CH3 \~H~
Comparative Example 1 Example 1 is repeated, except that the 0.57 g/l of the dye of the formula (15) is replace by 1.26 g/l of the non fibre-reactive dye of the formula !~ ,il, ,i!, ~i ~CH3 (28) \ _ / 3 \SO ~NHCH2CH20H
afford;ng a carpet of brown shade which, according to the test method for ozone fastness ~AATCC 129-1975] has a fast-ness level for the change of sha~e rSNV standard 95805 of only 2.
Comparative Example 2 Example 1 is repeated, except that the 0.57 g/l of the dye of the formula (15) is replaced by 1.D9 g/l of the non fibre-reactive dye of the formula - ~J~S~o;~
~'H2 .~ \~/ \ /-~ /S03~
C~3 /cl~2~ co-.~ ~. (29), \ -./ 3 c~3 affording a carpet dyed in a brown shade ~hich, according to the test method indicated in Comparative Example 1, has an ozone fastness level of 2.
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the continuous trichromatic dyeing of synthetic polyamide materials which comprises using at least one blue-dyeing dye of the formula (13) in which G1, G3 and G5 are each methyl, G4 is ?-chloro-acryloylaminomethyl or ?-bromoacryloylaminomethyl, ?,.beta.-dibromo-propionylaminomethyl, .beta.-(.beta.-sulfatoethylsulfonyl)-propionyl-aminomethyl, ?,.beta.-dibromopropionylamino, -CH(COOH)-NH-CO-CHBr-CH2Br or chloroacetylaminomethyl and G2 is hydrogen, sulfo or chloroacetylaminomethyl or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which G1 is hydrogen or methoxy, G2, G3 and G5 are each hydrogen and G4 is sulfatoethylsulfonyl, chloro-acetylamino, ?,.beta.-dibromopropionylamino, vinylsulfonyl, 2-methoxy-4-fluoro-s-triazinylamino or 2-ethylamino-4-fluoro-s-triazinylamino, or in which G1, G2, G4 and G5 are each hydrogen and G3 is chloroacetylamino, ?,.beta.-dibromopropionyl-amino, 2,6-difluoro-5 chloropyrimidin-4-ylamino or 2-chloro-4-amino- or 4-N,N-dimethylamino-s-triazinylamino, or in which G1 iS methyl, G2 is .beta.-sulfatoethylsulfonyl and G3, G4 and G5 are each hydrogen, or in which G1 or G2 is sulfo, G3 is ?-bromoacryloylamino or N-methyl-N-[3-(.beta.-chloroethyl-sulfonyl)-benzoyl]-amino and G2 or G1 and G4 and G5 are each hydrogen, or G1, G2 and G5 are each hydrogen, G3 is methyl and G4 is chloroacetylamino, or in uhich G1 is methyl and G2 is 2,6-dichloro-5-chloropyrimidinylamino, G4 is sulfo and G3 and G5 are each hydrogen, or at least one blue dye of the formula (1) in which Y1 is cyclohexyl, Y2 is hydrogen, Y3 is 4-(4'-methylphen-oxy)-phenyl and ? is chloroacetylaminomethyl and the dye contains a single sulfo group, or in which Y1 is isopropyl, Y2 is hydrogen and Y3 is a phenyl-sec.-butyl radical which is substituted in the phenyl ring by sulfo or chloroacetylaminomethyl or is a diphenyl ether radical which is substituted in the phenoxy radical by sulfo and acryloylaminomethyl, or in which Y1 and Y3 both denote a phenyl-sec.-butyl radical which is substituted in the phe-nyl ring by sulfo and chloroacetylaminomethyl, and Y2 is hydrogen, or in which Y1 and Y3 both denote a 4-?-bromo-acryloylamino-3-sulfophenyl radical and Y2 is hydrogen, together with at least one red dye of the formula (2) in which A is hydrogen, substituted or unsubstituted C1-4-alkyl, , or -SO2R3, where R1 is C1-4-alkyl, R2 is substituted or unsubstituted C5-7-cycloalkyl or substituted or unsubstituted phenyl, and R3 is substituted or unsubstituted phenyl or substituted or unsubstituted phenoxy, and B is hydrogen, halogen, C2-4-alkanoylamino, C5-8-cycloalkoxycarbonylamino, C1-4-alkoxycarbonylamino, C1-4-alkylsulfonylamino or substituted or unsubstituted phenylsulfonylamino, and with at least one yellow or orange dye of the formulae (3) in which B1, B2 and E1 are each hydrogen, C1-4-alkyl or C1-4-alkoxy and X is straight-chain or branched C1-4-alkyl or straight-chain or branched C2-4-hydroxyalkyl, or (4) in which Z1, Z2 and Z3, independently of one another are each hydrogen, halogen, C1-4-alkyl or C1-4-alkoxy, or mixtures of dyes of the formulae (3) and (4), or a yellow dye of the formula (5) in which W1 is hydrogen, C1-4-alkyl, C1-4-alkoxy, halogen, C2-4-alkanoylamino or a substituted or unsubstituted arylsulfonyl, aryloxy or arylcarbonyl radical, W2 is hydro-gen, halogen, a substituted or unsubstituted alkyl, aryloxy or aryloxysulfonyl radical or a radical of the formula or W3 is a substituted or unsubstituted alkyl or aryl radical, W4 is hydrogen or alkyl and W5 and W6, independently of each other, are each hydrogen or a substituted or unsubstituted alkyl, cycloalkyl or aryl radical.
2. A process according to claim 1, wherein a blue dye of the formula (6) in which T is as defined in claim 1 and the phenyl ring L1 can be monosubstituted, disubstituted, trisubstituted or tetrasubstituted by C1-4-alkyl, C1-4-alkoxy or phenoxy, or a blue dye of the formula (7) in which Y4 is a C1-6-alkyl or C5-7-cycloalkyl radical, T is as defined in claim 1 and the phenyl ring L2 can be monosubstituted, disubstituted or trisubstituted by C1-4-alkyl, C1-4-alkoxy, phenoxy or C1-4-alkylphenoxy, or a blue dye of the formula (8), in which Y4 is as defined under the formula (7), T is as defined in claim 1 and the phenyl ring L3 can be mono-substituted or disubstituted by C1-4-alkyl or C1-4-alkoxy, or a blue dye of the formula (9), in which T is as defined in claim 1, is used.
3. A process according to claim 2, wherein a dye of the formula (6) or (7) is used.
4. A process according to claim 2, wherein use is made of anthraquinone dyes in which T is a fibre-reactive radical of the aliphatic, aromatic or heterocyclic series which can be bonded by a bridge member of the formula or via , and R4 is hydrogen or C1-4 alkyl.
5. A process according to claim 4, wherein use is made of anthraquinone dyes in which T is a chloroacetyl, bromo-actyl, acryloyl, .alpha.,.beta.-dichloropropionyl, .alpha.,.beta.-dibromopro-pionyl, .alpha.-bromoacryloyl or .alpha.-chloroacryloyl radical which is bonded via -NH-, -CH(COOH)-NH- or -CH2-NH- or is a radical of the formulae or in which R5 is C1-6-alkoxy, C1-6-alkylmercapto or a radi-cal of the formula where R6 and R7, independently of each other, are each hydrogen, C1-6-alkyl or substituted or unsubstituted phenyl or naphthyl, or is a vinylsulfonyl, .beta.-sulfatoethylsulfonyl, .beta.-acetoxyethylsulfonyl, .beta.-chloro-ethylsulfonyl or .beta.-(.beta.'-sulfatoethylsulfonyl)-propionylamino-methyl radical.
6. A process according to claim 1, wherein the blue dyes of the formulae (14) (15) (16) or (17) are used.
7. A process according to claim 1, wherein mixtures of two anthraquinone dyes according to the definition given in claim 1 are used.
8. A process according to claim 7, wherein use is made of a mixture in which one component conforms to a dye of the formula (13), (14) or (15) and the other component conforms to the dye of formula (7) in which Y4 is cyclohexyl, L2 is substituted by p-methylphenoxy and T is chloroacetylaminomethyl and the dye of the formula (7) contains only one sulfo group.
9. A process according to claim 1 or 7, wherein monosulfo-containing dyes of the formula (1) are used.
10. A process according to claim 1, wherein use is made of at least one red dye of the formula (2) in which A is hydrogen, methyl, trifluoromethyl, or -SO2R3, where R1 is methyl or ethyl, R2 is cyclohexyl or phenyl and R3 is phenyl, methylphenyl, phenoxy or chloro-phenoxy, and B is hydrogen, chlorine, acetylamino, propionyl-amino, cyclohexyloxycarbonylamino, phenylsulfonylamino or methylphenylsulfonylamino, A and B not being hydrogen at the same time.
11. A process according to claim 10, wherein use is made of a red dye of the formula (2) in which A is hydrogen, N-methyl-N-cyclohexylsulfamoyl, phenylsulfonyl, N-ethyl-N-phenylsulfamoyl, phenoxysulfonyl or trifluoromethyl and B- is hydrogen, acetylamino or cyclohexyloxycarbonylamino.
12. A process according to claim 11, wherein use is made of a red dye of the formula (2) in which A is hydrogen and B is acetylamino or cyclohexyloxycarbonylamino or A is trifluoro-methyl and B is acetylamino or A is phenylsulfonyl, N-methyl-N-cyclohexylsulfamoyl, N-ethyl-N-phenylsulfamoyl or phenoxysulfonyl and B is hydrogen.
13. A process according to claim 1 wherein at least one yellow or orange dye of the formula (10) in which A1 is hydrogen or methyl, F1 is hydrogen or methyl and X1 is methyl, ethyl, .beta.-hydroxyethyl .beta.-hydroxy-propyl, .beta.-hydroxybutyl or .alpha.-ethyl- .beta.-hydroxyethyl, or a mix-ture of at least one dye of the formula (10) and a yellow dye of the formula (11) in which Z5 and Z6' independently of each other, are each hydrogen, methyl or chlorine, or a yellow dye of the formula (12) = in which W1 is hydrogen, methyl, chlorine, methoxy, ethoxy, o-methylphenoxy, phenoxy, acetylamino, phenylsulfonyl, p-methyl-phenylsulfonyl, p-chlorophenylsulfonyl, naphthylsulfonyl, p-methyl-benzoyl or p-chlorobenzoyl, W2 is hydrogen, chlorine, methyl, trifluoromethyl, o-methylphenoxy, o-chlorophenoxy, o-chlorophenoxy-sulfonyl, -SO2NH2, N-C1-2-alkylaminosulfonyl, N,N-dimethylamino-sulfonyl, N-methyl-N-.beta.-hydroxyethylaminosulfonyl, N-methyl-N-cyclohexylaminosulfonyl, N-phenylaminosulfonyl, N-o-methylphenyl-aminosulfonyl, N-o-chlorophenylaminosulfonyl, N-m-trifluoromethyl-phenylaminosulfonyl, N-ethyl-N-phenylaminosulfonyl, -CONH2 or -CON(CH3)2, W3 is methyl or phenyl and W4 is hydrogen, methyl, ethyl or octyl is used.
14. A process according to claim 13, wherein the yellow dye of the formula (18) or the orange dye of the formula (19) or a mixture of the yellow dye of the formula (18) with the orange dye of the formula (19), or a mixture of the dyes of formulae (18) and/or (19) with the dye of the formula (20) are used in weight ratios of the dyes of formulae (18) and (19) of 60:40 to 40:60 and in particular 1:1 and in ratios of the dyes of the formulae (18) or (19) and (20) of 80:20 to 20:80 and in particular 70:30, and in weight ratios of the dyes of the formulae (18), (19) and (20) of 60:20:20, 20:60:20 to 20:20:60 and in particular 1:1:1, or the yellow dye of the formula (21) is used.
15. A process according to claim 1, wherein a blue dye of the formula (14), (15), (16) or (17) or a mixture of the dyes of the formulae (15) and (17) is used in a weight ratio of in particular 70:30 together with a red dye of the formulae = (22) = (23) or (24) and the yellow dye of the formulae(18), (19) or (21) or the mixture of the yellow dyes of the formulae (18) and (20) in a weight ratio of 70:30.
16. A process accordi.ng to claim 15, wherein one of the blue dyes of the formulae (14) or (15) is used together with the red dye of the formula = (22) and the orange dye of the formula (19) = =
17. A process for the trichromatic dyeing of materials made of synthetic polyamide which comprises continuously treating these materials with a dyeing liquor which contains the mixture of dyes according to claim 1 and water and can, if desired, also contain further additives.
18. An aqueous dyeing liquor which contains water and 0.0002 to 6% by weight on weight of water of the mixture of dyes according to claim 1 and can, if desired, also contain further additives.
19. The synthetic polyamide textile material, dyed using the process according to claim 17 and/or the dyeing liquor according to claim 18.
20. The synthetic polyamide carpets, dyed according to
19. The synthetic polyamide textile material, dyed using the process according to claim 17 and/or the dyeing liquor according to claim 18.
20. The synthetic polyamide carpets, dyed according to
claim 19.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66954984A | 1984-11-08 | 1984-11-08 | |
| US669,549 | 1984-11-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1249902A true CA1249902A (en) | 1989-02-14 |
Family
ID=24686762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000494712A Expired CA1249902A (en) | 1984-11-08 | 1985-11-06 | Process for the continuous trichromatic dyeing of synthetic polyamide materials |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0181292B1 (en) |
| JP (1) | JPS61119781A (en) |
| KR (1) | KR860004202A (en) |
| CA (1) | CA1249902A (en) |
| DE (1) | DE3578870D1 (en) |
| DK (1) | DK165338C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0181293B1 (en) * | 1984-11-08 | 1990-10-24 | Ciba-Geigy Ag | Process for dyeing synthetic polyamide materials with anthrachinone reactive dyes |
| EP0360735A1 (en) * | 1988-08-26 | 1990-03-28 | Ciba-Geigy Ag | Process for trichromic dyeing or printing |
| GB2236542B (en) * | 1989-10-06 | 1992-04-15 | Sandoz Ltd | Dye mixtures and their use in trichromatic dyeing processes |
| EP0425435A1 (en) * | 1989-10-23 | 1991-05-02 | Ciba-Geigy Ag | Process for trichromic dyeing or printing |
| US5090964A (en) * | 1989-11-28 | 1992-02-25 | Ciba-Geigy Corporation | Red dye mixtures and their use: dyeing natural or synthetic polyamides |
| US5092906A (en) * | 1989-11-28 | 1992-03-03 | Ciba-Geigy Corporation | Anionic azo dye mixtures and their use for dyeing natural and synthetic polyamides |
| US5096460A (en) * | 1989-11-28 | 1992-03-17 | Ciba-Geigy Corporation | Red dye mixtures and their use: dyeing natural or synthetic polyamides |
| CA2074776C (en) * | 1991-09-27 | 2001-08-14 | Minoru Abe | Dye composition, dyeing method, and dyed protein fiber |
| DE59306811D1 (en) * | 1992-04-01 | 1997-07-31 | Ciba Geigy Ag | Process for dyeing leather with dye mixtures |
| ES2090939T3 (en) * | 1992-09-30 | 1996-10-16 | Ciba Geigy Ag | PROCEDURE FOR DYING NATURAL AND SYNTHETIC POLYAMIDE FIBER MATERIALS WITH DYEING MIXTURES. |
| DE59607383D1 (en) * | 1995-02-10 | 2001-09-06 | Ciba Sc Holding Ag | Dye mixtures and their use |
| JP2003082254A (en) * | 2001-09-17 | 2003-03-19 | Yamada Chem Co Ltd | Navy reactive dye composition and method for dyeing natural protein fiber or blend thereof using the same |
| CA2586610C (en) * | 2005-02-07 | 2013-06-25 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Acid dye mixture |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1016230B (en) * | 1953-12-15 | 1957-09-26 | Ciba Geigy | Process for producing real tints |
| GB1009955A (en) * | 1961-07-06 | 1965-11-17 | Sandoz Ltd | Process for the level dyeing of textile materials of polyamide fibers possessing irregular affinity for dyestuffs |
| GB1371781A (en) * | 1970-09-22 | 1974-10-30 | Sandoz Ltd | Finishing process |
| DE3363011D1 (en) * | 1982-03-12 | 1986-05-22 | Ciba Geigy Ag | Process for dyeing fibrous material from natural polyamides |
| EP0092512B1 (en) * | 1982-04-08 | 1986-04-30 | Ciba-Geigy Ag | Process for trichromatic dyeing or printing |
| US4514187A (en) * | 1982-07-21 | 1985-04-30 | Ciba-Geigy Corporation | Process for dyeing differential-dyeing polyamide fibres |
| US4563192A (en) * | 1983-09-19 | 1986-01-07 | Ciba-Geigy Corporation | Process for dyeing fibre material made of synthetic polyamides with anionic dyes and an auxiliary mixture |
-
1985
- 1985-11-04 DE DE8585810510T patent/DE3578870D1/en not_active Expired - Lifetime
- 1985-11-04 EP EP85810510A patent/EP0181292B1/en not_active Expired - Lifetime
- 1985-11-06 CA CA000494712A patent/CA1249902A/en not_active Expired
- 1985-11-07 DK DK513685A patent/DK165338C/en not_active IP Right Cessation
- 1985-11-07 KR KR1019850008311A patent/KR860004202A/en not_active Withdrawn
- 1985-11-08 JP JP60250606A patent/JPS61119781A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DK513685D0 (en) | 1985-11-07 |
| DE3578870D1 (en) | 1990-08-30 |
| EP0181292A3 (en) | 1987-10-14 |
| DK513685A (en) | 1986-05-09 |
| EP0181292A2 (en) | 1986-05-14 |
| EP0181292B1 (en) | 1990-07-25 |
| KR860004202A (en) | 1986-06-18 |
| DK165338B (en) | 1992-11-09 |
| JPS61119781A (en) | 1986-06-06 |
| DK165338C (en) | 1993-03-29 |
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