CA1101154A - Disperse azo dyestuffs - Google Patents
Disperse azo dyestuffsInfo
- Publication number
- CA1101154A CA1101154A CA302,224A CA302224A CA1101154A CA 1101154 A CA1101154 A CA 1101154A CA 302224 A CA302224 A CA 302224A CA 1101154 A CA1101154 A CA 1101154A
- Authority
- CA
- Canada
- Prior art keywords
- dyestuff
- mixture
- formula
- dyestuffs
- hydrogen
- 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
- 239000000975 dye Substances 0.000 claims abstract description 80
- 239000000203 mixture Substances 0.000 claims abstract description 73
- 229920000728 polyester Polymers 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000000460 chlorine Substances 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052794 bromium Chemical group 0.000 claims abstract description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 47
- 229920002678 cellulose Polymers 0.000 claims description 31
- 239000001913 cellulose Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 239000004753 textile Substances 0.000 claims description 21
- 238000005859 coupling reaction Methods 0.000 claims description 17
- 230000008878 coupling Effects 0.000 claims description 15
- 238000010168 coupling process Methods 0.000 claims description 15
- 238000004043 dyeing Methods 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 9
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 9
- 238000007639 printing Methods 0.000 claims description 9
- 238000004040 coloring Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000001989 diazonium salts Chemical class 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 5
- 125000001246 bromo group Chemical group Br* 0.000 claims description 5
- 238000012505 colouration Methods 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 125000000714 pyrimidinyl group Chemical group 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 37
- 239000006185 dispersion Substances 0.000 description 29
- -1 methyl ethyl Chemical group 0.000 description 29
- 239000000306 component Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 239000000986 disperse dye Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000985 reactive dye Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- KWMDHCLJYMVBNS-UHFFFAOYSA-N 2-bromo-4,6-dinitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1[N+]([O-])=O KWMDHCLJYMVBNS-UHFFFAOYSA-N 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 229960004279 formaldehyde Drugs 0.000 description 3
- BTJCIVXKBILNPY-UHFFFAOYSA-N n-[3-(diethylamino)-4-methoxyphenyl]acetamide Chemical compound CCN(CC)C1=CC(NC(C)=O)=CC=C1OC BTJCIVXKBILNPY-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 1
- GRGSHONWRKRWGP-UHFFFAOYSA-N 2-amino-4-sulfobenzoic acid Chemical compound NC1=CC(S(O)(=O)=O)=CC=C1C(O)=O GRGSHONWRKRWGP-UHFFFAOYSA-N 0.000 description 1
- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical group ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 1
- LHRIICYSGQGXSX-UHFFFAOYSA-N 2-chloro-4,6-dinitroaniline Chemical compound NC1=C(Cl)C=C([N+]([O-])=O)C=C1[N+]([O-])=O LHRIICYSGQGXSX-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000084 Gum arabic Polymers 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
- 229920001407 Modal (textile) Polymers 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000010407 ammonium alginate Nutrition 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 229960000443 hydrochloric acid Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- OSAFFDYLMYICLO-UHFFFAOYSA-N n,n-diphenyl-1,3,5-triazin-2-amine Chemical compound C1=CC=CC=C1N(C=1N=CN=CN=1)C1=CC=CC=C1 OSAFFDYLMYICLO-UHFFFAOYSA-N 0.000 description 1
- SJWQCBCAGCEWCV-UHFFFAOYSA-N n-(3-amino-4-methoxyphenyl)acetamide Chemical compound COC1=CC=C(NC(C)=O)C=C1N SJWQCBCAGCEWCV-UHFFFAOYSA-N 0.000 description 1
- PEMGGJDINLGTON-UHFFFAOYSA-N n-(3-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(N)=C1 PEMGGJDINLGTON-UHFFFAOYSA-N 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
- 125000005184 naphthylamino group Chemical group C1(=CC=CC2=CC=CC=C12)N* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VQTGUFBGYOIUFS-UHFFFAOYSA-N nitrosylsulfuric acid Chemical compound OS(=O)(=O)ON=O VQTGUFBGYOIUFS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 238000010020 roller printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- 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
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0051—Mixtures of two or more azo dyes mixture of two or more monoazo 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/081—Amino benzenes free of acid groups characterised by the amino group substituted amino group unsubstituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino, aralkylamino or arylamino
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
-
- 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
- D06P1/16—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 dispersed, e.g. acetate, dyestuffs
- D06P1/18—Azo dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Dyestuff mixtures comprising two or more monoazo disperse dyestuffs of the formula
Dyestuff mixtures comprising two or more monoazo disperse dyestuffs of the formula
Description
1~01154 This invention relates to disperse azo dyestuffs and more particularly to mixtures of two or more disperse monoazo dyestuffs of closely related structure, to a process of manufacture of the said mixtures and to the application of the said mixtures to aromatic polyester textile materials and aromatic polyester/cellulose unions According to the present invention there is provided a mixture of two or more monoazo dyestuffs of the formula:
2 ~ ~ \
W ~HCOR
' ' ".
wherein W is a chlorine atom or a bro~ine atom;
X is hydrogen or -OR and R, R , Z and Y are lower alkyl groups;
:: . provided that the mixture contains at least one component in which X = H and another in which X=OR .
Throughout this specification by "lower alkyl group"
we mean an alkyl group containing from 1 to 4 carbon atoms As specific examples of lower alkyl groups represented by R, R , Y and æ there may be mentioned methyl ethyl, ~: 20 n-propyl, isopropyl, n-butyl, sec-butyl and isobutyl groups, b~ ~
' . ' ' ' :
11C~1154 In the case in which the mixture of dyestuffs as deined above comprises two components, then these components may be present in the mixture in amounts from 95:5 to 5:95 parts by weight, preferably from 20:80 to 80:20 parts by weight, When three or more component dyestuffs are present in the mixture, no single dyestuff will comprise less than 5% by weight of the total weight of the mixture.
A preferred mixture of dyestuffs according to the 10 invention is that comprising two dyestuffs having the formula:
2 xl / 2 5 2~ =R ~ ~
`
: ~' , .
: : ~ in which the two dyestuffs have W = Br, X = H and W = Br, X = methoxy respectively, : Another preferred mixture of dyestuffs according ,. :
to the invention is that comprising two dyestuffs of formula (II) in which W~= Br, X = H and W = Br, Xl = ethoxyt respectively, : :Yet another preferred mixture of dye~tuffs according : -~;~ 2~0 to~the~invention:is ;that comprising two dyestuffs of formula (II) in which W:= Cl, X = H and W = Cl, Xl = methoxy, respectively.
, ::: ~ ~: : ' ~ 2-., :
"~L7' ,: ; : ~ .: :
- . . .
,,.
. . - . . , . . ~ - ' . : : - :
llQllS4 Still another preferred mixture of dyestuffs accord-ing to the invention is that comprising two dyestuffs of formula (II) in which W = Cl, Xl = H and W = Cl, Xl = ethoxy, respectively It is further preferred that in each of the above-defined mixtures the dyestuffs of formula (II) in which Xl =
H and the dyestuff of formula (II) in which Xl is either methoxy or ethoxy should be in the proportions between approximately 4:1 and approximately 2:1 by weight, respectively Particularly preferred is a mixture comprising two dyestyfs of formula ~II) in which W = Br, X = H and W =
Br, Xl = methoxy, in the proportions of approximately 3:1 by weight respectively.
According to a further feature of the invention there is provided a process for the manufacture of the ~:~ - mixtures o disperse monoazo dyestuffs of formula (I) which comprises coupling a mixture of at least two coupling .
~components of formula X ' : NHCOR
wherein R, X, Y:and Z have the meanings stated above, with a~t least one diazonium compound obtained by diazotisation of an amine of the formula: ~
., - ~ .
-: . ~: , :
~ 3-.
h .
.
~2 2~ 2 (IV) W
wherein W has the meaning stated above, provided that the mixture of coupliny components contains at least one com-ponent in which X is hydrogen and at least one component in which X is o~ .
In the case in which two diazonium compounds are employed in a process as defined above, these may be used by individually diazotising the amines and adding ~he dia-zonium compounds so obtained simultaneously or consecutively to the mixture of coupling components, or the amines may be diazotised in admixture and the mixed diazonium compounds ' ~ so obtained then added to the mixture of coupling components, or the individually prepared diazonium compounds may be mixed together before addition to the mixture of coupling :`: components, :The amine of formula (IV) may be 2, 4-dinitro-6-chloroaniline or 2,4-dinitro-6-bromoaniline, Examples of coupling components of formula (III) -:
: are 5-acetylamino-2-methoxy-N,N-diethylaniline, N,~-diethyl-m-aminoacetani;lide,~ The diazotisation and coupling may be :~
carried out by methods conventionally used for these reactions. Thus diazotisation of the amine or amines of formula ~IV) may be carried out in nitrosylsulphuric acid in known manner, followed by addition of the resulting solution of the diazo compound to a solution or suspension : : ~ of the coupling components in water or in a mixture of water : ~ ~
.' ~ , ' :
-. . .
.~, . . . .
. .
, . ' . i . . ~: . ' .: : . ~
11(~1154 and a water-miscible organic liquid, if necessary adjusting the pH of the mixture to facilitate the coupling reaction, and finally isolating the resulting dyestuff by conventional methods.
In addition to preparing mixtures of dyestuffs according to the invention from mixed coupling components and a single diazo component or mixture of diazo components as defined above, such mixtures may of course be obtained - by mixing together the individually prepared component dye-stuffs of the mixture, obtained by conventional diazotisation and coupling reactions from an amine of formula (IV) and a coupling component of formula (III) The dyestuffs may be applied to polyester textile materials by aqueous dyeing, padding or printing methods in the form of aqueous dispersions which are prepared by conventional methods, for example, by milling the dyestuffs with water and a suitable dispersing agent such as the :~ sodium salt of a naphthalene-2-sulphonic acid/formaldehyde : condensate, and this colouration process constitutes a ::. 20 further feature of the invention The dyestuff mixtures of the present invention , provide navy shades on aromatic polyester textile materials which have very good build-up properties and high tinctorial ~: ; strength superior to the effect achieved by the application of any single component of the dyestuff mixture on its own.
:. :
According to a yet further feature of the invention there is provided a process.for the colouration of aromatic polyester/cellulose unions which comprises applying to the said unions by an aqueous dyeing, padding or printing 30. : process a:mixture of two or more disperse monoazo dyestuffs ;~ ~ - as hereinbe:fore defined.
~ _5_ .
' ~ ' ' ' ' . - ' ' , It is known that the polyester component of a polyester/cellulosic blend can be dyed with disperse dyes, but these dyes suffer from the disadvantage that, particularly when applied by a padding or printing process, they also adhere to the cellulosic component. Because disperse dye-stuffs have low fastness properties on cellulosic materials, that portion of the applied dyestuffs which has stained the cellulose is easily washed off and fades rapidly on exposure to light. Consequently a polyester/cellulose union coloured in this way has poor fastness properties due to loose dye on - the cellulose, In order that the coloured union has the maximum fastness properties it is essential that any unfixed dyestuf f be removed. This is usually achieved by a "reduction clear" treatment of the coloured union (i,e, a treatment in a warm aqueous alkaline solution of sodium hydrosulphite). However, the disposal of the liquors from ; ~ the "reduction clear" treatment causes ecological problems due to the presence of the reducing agent, Also a reduction clear treatment cannot be used after the cellulose poxtion of the blend has been dyed with a dye which is sensitive to this treatment, Further, in the absence of a "reduction clear"
treatment, any dyestuff which is removed by, for example, an~ordinary washing treatment can give rise, especially in the case of printing, to back staining resulting in the " ~ . ~
staining of other ~areas of the print, or dull tones.
The above described problems are minimised by the use of mixtures o~ disperse monoazo dyestuffs as herein-i: :
before d~fined, which cause a minimum of staining of the ; ~cellulose portion of ths blend, ~ :
~ 6-:: : .
-:, ~ ~ , .
- : . - , .
ll~llS4 The process may be carried out by immersing the polyester/cellulose union in a dyebath comprising an aqueous dispersion of the two or more monoazo dyestuffs as defined above, which dyebath preferably contains a non-ionic, cationic and/or anionic surface-active agent, and thereafter heating the dyebath for a period at a suitable temperature, The dyeing process can either be carried out at a temperature between 95 and 100C, preferably in the presence of a carrier such as diphenyl,o-hydroxydiphenyl, methyl naphthalene, methyl salicylate or trichlorbenzene, or at a temperature from 120C to 140C, under superatmospheric pressure, The process of the invention may also be carried out by padding on to the polyester/cellulose union an aqueous dispersion of two or more disperse monoazo dyestuffs as here-inbefore defined, the dyestuffs then being fixed on the union by steaming it for short periods at a temperature between 100 and 180C or baking it at temperatures between 160 i and 220C, If desired the padding liquor can contain the : conventional additives, for example, dispersing agents, thickeners, migration inhibitors or urea, As a further method of application a thickened : printing paste containing the two or more disperse monoazo dyestuffs~in dispersed form can be applied to the surface of ~ the polyesterjcellulose union by any of the methods ': , conventionally used for applying printing pastes to textile : materials, for example by block, screen or roller printing, The printed textile material~ optionally after being dried, `then steamed for short periods at temperatures between :
.
~ ~ 100 and 180C, or is baked at temperatures between 160C
:~ 30 and 220C.~ Suitable thickening agents which are present in ~: the printi~ng paste include gum tragacanth, gum arabic, alginates, for example, sodium or ammonium alginates, oil-.
: ~ in-water or water-in-oil emulsions, or thickening agents of . ~ -7-, -, " ll(~llS4 synthetic origin based on ethylene/maleic anhydride copolymers or polyacrylic acids The printing pastes can also contain conventional additives such as urea, sodium m-nitrobenzene sulphonate, diimides, acids or alkalis to assist in bringing about fixation of the various dyestuffs.
After the dyeing, padding or printing process has been carried out, the coloured textile material is then rinsed in water.
The aromatic polyester/cellulose unions used in the process of the invention can be any textile materials which are mixtures of aromatic polyester fibres and cellulose fibres. Such unions are usually in the form of knitted, or preferably woven goods. The percentage of aromatic polyester fibres is usually in the range of 20 to 95%, and preferably 30 to 85%, by weight of the weight of the union The aromatic polyester fibres are preferably polyethylene terephthalate fibres and the cellulose fibres '~ are preferably cotton, linen, viscose rayon or polynosic ~ rayon fibres, By the use of mixtures of disperse monoazo dyestuffs as hereinbefore defined in the process of the invention the aromatic polyester part of the polyester/cellulose union is coloured in navy shades with excellent reserve of the cellulose part of the union, i.e. the cellulose remains uncoloured or virtually so Any staining of the cellulose ~which does occur can be removed by a "reduction clear"
treatment which is very much milder than that conventionally ; employed, with a corresponding reduction in the effluent disposal problem The process of the present invention can also be appl1ed to the colouration of unions containing aromatic ~' ' .
, 11~1154 polyester and cellulose whereby the mixture of disperse monoazo dyestuffs as hereinbefore defined is applied in conjunction with one or more suitable colouring matters for the cellulose, and this constitutes a still ~urther feature of the invention.
Suitable colouring matters for the cellulose part of the polyester/cellulose unions are Direct Dyestuffs, Vat Dyestuffs, Sulphur Dyestuffs, Azoic Colouring Matters, or Reactive Dyestuf~s.
The mixture of disperse monoazo dyestuffs for the -~
aromatic polyester part of the union and a colouring matter from one of the above-defined classes for the cellulose part of the union may in general be applied concurrently or consecutively, by the conventional processes.
Though the dyes employed in this invention can be applied to a polyester/cellulosic blend by all conventional processes and together with all classes of dyes for cellulose, ;~ a particular advantage of these dyes is that since they have good cellulose reserve and dyeings of high fastness can be obtained using processes which do not involve a reduction clearing treatment. This permits the use of simple and economical processes, as exemplified below, Thus, the polyester!cellulosic material may be padded with a liquor containing disperse and reactive dyes, dried, baked or steamed at high temperature to fix the disperse dyes on the polyester component, padded in aqueous alkali, :
steamed to fix the reactive dye on the cellulosic component, washed and dried.
Alternatively, the pad liquor can contain alkali, 30 ~ and fixation of the reactive dye be achieved during drying _ g_ .~
llQ1154 prior to baking, thus avoiding the need for an alkali pad-steam treatment, In batchwise processing the polyester component can be dyed in any conventional manner, the dyeing given a mild reduction clearing treatment, or no treatment at all, the cellulosic portion then being dyed by any process, using any class of dye for ~ellulose.
The cellulosic portion can first be dyed with a reactive dye, the material rinsed until neutral, and the polyester component then dyed with the mixture of disperse dyes in a separate dyebath either under pressure or with a carrier, washed and dried. Or the cellulose can be dyed first with a reactive dye, after which the mixture of disperse dyes is added to the exhausted dyebath, the pH
adjusted and any auxiliary products added, and the polyester component dyed either at the boil with a carrier, or under pressure.
The reactive dyestuffs used in the process of the invention can be any water-soluble dyestuffs which contain at least one fibre-reactive group, this being defined as ~ a group whose presence in the dyestuff molecule renders `~ the dyestuff capable of chemically combining with hydroxy groups present in cellulose textile materials so that the dyestuff molecule becomes attached to the cellulose molecule through a covalent chemical bond or bonds. Each fibre-reactive group is attached to a carbon atom pxesent in the dyestuff molecule and preferably to a carbon atom of an aromatic ring, preferably a benzene ring, present in the dyestuff molecule. The said dyestuffs are preferably dye-stuffs of the azo, including monoazo and polyazo and metallised azo dyes, anthraquinone, formazan, triphendioxazine, nitro and phthalocyanine series containing at least one fibre-reactive group, l~Q11~4 As examples of fibre-reactive groups there may be mentioned acylamino radicals derived from olefinically unsaturated aliphatic carboxylic acids such as acryloylamino and crotonylamino, or from halogen-substituted aliphatic carboxylic acids such as ~-chloropropionylamino, ~-bromo-propionylamino, ~ -trichlorocrotonylamino and tetra-fluorocyclobutylacryloylamino Alternatively the fibre-reactive group can be a vinyl sulphone, ~-chloroethyl sul-phone, ~-sulphatoethylsulphonyl, ~-chloroethylsulphonamide or an optionally N-substituted ~-aminoethylsulphonyl group The fibre-reactive group is preferably a heterocyclic radical having two or three nitrogen atoms in the hetero-cyclic ring and at least one labile substituent attached to a carbon atom of the heterocyclic ring As examples of labile substituents there may be mentioned chlorine, bromine, fluorine, quaternary ammonium groups, thiocyano, sulphonic acid, hydrocarbylsulphonyl groups, groups of the formula -SC - N wherein the .~ . S
nitrogen atom carries optionally substituted hydrocarbon ; 20 or heterocyclic radicals, and groups of the formula:--- S -- C `~
\ S ,_ wherein the dotted line indicates the atoms necessary to form an optionally substituted or fused heterocyclic ring.
, 11~1154 As specific examples of such fibre-reactive heterocyclic radicalst there may be mentioned 3:6-dichloro-pyridaæine-4-carbonylamino, 2:3-dichloroquinoxaline-5- or 6-(sulphonyl or carbonyl)amino, 2:4-dichloroquinazoline-6-or 7-sulphonylamino, 2:4:6-trichloroquinazoline-7- or 8-sulphonylamino, 2:4:7- or 2:4:8-trichloroquinazoline-6-- sulphonylamino, 2:4-dichloroquinazoline-6-carbonylamino, 1:4-dichlorophthalazine-6-carbonylamino, 4:5-dichloro-pyridazon-l-ylamino, 2:4-dichloropyrimid-5-yl-carbonylamino, : . 10 1-(phenyl-4'-carbonylamino)-4:5-dichloxopyridazone, 2:4-and/or 2:6-dichloro- or bromo-pyrid-6-(and/or -4)ylamino, difluorochloro-pyrimidylamino, trichloropyrimidylamino, tribromopyrimidylamino, dichloro-5-(cyano, nitro, methyl or carbomethoxy)pyrimidylamino, 2-methylsulphonyl-6-chloropyrimid-4-ylcarbonylamino and 5-chloro-6-methyl-2-methylsulphonylpyrimid-4-ylamino, and more particularly . 1:3:5-triazin-2-ylamino radicals which contain a fluorine ~.
,~ or a bromine and, above all, a chlorine atom on at least one of the 4- and 6- positions, for example 4:6-dichloro-1:3:5-triazin-2-ylamino When the triazine nucleus contains only a single halogen atom, preferably a chlorine atom, then the third carbon atom of the triazine ring can be : substituted by a hydrocarbon radical, such as methyl or : phenyl, but more particularly by an optionally substituted hydroxy, mercapto or amino group, such as methoxy, phenoxy, ; : a- and ~-naphthoxy, methylmercapto, phenylthio, methylamino, diethylamino, cyclohexylamino and anilino and ~-alkylanilino and substituted derivatives thereo~ such as anisidino, toluidino, carboxylanilino, sulphoanilino, disulphoanilino and sulphonated naphthylamino.
.
.
.. ... .
Thus a preferred class of the reactive dyestuffs comprises those dyestuffs which contain as the fibre~reactive group a group of the formula:
~ `\
Cl - C C - N -N ~ Cr_lH2r_ ~ C/
Q
wherein r is 1 or 2, and Q is a chlorine atom, an optionally substituted amino group or an etherified hydroxyl group.
The optionally substituted amino groups represented by Q are preferably optionally substituted alkylamino, anilino, or ~-alkylanilino groups, e g, methylamino, ethyl-amino, ~-hydroxyethylamino, di(~-hydroxy-ethyl)amino, ~-methoxyethylamino, ~-sulphatoethylamono, o-, m- and ~-sulphoanilino, 4- and 5-sulpho-2-carboxyaniline, 4- and 5-sulpho-2-methoxyanilino, 4- and 5-sulpho-2-methylanilino, 4-and 5-sulpho-2-chloroanilino, 4- and 5-sulpho-2-chloro-anilino, 2,4-, 2,5- and 3,5-disulphoanilino, N-methyl-m-and p-sulphoanilino.
If desired the fibre-reactive group can be of the type:
~H Jl M J2 wherein Jl is a pyrimidine or triazine ring optionally carrying a labile substituent, J is a pyrimidine or tria-zine ring carrying at least one labile substituent and ~
is a bridging member which is linked to J and J through optionally substituted imino groups, said imino groups being linked together through an alkylene or arylene radical such as ethylene, 1:4 -phenylene or 2-sulpho-1:4-phenylene.
' .. . . . .
Other linking groups of particular interest represented by M are the divalent radicals of stilbene, diphenyl, diphenyloxide, diphenylamine, diphenylurea, diphenoxyethane and diphenylamino-s-triazine, which contain a sulphonic acid group in each benzene nucleus, It is preferred that Jl and J2 should each represent a chloro-s-triazine group, Thus, a further class of reactive dyestuffs comprises those dyestuffs which con-tain as the fibre-reactive group a group of the formula:
~ N \
N~ " N Cr_lH2r-1 ¦
C ~ (7) ~ I M ~ ~ ~ l - Cl ., , I ~
Cp lH2p 1 C lH2 :
wherein r, ~ and ~ are each independently 1 or 2, and M and - Q have the meanings stated above, The group Q, as previously defined, includes within its scope groups which contain a chromophoric system linked ~to the carbon atom of the triazine ring through -~H- or -O-. ~.
.~ ~ '.''' Such reactive dyestuffs can be obtained in conven- ;
tional manner for example by reacting a water-soluble dyestuff containing a primary or secondary amino group with a compound which contains the said fibre-reactive group As examples of such compounds there may be mentioned acryloyl chloride, cyanuric chloride, 2:4:6-trichloropyrimidine, 2:4:6-trichloro-5-(cyano- or chloro-)pyrimidine and 6-methoxy-2:4-dichloro-1:3:5-triazine, Other preferred reactive dyestuffs are those containing one or more phosphorus acid groups, particularly phosphonic acid groups, which are applied to cellulose textile materials by the methods described in U.K, Patent Specification ~o. 1411306.
By this process of the invention aromatic polyester/cellulose unions are coloured in a variety of shades which have excellent fastness to the tests commonly applied to such textile materials, and there is excellent reserve of the white unprinted portions of such textile materials, The preparation of certain coupling components and dyestuffs for the particularly preferred mixtures according to the present invention is described below, Parts are by weight unless otherwise indicated, the : ratio of parts by weight to parts by volume being that of the kilogram to the litre.
11C~1154 Preparation of 5-acetylamino-2-methoxy-N,N-diethylaniline 18 parts of 5-acetylamino-2-methoxyaniline are stirred in 50 parts by volume of water. Aqueous sodium hydroxide solution (70O Tw) is added to adjust the pH to 9-10, The mixture is heated to 65OC and a dispersing agent )polyglycerolricinoleate,0,5 part) is added followed by 29.4 parts of sodium bicarbonate (e~uivalent to 3,5 mols per mole of the aniline ...
starting material). 54 parts of diethylsulphate ~3,5 mols per mol of mol of starting material) is then added over a period of 2 hours at 65C, Reaction proceeded smoothly, Stirring of the mixture at 65C was continued for.a further 2 hours after addition of the diethyl-sulphate to complete the reaction. The reaction mixture . was cooled to room temperature and the 5-acetylamino-2-methoxy-~,~-diethylaniline was collected, washed with water (500 parts of volume) and dried at 70C, ~,~-Diethyl-m-aminoacetanilide is prepared in similar manner starting from m-aminoacetanilide, Preparation of the dyestuff _f formula (II) in which Xl ~.
is methoxy . .:
70 parts (by volume) of 100% sulphuric acid : are added to 4 parts of water, 7 parts of sodium nitrite are then added portionwise to the stirred acid .
at a rate such as to raise the temperature of the mixture to 70~ 2C and to maintain it at that level, : :
On completion of the addition of sodium nitrite.the - .
.' .
, ~.
, , . .
l~llS4 solution is stirred for 1 hour, the temperature being allowed to fall to room temperature 26 2 parts of 2,4-dinitro-6-bromoaniline are added to the stirred sodium nitrite solution at 25-28C during 30 minutes.
On completion of the addition the solution is stirred for 2 hours at room temperature.
23,6 parts of 5-acetylamino-2-methoxy-N,N-diethylaniline are stirred in 500 parts of water and 10 parts by volume o concentrated hydro-chloric acid are added. Ice is added to the solution to lower the temperature to 0C and anhydrous sodium acetate is added to adjust the pH to 3-4. The diazotised amine solution is then added dropwise during 30 minutes at 0C and pH 4 (controlled by the addition of ice and sodium acetate) until only a trace of excess coupling component remains as shown by testing the mixture with diazotised p-nitroaniline, The mixture is stirred for a further 15 minutes at 0-5C, and the dyestuff is collected and washed free from inorganic contaminants with water. The d~estuff is dissolved in boiling acetone, the solution is filtered and the dyestuff is re-precipitated by the addition of ice and water to the acetone solution. The product is again collected, washed with water and dried at 70C.
Preparation of the dyestuff of formula (II) in which X is hydroqen 2,4-Dinitro-6-bromoaniline (2~ 2 parts~ is diazotised and coupled with 20,6 parts of N,N-diethyl-m-aminoacetanilide exactly as described for the preceding preparation, ~lV1~54 The invention illustrated butnot limited by the following Examples in which parts and percentages are by weight Example 1 10 Parts of the dyestuffs o~ formula (II) in which W = Br, Xl = methoxy and W = Br, X = hydrogen respectively are individually gravel milled with 12.8 parts of an aqueous solution of a dispersing agent (sodium salt of a naphthalene-2- sulphonic acid/formal-dehyde condensate), containing 39 2% by weight of theagent, and 77 2 parts of water After 48 hours milling the particle size of each dyestuff in its dispersion is 3-4 microns ~ 0.3 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which,W = Br, X
hydrogen, and 0,075 part of the 10% aqueous dispersion .::
, of the dyestuff of formula (II) in which.W = Br, X
methoxy, both dispersions being obtained as described above, are transferred into a dyeing vessel. 0.5 part by volume of a buffer solution is added, followed by 5 parts of polyester piece textile material. The dye-bath is then made up to 50 parts with water and dyeing ~ is effected under superatmospheric pressure at 130C
:~ for 1 hour.
On completion of dyeing the dyed material is stirred in a reduction clearing bath comprising 5 parts of sodium hydrosulphite, 3 parts by volume of sodium hydroxide solution (70 Tw), 3 parts by volume of a dispersing agent and 490 parts by volume of water, for 30 minutes at 70C. The fibre is then thoroughly washed in a soap solution, rinsed well in water and .~.,~'i ll~llS4 and dried.
The polyester is dyed in a navy blue shade having very good build up and high tinctorial strength.
Example 2 - The dyeing procedure described in Example 1 is repeated except that the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, Xl = H and the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, Xl - methoxy are used in the following amounts:-(II W - Br,X - H(II)W = Br,Xl= methoxv (a) 0.10 0,30 (b) 0,20 0,20 (c) 0,25 0.15 :
(d) 0.30 0,10 (c) 0,35 0,05 In each case a strong navy blue shade on polyester textile material is obtained, Example 3 The dyeing procedure described in Example 1 is repeated except that the 0,075 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X - methoxy is replaced by 0,1 part of a 10% aqueous dispersion of one of the following dyestuffs of formula (I), W, X, Y, Z and R in the table below have the same significance as in formula (I), lS4 W X Y Z R
ta) Br OCH3 CH3 CH3 CH3 (b) Br OCH3C3H7~n) C3H(n) CH3 (c) Br C4 9(-) C2H5 C2H5 CH3 (d) Br OCH3 C2H5 C2H5 C2H5 (e) Cl OCH3 C2H5 C2H5 3 (f) Br 0C2H5 C2H5 C2 5 : (g) Br 3 7(-1 C2H5 C2H5 3 (h) Br OCH3 C4Hg( ) C4Hg(~) CH3 (i) Br OCH3 CH3 C4H9(_) CH3 (j) Br OCH3 C2H5 C2H5 C3H7(n) (k) Br OCH3 C2H5 C2H5 C3H7 (i80) : Each dyestuff mixture when applied to aromatic ; polyester textile material as described in Example 1 gives a strong navy blue shade Example 4 The dyeing procedure described in Example 1 i9 repeated except that the 0, 075 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X = methoxy ~:20 is replaced by 0,1 part of the same dyestuff dispersion, and the 0.3~part of the 10% aqueous dispersion of the formula (II) ` ; ~ in which W = Br, X = hydrogen is replaced by 0.3 part of a :10% aqueous dispersion of one of the following dyestuffs of formula (I). W, X, Y, Z and R in the table below have the same significances as in formula (I).
,~
.
~l~tllS4 W X Y Z R
(a) Br 2 5 C2 5 C2H5 (b) Cl HC2H5 C2H5 CH3 (c) Br HCH3 CH3 CH3 (d) Br H3 7(_) C3H7(_) CH3 (e) Br HC4Hg(_)C4Hg ~) CH3 (f) Br HCH3 CH2cH(cH3) 2 CH3 ~`
(g) Br HC2H5 C2H5 C3H7 ~) Each dyestuff mixture when applied to aromatic polyester textile material as described in Example 1 gives a strong navy blue shade.
ExamPle 5 :, 0 3 part of a 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X = hydro~en, 0.5 par~ of a 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, Xl = methoxy and 0.05 part of a 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X = ethoxy are mixed together. This mixture when applied to aroma~ic polyester textile material by the method described in Example 1 gives strong navy blue shades.
~ ~ .
Similar results are obtained if the dyestuff of formula (II) in which W = Br, Xl = ethoxy is replaced by the dyestuff of formula (I) in which W is bromine, X is methoxy, Y and Z are each n-propyl and R is methyl.
Example 6 A mixture is made in the proportions given below, of the 10% aqueous dispersions of four dyestuffs of formula (I) in which Y and Z are each ethyl, R is methyl and W and X have the meanings given below -21- ~
~j :
, . , 110~
- x -Br H 1.5 part Cl H 1 5 part Br OCH3 0 5 part Cl OCH3 0.5 part This mixture when applied to aromatic polyester textile material by the method described in Example 1 gives strong navy blue shades.
Example 7 26.2 Parts of 2,4-dinitro-6~bromoaniline are diazotised by the method described previously and the diazonium compound so obtained is coupled with a mixture of 6.0 parts of 5-acetylamino-2-methoxy-~ diethyl-aniline and 15.4 parts of ~,~-diethyl-m-aminoacetanilide by the method described previously. The mixed dyestuff so obtained when applied in the form of an aqueous dispersion to aromatic polyester textile material as described in Example 1 gives strong navy blue shades Example 8 The dyeing procedure described in Example 1 is repeated except that the 0 3 part of a 10% aqueous dispersion of the dyestuff of formula (II~ in which W = Br, ~: .
~ xI = hydrogen is replaced by 0.3 part of a l~/o aqueous .
dispersion of the dyestuff of formula (II) in which W =
Cl, X ~= hydrogen, and the 0.075 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which W -Br, X = methoxy is replaced by 0 1 part of a 10% aqueous dispersion of one of the following dyestuffs of formula (I~.
:
W, X, Y, Z and R in the table below have the same signifi-cance as iD formula (I) :
~ ~ -22-, llalls4 W X Y Z R
(a) Cl OCH3 C2H5 C2H5 CH3 (b) Cl C2H5 C2H5 C2H5 CH3 (c) Cl OCH3 C2H5 C2H5 C2H5 (d) Cl OCH3 C3H7(n) C3H7(_) CH3 Each dyestuff mixture when applied to aromatic polyester textile m~terial as described in Example 1 gives a strong navy blue shade.
ExamPle 9 A 67/33 woven blend of polyester/cotton fibres is padded in a pad-liquor of the following constitution, so that the material retains 50% of its weight of the padding liquor, 1 part of the dyestuff of formula (II) in which W = Br, X = hydrogen, as a 10% a~ueous dispersion, 4 parts of the dyestuff of formula (II) in which W = Br, X = methoxy, as a 10% aqueous dispersion, ~- ~ 10 parts urea, 10 parts Matexil FA-MIV (a migration inhibitor marketed by Imperial Chemical Industries Limited;
~ "Matexil" is a Registered Trade Mark) :~ 10 parts sodium bicarbonate per 1000 parts of : pad liquor The dyes are preferably in the form of an aqueous . ~ ~ dispersion, milled in the presence of an equal weight of : a protective agent such as the sodium salt of a naphthalene-2-sulphonic acid/formaldehyde condensate.
-23- :
.
, :~
:' ~.
,. ..
.
The padded material is dried for 30 seconds at 110C, baked for 60 seconds at 210C, rinsed in hot water, treated for 30 seconds at 80C in a solution containing 2 g/litre Synperonic BD (a synthetic detergent marketed by Imperial Chemical Industries Limited, "Synperonic" is a Registered Trade Mark) rinsed in cold water and dried.
The above series of operations can conveniently be carried out as a continuous sequence The polyester portion of the blend is dyed to a full, reddish navy shade while the cotton portion is only slightly stained, and the fabric has good fastness to light and washing.
Example 10 The padding procedure described in Example 9 is repeated except that the dyestuff of formula (II) in which W = Br, Xl = hydrogen and the dyestuff of formula (II) in which W = Br, X = methoxy are used in the following proportions:-(II) W = Br, X = H (II) W = Br, Xl =
. M methoxy (a) 1 0 3.0 (b) 2,0 2.0 : ~c) 2,5 l S
: ~ (d) 3.0 1.0 : (e) 3.5 0 5 In each case a similar result to that describedin Example g is obtained Example 11 The padding procedure described in Example 9 is 30 repeated except that the 1 part of the dyestuff of formula :~
(II) in which W = Br, X = hydrogen.is increased to 3 parts, and the 4 parts of the dyestuff of formula (II) in which . -24-' ' ' ~ '.
11~115~
W = Br, Xl = methoxy are replaced by 1 part of one of the following dyestuffs of formula (I) W,X, Y, Z and R in the table below have the same significance as in formula (I).
W X Y z R
ta) Br OC~3 CH3 CH3 CH3 (b) Br OCH3 C3H7(n) . C3H7(n) CH3 (c) Br OC4Hg~) C2H5 C2H5 CH3 (d) Br OCH3 C2H5 C2H5 CH5 Cl OCH3 C2H5 C2H5 CH3 (f) Br C2H5 C2H5 C2H5 CH3 (g) Br OC3H7(_) C2H5 C2H5 CH3 (h) Bx OCH3 C4Hg(_) C4Hg ~) CH3 (i) Br OCH3 CH3 C4Hg(_) CH3 (i) Br OCH3 C2H5 C2H5 C3H7(n) (k) Br OCH3 C2H5 C2H5 c3H7(iso) In each case a similar result to that described in Example 9 is obtained.
Example 12 The padding procedure described in Example 9 is repeated except that the 4 parts of the dyestuff of formula (II) in which W = Br, Xl = methoxy are reduced to 1 part, and the 1 part of the dyestuff of formula (II) in which W = Br, Xl = hydrogen is replaced by 3 parts of -one of the foll~wing dyestuff of formula (I). W, X, Y, Z and R in the table below have the same significance as - . ..... ................................................................... : .
in formula (I) . ,~' -W X Y Z R
(a) Br H 2 5 C2H5 C2H5 (b) Cl H C2~5 C2H5 CH3 (c) Br H CH3 CH3 3 (d) Br H C3H7(n) C3H7(_) CH3 (e) Br H C4Hg(_) C4H9(n) CH3 (f) Br H CH3 CH2CH(cH3)2 CH3 (g) Br H C2 5 C2Hs C3H7(n) In each case a similar result to ~hat described in Example 9 is obtained.
ExamPle-l3 The padding procedure described in Example 9 is repeated except that the 1 part of the dyestuff of ~ formula (II) in which W = Br, X = hydrogen and the 4 I ~ parts of the dyestuff of formula (II) in which W = Br, xl = methoxy are replaced by 3 parts of the dyestuff of formula (II) in which W = Br, Xl = hydrogen, 0.5 part of the dyestuff of formula (II) in which W = Br, X
methoxy and 0.5 part of the dyestuff of formula (II) in which W = Br, Xl = ethoxy.
A similar result to that described in Example 9 is obtained.
If the dyestuff of formula (II~ in which W = Rr, X = ethoxy is replaced by the same amount of the dyestuff ., ~
of formula (I) in which W is hromine~ R is methyl, X is methoxy, and Y and Z are each n-propyl, a similar result is obtained.
. ~ .
~ -26-~ ' ' .
Example 14 The padding procedure described in Example 9 is repeated except that the 1 part of the dyestuff of formula (II) in which W = Br, Xl = hydrogen and the 4 parts of the dyestuff of formula (II) in which W = Br, Xl =
methoxy are replaced, in the proportions given below, by four dyestuffs of formula (I) in which Y and Z are each ethyl, R is methyl and W and X have the meanings given below:-W X
Br H 1.5 parts Cl H 1.5 parts Br OCH3 0.5 parts Cl OCH3 0.5 parts : A similar result to that described in Example 9 is obtained.
Example 15 A mixture of dyestuffs of formula (II) in which W = Br, Xl = hydrogen and W = Br, Xl = methoxy respectively is prepared as described in Example 7 and converted into 10% aqueous dispersion.
When this dispersion is applied to a polyester/
cotton blend as described in Example 9 a similar result is obtained, Example 16 The padding procedure described in Example 9 is repeated except that the 1 part of the dyestuff of formula (II) in which W = Br, Xl = hydrogen and the 4 parts of the dyestuff of formula (II) in which W = Br, Xl = methoxy are r placed by 3 parts of the dyestuff of ' l~llS4 formula (II) in which W = C1, Xl = hydrogen and 1 part of one of the following dyestuffs of formula (I) respectively.
W, X, Y, Z and R in the table below have the same signifi- -cance as in formula (I), W X Y Z R
(a) C2H5 C2H5 ~H3 (b) Cl C2H5 C2H5 C2H5 CH3 (c) Cl OCH3 C2H5 C2H5 C2H5 (d) Cl OCH3 C3H7~_) C3H7(-) CH3 In each case a result similar to that described in Example 9 is obtained.
-...
' ~ .
'
W ~HCOR
' ' ".
wherein W is a chlorine atom or a bro~ine atom;
X is hydrogen or -OR and R, R , Z and Y are lower alkyl groups;
:: . provided that the mixture contains at least one component in which X = H and another in which X=OR .
Throughout this specification by "lower alkyl group"
we mean an alkyl group containing from 1 to 4 carbon atoms As specific examples of lower alkyl groups represented by R, R , Y and æ there may be mentioned methyl ethyl, ~: 20 n-propyl, isopropyl, n-butyl, sec-butyl and isobutyl groups, b~ ~
' . ' ' ' :
11C~1154 In the case in which the mixture of dyestuffs as deined above comprises two components, then these components may be present in the mixture in amounts from 95:5 to 5:95 parts by weight, preferably from 20:80 to 80:20 parts by weight, When three or more component dyestuffs are present in the mixture, no single dyestuff will comprise less than 5% by weight of the total weight of the mixture.
A preferred mixture of dyestuffs according to the 10 invention is that comprising two dyestuffs having the formula:
2 xl / 2 5 2~ =R ~ ~
`
: ~' , .
: : ~ in which the two dyestuffs have W = Br, X = H and W = Br, X = methoxy respectively, : Another preferred mixture of dyestuffs according ,. :
to the invention is that comprising two dyestuffs of formula (II) in which W~= Br, X = H and W = Br, Xl = ethoxyt respectively, : :Yet another preferred mixture of dye~tuffs according : -~;~ 2~0 to~the~invention:is ;that comprising two dyestuffs of formula (II) in which W:= Cl, X = H and W = Cl, Xl = methoxy, respectively.
, ::: ~ ~: : ' ~ 2-., :
"~L7' ,: ; : ~ .: :
- . . .
,,.
. . - . . , . . ~ - ' . : : - :
llQllS4 Still another preferred mixture of dyestuffs accord-ing to the invention is that comprising two dyestuffs of formula (II) in which W = Cl, Xl = H and W = Cl, Xl = ethoxy, respectively It is further preferred that in each of the above-defined mixtures the dyestuffs of formula (II) in which Xl =
H and the dyestuff of formula (II) in which Xl is either methoxy or ethoxy should be in the proportions between approximately 4:1 and approximately 2:1 by weight, respectively Particularly preferred is a mixture comprising two dyestyfs of formula ~II) in which W = Br, X = H and W =
Br, Xl = methoxy, in the proportions of approximately 3:1 by weight respectively.
According to a further feature of the invention there is provided a process for the manufacture of the ~:~ - mixtures o disperse monoazo dyestuffs of formula (I) which comprises coupling a mixture of at least two coupling .
~components of formula X ' : NHCOR
wherein R, X, Y:and Z have the meanings stated above, with a~t least one diazonium compound obtained by diazotisation of an amine of the formula: ~
., - ~ .
-: . ~: , :
~ 3-.
h .
.
~2 2~ 2 (IV) W
wherein W has the meaning stated above, provided that the mixture of coupliny components contains at least one com-ponent in which X is hydrogen and at least one component in which X is o~ .
In the case in which two diazonium compounds are employed in a process as defined above, these may be used by individually diazotising the amines and adding ~he dia-zonium compounds so obtained simultaneously or consecutively to the mixture of coupling components, or the amines may be diazotised in admixture and the mixed diazonium compounds ' ~ so obtained then added to the mixture of coupling components, or the individually prepared diazonium compounds may be mixed together before addition to the mixture of coupling :`: components, :The amine of formula (IV) may be 2, 4-dinitro-6-chloroaniline or 2,4-dinitro-6-bromoaniline, Examples of coupling components of formula (III) -:
: are 5-acetylamino-2-methoxy-N,N-diethylaniline, N,~-diethyl-m-aminoacetani;lide,~ The diazotisation and coupling may be :~
carried out by methods conventionally used for these reactions. Thus diazotisation of the amine or amines of formula ~IV) may be carried out in nitrosylsulphuric acid in known manner, followed by addition of the resulting solution of the diazo compound to a solution or suspension : : ~ of the coupling components in water or in a mixture of water : ~ ~
.' ~ , ' :
-. . .
.~, . . . .
. .
, . ' . i . . ~: . ' .: : . ~
11(~1154 and a water-miscible organic liquid, if necessary adjusting the pH of the mixture to facilitate the coupling reaction, and finally isolating the resulting dyestuff by conventional methods.
In addition to preparing mixtures of dyestuffs according to the invention from mixed coupling components and a single diazo component or mixture of diazo components as defined above, such mixtures may of course be obtained - by mixing together the individually prepared component dye-stuffs of the mixture, obtained by conventional diazotisation and coupling reactions from an amine of formula (IV) and a coupling component of formula (III) The dyestuffs may be applied to polyester textile materials by aqueous dyeing, padding or printing methods in the form of aqueous dispersions which are prepared by conventional methods, for example, by milling the dyestuffs with water and a suitable dispersing agent such as the :~ sodium salt of a naphthalene-2-sulphonic acid/formaldehyde : condensate, and this colouration process constitutes a ::. 20 further feature of the invention The dyestuff mixtures of the present invention , provide navy shades on aromatic polyester textile materials which have very good build-up properties and high tinctorial ~: ; strength superior to the effect achieved by the application of any single component of the dyestuff mixture on its own.
:. :
According to a yet further feature of the invention there is provided a process.for the colouration of aromatic polyester/cellulose unions which comprises applying to the said unions by an aqueous dyeing, padding or printing 30. : process a:mixture of two or more disperse monoazo dyestuffs ;~ ~ - as hereinbe:fore defined.
~ _5_ .
' ~ ' ' ' ' . - ' ' , It is known that the polyester component of a polyester/cellulosic blend can be dyed with disperse dyes, but these dyes suffer from the disadvantage that, particularly when applied by a padding or printing process, they also adhere to the cellulosic component. Because disperse dye-stuffs have low fastness properties on cellulosic materials, that portion of the applied dyestuffs which has stained the cellulose is easily washed off and fades rapidly on exposure to light. Consequently a polyester/cellulose union coloured in this way has poor fastness properties due to loose dye on - the cellulose, In order that the coloured union has the maximum fastness properties it is essential that any unfixed dyestuf f be removed. This is usually achieved by a "reduction clear" treatment of the coloured union (i,e, a treatment in a warm aqueous alkaline solution of sodium hydrosulphite). However, the disposal of the liquors from ; ~ the "reduction clear" treatment causes ecological problems due to the presence of the reducing agent, Also a reduction clear treatment cannot be used after the cellulose poxtion of the blend has been dyed with a dye which is sensitive to this treatment, Further, in the absence of a "reduction clear"
treatment, any dyestuff which is removed by, for example, an~ordinary washing treatment can give rise, especially in the case of printing, to back staining resulting in the " ~ . ~
staining of other ~areas of the print, or dull tones.
The above described problems are minimised by the use of mixtures o~ disperse monoazo dyestuffs as herein-i: :
before d~fined, which cause a minimum of staining of the ; ~cellulose portion of ths blend, ~ :
~ 6-:: : .
-:, ~ ~ , .
- : . - , .
ll~llS4 The process may be carried out by immersing the polyester/cellulose union in a dyebath comprising an aqueous dispersion of the two or more monoazo dyestuffs as defined above, which dyebath preferably contains a non-ionic, cationic and/or anionic surface-active agent, and thereafter heating the dyebath for a period at a suitable temperature, The dyeing process can either be carried out at a temperature between 95 and 100C, preferably in the presence of a carrier such as diphenyl,o-hydroxydiphenyl, methyl naphthalene, methyl salicylate or trichlorbenzene, or at a temperature from 120C to 140C, under superatmospheric pressure, The process of the invention may also be carried out by padding on to the polyester/cellulose union an aqueous dispersion of two or more disperse monoazo dyestuffs as here-inbefore defined, the dyestuffs then being fixed on the union by steaming it for short periods at a temperature between 100 and 180C or baking it at temperatures between 160 i and 220C, If desired the padding liquor can contain the : conventional additives, for example, dispersing agents, thickeners, migration inhibitors or urea, As a further method of application a thickened : printing paste containing the two or more disperse monoazo dyestuffs~in dispersed form can be applied to the surface of ~ the polyesterjcellulose union by any of the methods ': , conventionally used for applying printing pastes to textile : materials, for example by block, screen or roller printing, The printed textile material~ optionally after being dried, `then steamed for short periods at temperatures between :
.
~ ~ 100 and 180C, or is baked at temperatures between 160C
:~ 30 and 220C.~ Suitable thickening agents which are present in ~: the printi~ng paste include gum tragacanth, gum arabic, alginates, for example, sodium or ammonium alginates, oil-.
: ~ in-water or water-in-oil emulsions, or thickening agents of . ~ -7-, -, " ll(~llS4 synthetic origin based on ethylene/maleic anhydride copolymers or polyacrylic acids The printing pastes can also contain conventional additives such as urea, sodium m-nitrobenzene sulphonate, diimides, acids or alkalis to assist in bringing about fixation of the various dyestuffs.
After the dyeing, padding or printing process has been carried out, the coloured textile material is then rinsed in water.
The aromatic polyester/cellulose unions used in the process of the invention can be any textile materials which are mixtures of aromatic polyester fibres and cellulose fibres. Such unions are usually in the form of knitted, or preferably woven goods. The percentage of aromatic polyester fibres is usually in the range of 20 to 95%, and preferably 30 to 85%, by weight of the weight of the union The aromatic polyester fibres are preferably polyethylene terephthalate fibres and the cellulose fibres '~ are preferably cotton, linen, viscose rayon or polynosic ~ rayon fibres, By the use of mixtures of disperse monoazo dyestuffs as hereinbefore defined in the process of the invention the aromatic polyester part of the polyester/cellulose union is coloured in navy shades with excellent reserve of the cellulose part of the union, i.e. the cellulose remains uncoloured or virtually so Any staining of the cellulose ~which does occur can be removed by a "reduction clear"
treatment which is very much milder than that conventionally ; employed, with a corresponding reduction in the effluent disposal problem The process of the present invention can also be appl1ed to the colouration of unions containing aromatic ~' ' .
, 11~1154 polyester and cellulose whereby the mixture of disperse monoazo dyestuffs as hereinbefore defined is applied in conjunction with one or more suitable colouring matters for the cellulose, and this constitutes a still ~urther feature of the invention.
Suitable colouring matters for the cellulose part of the polyester/cellulose unions are Direct Dyestuffs, Vat Dyestuffs, Sulphur Dyestuffs, Azoic Colouring Matters, or Reactive Dyestuf~s.
The mixture of disperse monoazo dyestuffs for the -~
aromatic polyester part of the union and a colouring matter from one of the above-defined classes for the cellulose part of the union may in general be applied concurrently or consecutively, by the conventional processes.
Though the dyes employed in this invention can be applied to a polyester/cellulosic blend by all conventional processes and together with all classes of dyes for cellulose, ;~ a particular advantage of these dyes is that since they have good cellulose reserve and dyeings of high fastness can be obtained using processes which do not involve a reduction clearing treatment. This permits the use of simple and economical processes, as exemplified below, Thus, the polyester!cellulosic material may be padded with a liquor containing disperse and reactive dyes, dried, baked or steamed at high temperature to fix the disperse dyes on the polyester component, padded in aqueous alkali, :
steamed to fix the reactive dye on the cellulosic component, washed and dried.
Alternatively, the pad liquor can contain alkali, 30 ~ and fixation of the reactive dye be achieved during drying _ g_ .~
llQ1154 prior to baking, thus avoiding the need for an alkali pad-steam treatment, In batchwise processing the polyester component can be dyed in any conventional manner, the dyeing given a mild reduction clearing treatment, or no treatment at all, the cellulosic portion then being dyed by any process, using any class of dye for ~ellulose.
The cellulosic portion can first be dyed with a reactive dye, the material rinsed until neutral, and the polyester component then dyed with the mixture of disperse dyes in a separate dyebath either under pressure or with a carrier, washed and dried. Or the cellulose can be dyed first with a reactive dye, after which the mixture of disperse dyes is added to the exhausted dyebath, the pH
adjusted and any auxiliary products added, and the polyester component dyed either at the boil with a carrier, or under pressure.
The reactive dyestuffs used in the process of the invention can be any water-soluble dyestuffs which contain at least one fibre-reactive group, this being defined as ~ a group whose presence in the dyestuff molecule renders `~ the dyestuff capable of chemically combining with hydroxy groups present in cellulose textile materials so that the dyestuff molecule becomes attached to the cellulose molecule through a covalent chemical bond or bonds. Each fibre-reactive group is attached to a carbon atom pxesent in the dyestuff molecule and preferably to a carbon atom of an aromatic ring, preferably a benzene ring, present in the dyestuff molecule. The said dyestuffs are preferably dye-stuffs of the azo, including monoazo and polyazo and metallised azo dyes, anthraquinone, formazan, triphendioxazine, nitro and phthalocyanine series containing at least one fibre-reactive group, l~Q11~4 As examples of fibre-reactive groups there may be mentioned acylamino radicals derived from olefinically unsaturated aliphatic carboxylic acids such as acryloylamino and crotonylamino, or from halogen-substituted aliphatic carboxylic acids such as ~-chloropropionylamino, ~-bromo-propionylamino, ~ -trichlorocrotonylamino and tetra-fluorocyclobutylacryloylamino Alternatively the fibre-reactive group can be a vinyl sulphone, ~-chloroethyl sul-phone, ~-sulphatoethylsulphonyl, ~-chloroethylsulphonamide or an optionally N-substituted ~-aminoethylsulphonyl group The fibre-reactive group is preferably a heterocyclic radical having two or three nitrogen atoms in the hetero-cyclic ring and at least one labile substituent attached to a carbon atom of the heterocyclic ring As examples of labile substituents there may be mentioned chlorine, bromine, fluorine, quaternary ammonium groups, thiocyano, sulphonic acid, hydrocarbylsulphonyl groups, groups of the formula -SC - N wherein the .~ . S
nitrogen atom carries optionally substituted hydrocarbon ; 20 or heterocyclic radicals, and groups of the formula:--- S -- C `~
\ S ,_ wherein the dotted line indicates the atoms necessary to form an optionally substituted or fused heterocyclic ring.
, 11~1154 As specific examples of such fibre-reactive heterocyclic radicalst there may be mentioned 3:6-dichloro-pyridaæine-4-carbonylamino, 2:3-dichloroquinoxaline-5- or 6-(sulphonyl or carbonyl)amino, 2:4-dichloroquinazoline-6-or 7-sulphonylamino, 2:4:6-trichloroquinazoline-7- or 8-sulphonylamino, 2:4:7- or 2:4:8-trichloroquinazoline-6-- sulphonylamino, 2:4-dichloroquinazoline-6-carbonylamino, 1:4-dichlorophthalazine-6-carbonylamino, 4:5-dichloro-pyridazon-l-ylamino, 2:4-dichloropyrimid-5-yl-carbonylamino, : . 10 1-(phenyl-4'-carbonylamino)-4:5-dichloxopyridazone, 2:4-and/or 2:6-dichloro- or bromo-pyrid-6-(and/or -4)ylamino, difluorochloro-pyrimidylamino, trichloropyrimidylamino, tribromopyrimidylamino, dichloro-5-(cyano, nitro, methyl or carbomethoxy)pyrimidylamino, 2-methylsulphonyl-6-chloropyrimid-4-ylcarbonylamino and 5-chloro-6-methyl-2-methylsulphonylpyrimid-4-ylamino, and more particularly . 1:3:5-triazin-2-ylamino radicals which contain a fluorine ~.
,~ or a bromine and, above all, a chlorine atom on at least one of the 4- and 6- positions, for example 4:6-dichloro-1:3:5-triazin-2-ylamino When the triazine nucleus contains only a single halogen atom, preferably a chlorine atom, then the third carbon atom of the triazine ring can be : substituted by a hydrocarbon radical, such as methyl or : phenyl, but more particularly by an optionally substituted hydroxy, mercapto or amino group, such as methoxy, phenoxy, ; : a- and ~-naphthoxy, methylmercapto, phenylthio, methylamino, diethylamino, cyclohexylamino and anilino and ~-alkylanilino and substituted derivatives thereo~ such as anisidino, toluidino, carboxylanilino, sulphoanilino, disulphoanilino and sulphonated naphthylamino.
.
.
.. ... .
Thus a preferred class of the reactive dyestuffs comprises those dyestuffs which contain as the fibre~reactive group a group of the formula:
~ `\
Cl - C C - N -N ~ Cr_lH2r_ ~ C/
Q
wherein r is 1 or 2, and Q is a chlorine atom, an optionally substituted amino group or an etherified hydroxyl group.
The optionally substituted amino groups represented by Q are preferably optionally substituted alkylamino, anilino, or ~-alkylanilino groups, e g, methylamino, ethyl-amino, ~-hydroxyethylamino, di(~-hydroxy-ethyl)amino, ~-methoxyethylamino, ~-sulphatoethylamono, o-, m- and ~-sulphoanilino, 4- and 5-sulpho-2-carboxyaniline, 4- and 5-sulpho-2-methoxyanilino, 4- and 5-sulpho-2-methylanilino, 4-and 5-sulpho-2-chloroanilino, 4- and 5-sulpho-2-chloro-anilino, 2,4-, 2,5- and 3,5-disulphoanilino, N-methyl-m-and p-sulphoanilino.
If desired the fibre-reactive group can be of the type:
~H Jl M J2 wherein Jl is a pyrimidine or triazine ring optionally carrying a labile substituent, J is a pyrimidine or tria-zine ring carrying at least one labile substituent and ~
is a bridging member which is linked to J and J through optionally substituted imino groups, said imino groups being linked together through an alkylene or arylene radical such as ethylene, 1:4 -phenylene or 2-sulpho-1:4-phenylene.
' .. . . . .
Other linking groups of particular interest represented by M are the divalent radicals of stilbene, diphenyl, diphenyloxide, diphenylamine, diphenylurea, diphenoxyethane and diphenylamino-s-triazine, which contain a sulphonic acid group in each benzene nucleus, It is preferred that Jl and J2 should each represent a chloro-s-triazine group, Thus, a further class of reactive dyestuffs comprises those dyestuffs which con-tain as the fibre-reactive group a group of the formula:
~ N \
N~ " N Cr_lH2r-1 ¦
C ~ (7) ~ I M ~ ~ ~ l - Cl ., , I ~
Cp lH2p 1 C lH2 :
wherein r, ~ and ~ are each independently 1 or 2, and M and - Q have the meanings stated above, The group Q, as previously defined, includes within its scope groups which contain a chromophoric system linked ~to the carbon atom of the triazine ring through -~H- or -O-. ~.
.~ ~ '.''' Such reactive dyestuffs can be obtained in conven- ;
tional manner for example by reacting a water-soluble dyestuff containing a primary or secondary amino group with a compound which contains the said fibre-reactive group As examples of such compounds there may be mentioned acryloyl chloride, cyanuric chloride, 2:4:6-trichloropyrimidine, 2:4:6-trichloro-5-(cyano- or chloro-)pyrimidine and 6-methoxy-2:4-dichloro-1:3:5-triazine, Other preferred reactive dyestuffs are those containing one or more phosphorus acid groups, particularly phosphonic acid groups, which are applied to cellulose textile materials by the methods described in U.K, Patent Specification ~o. 1411306.
By this process of the invention aromatic polyester/cellulose unions are coloured in a variety of shades which have excellent fastness to the tests commonly applied to such textile materials, and there is excellent reserve of the white unprinted portions of such textile materials, The preparation of certain coupling components and dyestuffs for the particularly preferred mixtures according to the present invention is described below, Parts are by weight unless otherwise indicated, the : ratio of parts by weight to parts by volume being that of the kilogram to the litre.
11C~1154 Preparation of 5-acetylamino-2-methoxy-N,N-diethylaniline 18 parts of 5-acetylamino-2-methoxyaniline are stirred in 50 parts by volume of water. Aqueous sodium hydroxide solution (70O Tw) is added to adjust the pH to 9-10, The mixture is heated to 65OC and a dispersing agent )polyglycerolricinoleate,0,5 part) is added followed by 29.4 parts of sodium bicarbonate (e~uivalent to 3,5 mols per mole of the aniline ...
starting material). 54 parts of diethylsulphate ~3,5 mols per mol of mol of starting material) is then added over a period of 2 hours at 65C, Reaction proceeded smoothly, Stirring of the mixture at 65C was continued for.a further 2 hours after addition of the diethyl-sulphate to complete the reaction. The reaction mixture . was cooled to room temperature and the 5-acetylamino-2-methoxy-~,~-diethylaniline was collected, washed with water (500 parts of volume) and dried at 70C, ~,~-Diethyl-m-aminoacetanilide is prepared in similar manner starting from m-aminoacetanilide, Preparation of the dyestuff _f formula (II) in which Xl ~.
is methoxy . .:
70 parts (by volume) of 100% sulphuric acid : are added to 4 parts of water, 7 parts of sodium nitrite are then added portionwise to the stirred acid .
at a rate such as to raise the temperature of the mixture to 70~ 2C and to maintain it at that level, : :
On completion of the addition of sodium nitrite.the - .
.' .
, ~.
, , . .
l~llS4 solution is stirred for 1 hour, the temperature being allowed to fall to room temperature 26 2 parts of 2,4-dinitro-6-bromoaniline are added to the stirred sodium nitrite solution at 25-28C during 30 minutes.
On completion of the addition the solution is stirred for 2 hours at room temperature.
23,6 parts of 5-acetylamino-2-methoxy-N,N-diethylaniline are stirred in 500 parts of water and 10 parts by volume o concentrated hydro-chloric acid are added. Ice is added to the solution to lower the temperature to 0C and anhydrous sodium acetate is added to adjust the pH to 3-4. The diazotised amine solution is then added dropwise during 30 minutes at 0C and pH 4 (controlled by the addition of ice and sodium acetate) until only a trace of excess coupling component remains as shown by testing the mixture with diazotised p-nitroaniline, The mixture is stirred for a further 15 minutes at 0-5C, and the dyestuff is collected and washed free from inorganic contaminants with water. The d~estuff is dissolved in boiling acetone, the solution is filtered and the dyestuff is re-precipitated by the addition of ice and water to the acetone solution. The product is again collected, washed with water and dried at 70C.
Preparation of the dyestuff of formula (II) in which X is hydroqen 2,4-Dinitro-6-bromoaniline (2~ 2 parts~ is diazotised and coupled with 20,6 parts of N,N-diethyl-m-aminoacetanilide exactly as described for the preceding preparation, ~lV1~54 The invention illustrated butnot limited by the following Examples in which parts and percentages are by weight Example 1 10 Parts of the dyestuffs o~ formula (II) in which W = Br, Xl = methoxy and W = Br, X = hydrogen respectively are individually gravel milled with 12.8 parts of an aqueous solution of a dispersing agent (sodium salt of a naphthalene-2- sulphonic acid/formal-dehyde condensate), containing 39 2% by weight of theagent, and 77 2 parts of water After 48 hours milling the particle size of each dyestuff in its dispersion is 3-4 microns ~ 0.3 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which,W = Br, X
hydrogen, and 0,075 part of the 10% aqueous dispersion .::
, of the dyestuff of formula (II) in which.W = Br, X
methoxy, both dispersions being obtained as described above, are transferred into a dyeing vessel. 0.5 part by volume of a buffer solution is added, followed by 5 parts of polyester piece textile material. The dye-bath is then made up to 50 parts with water and dyeing ~ is effected under superatmospheric pressure at 130C
:~ for 1 hour.
On completion of dyeing the dyed material is stirred in a reduction clearing bath comprising 5 parts of sodium hydrosulphite, 3 parts by volume of sodium hydroxide solution (70 Tw), 3 parts by volume of a dispersing agent and 490 parts by volume of water, for 30 minutes at 70C. The fibre is then thoroughly washed in a soap solution, rinsed well in water and .~.,~'i ll~llS4 and dried.
The polyester is dyed in a navy blue shade having very good build up and high tinctorial strength.
Example 2 - The dyeing procedure described in Example 1 is repeated except that the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, Xl = H and the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, Xl - methoxy are used in the following amounts:-(II W - Br,X - H(II)W = Br,Xl= methoxv (a) 0.10 0,30 (b) 0,20 0,20 (c) 0,25 0.15 :
(d) 0.30 0,10 (c) 0,35 0,05 In each case a strong navy blue shade on polyester textile material is obtained, Example 3 The dyeing procedure described in Example 1 is repeated except that the 0,075 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X - methoxy is replaced by 0,1 part of a 10% aqueous dispersion of one of the following dyestuffs of formula (I), W, X, Y, Z and R in the table below have the same significance as in formula (I), lS4 W X Y Z R
ta) Br OCH3 CH3 CH3 CH3 (b) Br OCH3C3H7~n) C3H(n) CH3 (c) Br C4 9(-) C2H5 C2H5 CH3 (d) Br OCH3 C2H5 C2H5 C2H5 (e) Cl OCH3 C2H5 C2H5 3 (f) Br 0C2H5 C2H5 C2 5 : (g) Br 3 7(-1 C2H5 C2H5 3 (h) Br OCH3 C4Hg( ) C4Hg(~) CH3 (i) Br OCH3 CH3 C4H9(_) CH3 (j) Br OCH3 C2H5 C2H5 C3H7(n) (k) Br OCH3 C2H5 C2H5 C3H7 (i80) : Each dyestuff mixture when applied to aromatic ; polyester textile material as described in Example 1 gives a strong navy blue shade Example 4 The dyeing procedure described in Example 1 i9 repeated except that the 0, 075 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X = methoxy ~:20 is replaced by 0,1 part of the same dyestuff dispersion, and the 0.3~part of the 10% aqueous dispersion of the formula (II) ` ; ~ in which W = Br, X = hydrogen is replaced by 0.3 part of a :10% aqueous dispersion of one of the following dyestuffs of formula (I). W, X, Y, Z and R in the table below have the same significances as in formula (I).
,~
.
~l~tllS4 W X Y Z R
(a) Br 2 5 C2 5 C2H5 (b) Cl HC2H5 C2H5 CH3 (c) Br HCH3 CH3 CH3 (d) Br H3 7(_) C3H7(_) CH3 (e) Br HC4Hg(_)C4Hg ~) CH3 (f) Br HCH3 CH2cH(cH3) 2 CH3 ~`
(g) Br HC2H5 C2H5 C3H7 ~) Each dyestuff mixture when applied to aromatic polyester textile material as described in Example 1 gives a strong navy blue shade.
ExamPle 5 :, 0 3 part of a 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X = hydro~en, 0.5 par~ of a 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, Xl = methoxy and 0.05 part of a 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X = ethoxy are mixed together. This mixture when applied to aroma~ic polyester textile material by the method described in Example 1 gives strong navy blue shades.
~ ~ .
Similar results are obtained if the dyestuff of formula (II) in which W = Br, Xl = ethoxy is replaced by the dyestuff of formula (I) in which W is bromine, X is methoxy, Y and Z are each n-propyl and R is methyl.
Example 6 A mixture is made in the proportions given below, of the 10% aqueous dispersions of four dyestuffs of formula (I) in which Y and Z are each ethyl, R is methyl and W and X have the meanings given below -21- ~
~j :
, . , 110~
- x -Br H 1.5 part Cl H 1 5 part Br OCH3 0 5 part Cl OCH3 0.5 part This mixture when applied to aromatic polyester textile material by the method described in Example 1 gives strong navy blue shades.
Example 7 26.2 Parts of 2,4-dinitro-6~bromoaniline are diazotised by the method described previously and the diazonium compound so obtained is coupled with a mixture of 6.0 parts of 5-acetylamino-2-methoxy-~ diethyl-aniline and 15.4 parts of ~,~-diethyl-m-aminoacetanilide by the method described previously. The mixed dyestuff so obtained when applied in the form of an aqueous dispersion to aromatic polyester textile material as described in Example 1 gives strong navy blue shades Example 8 The dyeing procedure described in Example 1 is repeated except that the 0 3 part of a 10% aqueous dispersion of the dyestuff of formula (II~ in which W = Br, ~: .
~ xI = hydrogen is replaced by 0.3 part of a l~/o aqueous .
dispersion of the dyestuff of formula (II) in which W =
Cl, X ~= hydrogen, and the 0.075 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which W -Br, X = methoxy is replaced by 0 1 part of a 10% aqueous dispersion of one of the following dyestuffs of formula (I~.
:
W, X, Y, Z and R in the table below have the same signifi-cance as iD formula (I) :
~ ~ -22-, llalls4 W X Y Z R
(a) Cl OCH3 C2H5 C2H5 CH3 (b) Cl C2H5 C2H5 C2H5 CH3 (c) Cl OCH3 C2H5 C2H5 C2H5 (d) Cl OCH3 C3H7(n) C3H7(_) CH3 Each dyestuff mixture when applied to aromatic polyester textile m~terial as described in Example 1 gives a strong navy blue shade.
ExamPle 9 A 67/33 woven blend of polyester/cotton fibres is padded in a pad-liquor of the following constitution, so that the material retains 50% of its weight of the padding liquor, 1 part of the dyestuff of formula (II) in which W = Br, X = hydrogen, as a 10% a~ueous dispersion, 4 parts of the dyestuff of formula (II) in which W = Br, X = methoxy, as a 10% aqueous dispersion, ~- ~ 10 parts urea, 10 parts Matexil FA-MIV (a migration inhibitor marketed by Imperial Chemical Industries Limited;
~ "Matexil" is a Registered Trade Mark) :~ 10 parts sodium bicarbonate per 1000 parts of : pad liquor The dyes are preferably in the form of an aqueous . ~ ~ dispersion, milled in the presence of an equal weight of : a protective agent such as the sodium salt of a naphthalene-2-sulphonic acid/formaldehyde condensate.
-23- :
.
, :~
:' ~.
,. ..
.
The padded material is dried for 30 seconds at 110C, baked for 60 seconds at 210C, rinsed in hot water, treated for 30 seconds at 80C in a solution containing 2 g/litre Synperonic BD (a synthetic detergent marketed by Imperial Chemical Industries Limited, "Synperonic" is a Registered Trade Mark) rinsed in cold water and dried.
The above series of operations can conveniently be carried out as a continuous sequence The polyester portion of the blend is dyed to a full, reddish navy shade while the cotton portion is only slightly stained, and the fabric has good fastness to light and washing.
Example 10 The padding procedure described in Example 9 is repeated except that the dyestuff of formula (II) in which W = Br, Xl = hydrogen and the dyestuff of formula (II) in which W = Br, X = methoxy are used in the following proportions:-(II) W = Br, X = H (II) W = Br, Xl =
. M methoxy (a) 1 0 3.0 (b) 2,0 2.0 : ~c) 2,5 l S
: ~ (d) 3.0 1.0 : (e) 3.5 0 5 In each case a similar result to that describedin Example g is obtained Example 11 The padding procedure described in Example 9 is 30 repeated except that the 1 part of the dyestuff of formula :~
(II) in which W = Br, X = hydrogen.is increased to 3 parts, and the 4 parts of the dyestuff of formula (II) in which . -24-' ' ' ~ '.
11~115~
W = Br, Xl = methoxy are replaced by 1 part of one of the following dyestuffs of formula (I) W,X, Y, Z and R in the table below have the same significance as in formula (I).
W X Y z R
ta) Br OC~3 CH3 CH3 CH3 (b) Br OCH3 C3H7(n) . C3H7(n) CH3 (c) Br OC4Hg~) C2H5 C2H5 CH3 (d) Br OCH3 C2H5 C2H5 CH5 Cl OCH3 C2H5 C2H5 CH3 (f) Br C2H5 C2H5 C2H5 CH3 (g) Br OC3H7(_) C2H5 C2H5 CH3 (h) Bx OCH3 C4Hg(_) C4Hg ~) CH3 (i) Br OCH3 CH3 C4Hg(_) CH3 (i) Br OCH3 C2H5 C2H5 C3H7(n) (k) Br OCH3 C2H5 C2H5 c3H7(iso) In each case a similar result to that described in Example 9 is obtained.
Example 12 The padding procedure described in Example 9 is repeated except that the 4 parts of the dyestuff of formula (II) in which W = Br, Xl = methoxy are reduced to 1 part, and the 1 part of the dyestuff of formula (II) in which W = Br, Xl = hydrogen is replaced by 3 parts of -one of the foll~wing dyestuff of formula (I). W, X, Y, Z and R in the table below have the same significance as - . ..... ................................................................... : .
in formula (I) . ,~' -W X Y Z R
(a) Br H 2 5 C2H5 C2H5 (b) Cl H C2~5 C2H5 CH3 (c) Br H CH3 CH3 3 (d) Br H C3H7(n) C3H7(_) CH3 (e) Br H C4Hg(_) C4H9(n) CH3 (f) Br H CH3 CH2CH(cH3)2 CH3 (g) Br H C2 5 C2Hs C3H7(n) In each case a similar result to ~hat described in Example 9 is obtained.
ExamPle-l3 The padding procedure described in Example 9 is repeated except that the 1 part of the dyestuff of ~ formula (II) in which W = Br, X = hydrogen and the 4 I ~ parts of the dyestuff of formula (II) in which W = Br, xl = methoxy are replaced by 3 parts of the dyestuff of formula (II) in which W = Br, Xl = hydrogen, 0.5 part of the dyestuff of formula (II) in which W = Br, X
methoxy and 0.5 part of the dyestuff of formula (II) in which W = Br, Xl = ethoxy.
A similar result to that described in Example 9 is obtained.
If the dyestuff of formula (II~ in which W = Rr, X = ethoxy is replaced by the same amount of the dyestuff ., ~
of formula (I) in which W is hromine~ R is methyl, X is methoxy, and Y and Z are each n-propyl, a similar result is obtained.
. ~ .
~ -26-~ ' ' .
Example 14 The padding procedure described in Example 9 is repeated except that the 1 part of the dyestuff of formula (II) in which W = Br, Xl = hydrogen and the 4 parts of the dyestuff of formula (II) in which W = Br, Xl =
methoxy are replaced, in the proportions given below, by four dyestuffs of formula (I) in which Y and Z are each ethyl, R is methyl and W and X have the meanings given below:-W X
Br H 1.5 parts Cl H 1.5 parts Br OCH3 0.5 parts Cl OCH3 0.5 parts : A similar result to that described in Example 9 is obtained.
Example 15 A mixture of dyestuffs of formula (II) in which W = Br, Xl = hydrogen and W = Br, Xl = methoxy respectively is prepared as described in Example 7 and converted into 10% aqueous dispersion.
When this dispersion is applied to a polyester/
cotton blend as described in Example 9 a similar result is obtained, Example 16 The padding procedure described in Example 9 is repeated except that the 1 part of the dyestuff of formula (II) in which W = Br, Xl = hydrogen and the 4 parts of the dyestuff of formula (II) in which W = Br, Xl = methoxy are r placed by 3 parts of the dyestuff of ' l~llS4 formula (II) in which W = C1, Xl = hydrogen and 1 part of one of the following dyestuffs of formula (I) respectively.
W, X, Y, Z and R in the table below have the same signifi- -cance as in formula (I), W X Y Z R
(a) C2H5 C2H5 ~H3 (b) Cl C2H5 C2H5 C2H5 CH3 (c) Cl OCH3 C2H5 C2H5 C2H5 (d) Cl OCH3 C3H7~_) C3H7(-) CH3 In each case a result similar to that described in Example 9 is obtained.
-...
' ~ .
'
Claims (12)
1. A mixture of two or more disperse monoazo dyestuffs of the formula:
wherein W is a chlorine atom or a bromine atom;
X is hydrogen or OR1 and R, R , Y and Z are lower alkyl groups, provided that the mixture contains at least one component in which X = H and another in which X - OR1,
wherein W is a chlorine atom or a bromine atom;
X is hydrogen or OR1 and R, R , Y and Z are lower alkyl groups, provided that the mixture contains at least one component in which X = H and another in which X - OR1,
2. A dyestuff mixture as claimed in claim 1 which comprises two components in amounts from 95:5 to 5:95 parts by weight.
3. A dyestuff mixture as claimed in claim 2 which comprises the two components in amounts from 80:20 to 20:80 parts by weight.
4. A dyestuff mixture as claimed in claim 1 which comprises two dyestuffs selected from dyestuffs having the formula:
in which W is a chlorine atom or a bromine atom and X1 is either hydrogen, or methoxy or ethoxy, provided that in one component of the mixture X1 is hydrogen and that in the other component X1 is methoxy or ethoxy.
in which W is a chlorine atom or a bromine atom and X1 is either hydrogen, or methoxy or ethoxy, provided that in one component of the mixture X1 is hydrogen and that in the other component X1 is methoxy or ethoxy.
5. A dyestuff mixture as claimed in claim 4 wherein the dyestuff in which X1 is hydrogen and the dyestuff in which X1 is methoxy or ethoxy are in the proportions between approximately 4:1 and approximately 2:1 by weight, respectively.
6. A dyestuff mixture as claimed in claim 4 which comprises the two dyestuffs in which W is bromine and X1 is hydrogen, and in which W is bromine and X1 is methoxy, in the proportions of approximately 3:1 by weight, respectively.
7. A process for the colouration of aromatic polyester textile materials and aromatic polyester/cellulose unions which comprises applying to the said textile material or union by an aqueous dyeing, padding or printing process a mixture of two or more disperse monoazo dyestuffs as claimed in claim 1.
8. A process as claimed in claim 7 wherein the mixture of two or more disperse monoazo dyestuffs is applied to an aromatic polyester/cellulose union in con-junction with one or more colouring matters for the cellulose component of the union
9. A process as claimed in claim 8 wherein the colouring matter for the cellulose component of the union is a Direct Dyestuff, Vat Dyestuff, Sulphur Dyestuff, Azoic Colouring Matter or Reactive Dyestuff.
10. A process as claimed in claim 9 wherein the coloring matter for the cellulose component of the union is.
a reactive dyestuff which contains as the fibre-reactive group a heterocyclic radical having two or three nitrogen atoms in the heterocyclic ring and at least one labile substituent attached to a carbon atom of the heterocyclic ring,
a reactive dyestuff which contains as the fibre-reactive group a heterocyclic radical having two or three nitrogen atoms in the heterocyclic ring and at least one labile substituent attached to a carbon atom of the heterocyclic ring,
11. A process as claimed in claim 10 wherein the reactive dyestuff contains a triazine or pyrimidine ring containing as the labile substituent at least one chlorine, bromine or fluorine atom
12. A process for the manufacture of the mixtures of disperse monoazo dyestuffs claimed in claim 1 which comprises coupling a mixture of at least two coupling components of formula:
wherein R,X, Y and Z have the meanings stated in claim 1, with at least one diazonium compound obtained by diazotisation of an amine of formula:
wherein W has the meaning stated in claim 1, provided that the mixture of coupling components contains at least one component in which X is hydrogen and at least one component in which X
is OR1.
wherein R,X, Y and Z have the meanings stated in claim 1, with at least one diazonium compound obtained by diazotisation of an amine of formula:
wherein W has the meaning stated in claim 1, provided that the mixture of coupling components contains at least one component in which X is hydrogen and at least one component in which X
is OR1.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB17793/77 | 1977-04-28 | ||
GB17792/77 | 1977-04-28 | ||
GB1779377 | 1977-04-28 | ||
GB17792/77A GB1582743A (en) | 1977-04-28 | 1977-04-28 | Mixtures of disperse azo dyestuffs |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1101154A true CA1101154A (en) | 1981-05-19 |
Family
ID=26252927
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA302,224A Expired CA1101154A (en) | 1977-04-28 | 1978-04-28 | Disperse azo dyestuffs |
Country Status (12)
Country | Link |
---|---|
JP (1) | JPS53137229A (en) |
BR (1) | BR7802641A (en) |
CA (1) | CA1101154A (en) |
CH (1) | CH633576A5 (en) |
DE (1) | DE2818653A1 (en) |
ES (1) | ES469268A1 (en) |
FR (1) | FR2388861B1 (en) |
HK (1) | HK61981A (en) |
IT (1) | IT1094970B (en) |
MX (1) | MX148450A (en) |
NL (1) | NL7804338A (en) |
PT (1) | PT67962B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10301474B2 (en) | 2014-09-15 | 2019-05-28 | Dystar Colours Distribution Gmbh | High wet fast disperse dyes and mixtures thereof |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3121320A1 (en) * | 1981-05-29 | 1982-12-16 | Hoechst Ag, 6000 Frankfurt | NEW COLOR PRESENTATIONS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COLORING AND PRINTING SYNTHETIC FIBER MATERIALS |
DE3142609A1 (en) * | 1981-10-28 | 1983-05-05 | Basf Ag, 6700 Ludwigshafen | NAVY BLUE DISPERSION DYE MIXTURES |
DE3347572A1 (en) * | 1983-12-30 | 1985-07-11 | Hoechst Ag, 6230 Frankfurt | MIXTURES OF BLUE DISPERSION AZO DYES FOR DYEING POLYESTER FIBERS |
DE3539771A1 (en) * | 1985-11-09 | 1987-05-14 | Cassella Ag | MIXTURES OF BLUE DISPERSION DYES AND THEIR USE FOR DYING POLYESTER |
GB8717309D0 (en) * | 1987-07-22 | 1987-08-26 | Ici Plc | Disperse dye |
JPH01210465A (en) * | 1988-02-17 | 1989-08-24 | Kiwa Kagaku Kogyo Kk | Mixed monoazo dye composition |
DE3819563A1 (en) * | 1988-06-09 | 1989-12-14 | Hoechst Ag | MULTICOMPONENT MIXTURES OF BLUE DISPERSION AZO-PURPOSES FOR THE ADVERTISING OF SYNTHETIC FIBERS |
DE3908445A1 (en) * | 1989-03-15 | 1990-09-20 | Cassella Ag | DYE MIXTURE |
DE4232558A1 (en) * | 1992-09-29 | 1994-03-31 | Basf Ag | Mixtures of azo dyes for navy blue to black shades |
JP3260517B2 (en) * | 1993-10-06 | 2002-02-25 | ダイスタージャパン株式会社 | Disperse dye composition and method for dyeing hydrophobic fiber using the same |
DE4330843A1 (en) * | 1993-09-11 | 1995-03-16 | Cassella Ag | Process for dyeing polyester and textile materials containing polyester |
DE102004018257B3 (en) * | 2004-04-15 | 2006-01-05 | Reitter, Gerd, Dipl.-Ing. (FH) | Multiple-ram press for deep drawing has first and second rams with through aperture in drawing direction |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE630388A (en) * | 1962-03-31 | |||
FR1382654A (en) * | 1964-02-14 | 1964-12-18 | Sandoz Sa | Mono-azo nitro dyes, their manufacture and applications |
-
1978
- 1978-04-18 MX MX173160A patent/MX148450A/en unknown
- 1978-04-24 NL NL7804338A patent/NL7804338A/en not_active Application Discontinuation
- 1978-04-27 JP JP5071878A patent/JPS53137229A/en active Granted
- 1978-04-27 FR FR7812501A patent/FR2388861B1/en not_active Expired
- 1978-04-27 CH CH459178A patent/CH633576A5/en not_active IP Right Cessation
- 1978-04-27 DE DE19782818653 patent/DE2818653A1/en active Granted
- 1978-04-27 PT PT67962A patent/PT67962B/en unknown
- 1978-04-27 BR BR7802641A patent/BR7802641A/en unknown
- 1978-04-28 ES ES469268A patent/ES469268A1/en not_active Expired
- 1978-04-28 CA CA302,224A patent/CA1101154A/en not_active Expired
- 1978-04-28 IT IT22839/78A patent/IT1094970B/en active
-
1981
- 1981-12-10 HK HK619/81A patent/HK61981A/en not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10301474B2 (en) | 2014-09-15 | 2019-05-28 | Dystar Colours Distribution Gmbh | High wet fast disperse dyes and mixtures thereof |
Also Published As
Publication number | Publication date |
---|---|
JPS53137229A (en) | 1978-11-30 |
DE2818653C2 (en) | 1988-01-07 |
DE2818653A1 (en) | 1978-11-02 |
MX148450A (en) | 1983-04-22 |
ES469268A1 (en) | 1979-09-16 |
CH633576A5 (en) | 1982-12-15 |
HK61981A (en) | 1981-12-18 |
PT67962A (en) | 1978-05-01 |
IT1094970B (en) | 1985-08-10 |
NL7804338A (en) | 1978-10-31 |
FR2388861A1 (en) | 1978-11-24 |
IT7822839A0 (en) | 1978-04-28 |
JPS626592B2 (en) | 1987-02-12 |
FR2388861B1 (en) | 1985-06-07 |
BR7802641A (en) | 1979-01-02 |
PT67962B (en) | 1979-11-14 |
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