CA1111844A - Reactive dyeing system and xylylene diphosphonic acid dyes - Google Patents
Reactive dyeing system and xylylene diphosphonic acid dyesInfo
- Publication number
- CA1111844A CA1111844A CA356,595A CA356595A CA1111844A CA 1111844 A CA1111844 A CA 1111844A CA 356595 A CA356595 A CA 356595A CA 1111844 A CA1111844 A CA 1111844A
- Authority
- CA
- Canada
- Prior art keywords
- dye
- acid
- cyanamide
- solution
- dyes
- 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
- -1 xylylene diphosphonic acid Chemical compound 0.000 title abstract description 28
- 238000004045 reactive dyeing Methods 0.000 title abstract description 7
- 239000000980 acid dye Substances 0.000 title description 12
- 239000000975 dye Substances 0.000 claims abstract description 216
- 239000002253 acid Substances 0.000 abstract description 63
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 abstract description 52
- 239000000758 substrate Substances 0.000 abstract description 37
- 238000004043 dyeing Methods 0.000 abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 25
- 239000011574 phosphorus Substances 0.000 abstract description 24
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 14
- 239000004753 textile Substances 0.000 abstract description 11
- 150000001718 carbodiimides Chemical class 0.000 abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 230000001476 alcoholic effect Effects 0.000 abstract description 3
- 150000001912 cyanamides Chemical class 0.000 abstract description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 3
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 95
- 239000000243 solution Substances 0.000 description 83
- 229920000742 Cotton Polymers 0.000 description 46
- 238000000034 method Methods 0.000 description 45
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 33
- 239000000835 fiber Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 235000014786 phosphorus Nutrition 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 230000008569 process Effects 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 20
- 229910001868 water Inorganic materials 0.000 description 20
- 229920002678 cellulose Polymers 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000001913 cellulose Substances 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 18
- 235000011007 phosphoric acid Nutrition 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 15
- 229960004838 phosphoric acid Drugs 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 10
- 239000001045 blue dye Substances 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 150000003863 ammonium salts Chemical class 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000004900 laundering Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000984 vat dye Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000000985 reactive dye Substances 0.000 description 8
- 235000017550 sodium carbonate Nutrition 0.000 description 8
- 210000002268 wool Anatomy 0.000 description 8
- MZZQBSHNCYWSTL-UHFFFAOYSA-N (3-aminophenyl)phosphonic acid Chemical compound NC1=CC=CC(P(O)(O)=O)=C1 MZZQBSHNCYWSTL-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 150000003017 phosphorus Chemical class 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 7
- 239000001044 red dye Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000001043 yellow dye Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 239000001048 orange dye Substances 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000080 wetting agent Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 5
- KYIFZWRWQAKTTI-UHFFFAOYSA-N [2-amino-4-(phosphonomethyl)phenyl]methylphosphonic acid Chemical compound NC1=CC(CP(O)(O)=O)=CC=C1CP(O)(O)=O KYIFZWRWQAKTTI-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920002113 octoxynol Polymers 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002964 rayon Substances 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 5
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910006069 SO3H Inorganic materials 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000986 disperse dye Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000009991 scouring Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- NEKHKXMBGWNTOO-UHFFFAOYSA-N (4-aminophenyl)methylphosphonic acid Chemical compound NC1=CC=C(CP(O)(O)=O)C=C1 NEKHKXMBGWNTOO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000004712 monophosphates Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical group [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- DACUJXBUANTBKE-UHFFFAOYSA-N 4-acetamido-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(NC(=O)C)=CC(S(O)(=O)=O)=CC2=C1 DACUJXBUANTBKE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229920004934 Dacron® Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910017974 NH40H Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 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 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000010014 continuous dyeing Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- OAGOUCJGXNLJNL-UHFFFAOYSA-N dimethylcyanamide Chemical compound CN(C)C#N OAGOUCJGXNLJNL-UHFFFAOYSA-N 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration 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
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- TXMRAEGWZZVGIH-UHFFFAOYSA-M sodium;1-amino-4-bromo-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C(Br)=CC(S([O-])(=O)=O)=C2N TXMRAEGWZZVGIH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 1
- MKAQEKVDYJJNMV-UHFFFAOYSA-N (3-chlorosulfonylphenyl)phosphonic acid Chemical group OP(O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1 MKAQEKVDYJJNMV-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RTLULCVBFCRQKI-UHFFFAOYSA-N 1-amino-4-[3-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-sulfoanilino]-9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S(O)(=O)=O)C=C1NC(C=1)=CC=C(S(O)(=O)=O)C=1NC1=NC(Cl)=NC(Cl)=N1 RTLULCVBFCRQKI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- CWJQQASJVVAXKL-UHFFFAOYSA-N 4-(3-Methyl-5-oxo-4,5-dihydro-1H-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC=C(S(O)(=O)=O)C=C1 CWJQQASJVVAXKL-UHFFFAOYSA-N 0.000 description 1
- RMJRVSQNBIHNTK-UHFFFAOYSA-N 5-oxo-4-phenylpyrazole-3-sulfonic acid Chemical compound O=C1N=NC(S(=O)(=O)O)=C1C1=CC=CC=C1 RMJRVSQNBIHNTK-UHFFFAOYSA-N 0.000 description 1
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- LQVXSNNAFNGRAH-QHCPKHFHSA-N BMS-754807 Chemical compound C([C@@]1(C)C(=O)NC=2C=NC(F)=CC=2)CCN1C(=NN1C=CC=C11)N=C1NC(=NN1)C=C1C1CC1 LQVXSNNAFNGRAH-QHCPKHFHSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 101001133936 Homo sapiens Prolyl 3-hydroxylase 2 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 101100166829 Mus musculus Cenpk gene Proteins 0.000 description 1
- 150000007945 N-acyl ureas Chemical class 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 102100034015 Prolyl 3-hydroxylase 2 Human genes 0.000 description 1
- 101100409194 Rattus norvegicus Ppargc1b gene Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- MKUXAQIIEYXACX-UHFFFAOYSA-N aciclovir Chemical compound N1C(N)=NC(=O)C2=C1N(COCCO)C=N2 MKUXAQIIEYXACX-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000728 ammonium alginate Substances 0.000 description 1
- 235000010407 ammonium alginate Nutrition 0.000 description 1
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- XMRUJYGYYCLRGJ-UHFFFAOYSA-N azanium;2-[2-[2-[2-(4-nonylphenoxy)ethoxy]ethoxy]ethoxy]ethyl sulfate Chemical compound [NH4+].CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOS([O-])(=O)=O)C=C1 XMRUJYGYYCLRGJ-UHFFFAOYSA-N 0.000 description 1
- 201000001493 benign recurrent intrahepatic cholestasis Diseases 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- PQZVCRPSQXDXJL-UHFFFAOYSA-N butylcyanamide Chemical compound CCCCNC#N PQZVCRPSQXDXJL-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 208000037516 chromosome inversion disease Diseases 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- SOGFATPCYLMCMQ-UHFFFAOYSA-N dibutylcyanamide Chemical compound CCCCN(C#N)CCCC SOGFATPCYLMCMQ-UHFFFAOYSA-N 0.000 description 1
- ZZTSQZQUWBFTAT-UHFFFAOYSA-N diethylcyanamide Chemical compound CCN(CC)C#N ZZTSQZQUWBFTAT-UHFFFAOYSA-N 0.000 description 1
- UBPGILLNMDGSDS-UHFFFAOYSA-N diethylene glycol diacetate Chemical compound CC(=O)OCCOCCOC(C)=O UBPGILLNMDGSDS-UHFFFAOYSA-N 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- FPVGTPBMTFTMRT-UHFFFAOYSA-L disodium;2-amino-5-[(4-sulfonatophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-UHFFFAOYSA-L 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- JOGZZTFIGKYTSV-UHFFFAOYSA-N ethylcyanamide Chemical compound CCNC#N JOGZZTFIGKYTSV-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019233 fast yellow AB Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical group [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 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 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MCLITRXWHZUNCQ-UHFFFAOYSA-N methylcyanamide Chemical compound CNC#N MCLITRXWHZUNCQ-UHFFFAOYSA-N 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- QZGIWPZCWHMVQL-UIYAJPBUSA-N neocarzinostatin chromophore Chemical compound O1[C@H](C)[C@H](O)[C@H](O)[C@@H](NC)[C@H]1O[C@@H]1C/2=C/C#C[C@H]3O[C@@]3([C@@H]3OC(=O)OC3)C#CC\2=C[C@H]1OC(=O)C1=C(O)C=CC2=C(C)C=C(OC)C=C12 QZGIWPZCWHMVQL-UIYAJPBUSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- BDFSIUDCODWSTA-UHFFFAOYSA-M potassium;2-carboxy-4-phosphonobenzoate Chemical compound [K+].OC(=O)C1=CC(P(O)(O)=O)=CC=C1C([O-])=O BDFSIUDCODWSTA-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CYFLXLSBHQBMFT-UHFFFAOYSA-N sulfamoxole Chemical group O1C(C)=C(C)N=C1NS(=O)(=O)C1=CC=C(N)C=C1 CYFLXLSBHQBMFT-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- 210000001550 testis Anatomy 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- RMPQIFXEQFYSEM-UHFFFAOYSA-N triazanium;4-sulfonatophthalate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)C1=CC=C(S([O-])(=O)=O)C=C1C([O-])=O RMPQIFXEQFYSEM-UHFFFAOYSA-N 0.000 description 1
- YQEHHPFEQLDFCN-UHFFFAOYSA-K trisodium 5-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-hydroxy-3-[(2-sulfonatophenyl)diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].Oc1c(N=Nc2ccccc2S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Cl)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O YQEHHPFEQLDFCN-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3882—Arylalkanephosphonic acids
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
- C09B1/34—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups sulfonated
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/36—Dyes with acylated amino groups
- C09B1/42—Dyes with acylated amino groups the acyl groups being residues of an aromatic carboxylic acid
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
- C09B67/0073—Preparations of acid or reactive dyes in liquid form
-
- 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
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/007—Dyestuffs containing phosphonic or phosphinic acid groups and derivatives
-
- 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
- D06P1/22—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 vat dyestuffs including indigo
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/68—Preparing azo dyes on the material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/28—Colorants ; Pigments or opacifying agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed herein is a novel red dyestuff of the following formula:
This dye is useful in reactive dyeing of cellulose fibers to give bright red dyeings exhibiting good lightfastness and color strength. Also disclosed are xylylene diphosphonic acid dyestuffs of the general formula:
where Dye is a chromophore and dyestuffs of the general formula
Disclosed herein is a novel red dyestuff of the following formula:
This dye is useful in reactive dyeing of cellulose fibers to give bright red dyeings exhibiting good lightfastness and color strength. Also disclosed are xylylene diphosphonic acid dyestuffs of the general formula:
where Dye is a chromophore and dyestuffs of the general formula
Description
BACKGRO~ND ~F THE INVENTION
l. Field ~f the Invention:
The present invention as disclosed relates to dyeing of fibers and more particularly to reactively dyed fibers in which a chromophore is linked through a condensa-tion residue to sites on the fiber. The invention as described herein also relates to a novel red dyestuff.
l. Field ~f the Invention:
The present invention as disclosed relates to dyeing of fibers and more particularly to reactively dyed fibers in which a chromophore is linked through a condensa-tion residue to sites on the fiber. The invention as described herein also relates to a novel red dyestuff.
2. Description of the Prior Art:
Dyes are retained in fibers by physical adsorption, salt or metal-complex formation, solution, mechanical retention, or the formation of covalent chemical bonds. Physical aasorp-tion and solution, in which the dye is partitioned between the fiber and the surrounding aqueous phase, are equilibrium reactions, and only by very careful selection of the dyes used, can good washfastness properties be achieved. Salt and metal complex formation are also equilibrium reactions and, though generally the retention of the dye is favored more than in physical adsorption, washfastness may still present a problem.
The dyes that are held ~y mechanical retention (azoics, vats and sulfurs) are virtually insoluble in water and show excellent fastness to washing, but have other disadvantages. They are, for example, difficult and expensive to apply; loose dye, which is not easily washed off, may be deposited on the sur-face, resulting in low fastness to rubbing (crockfastness), and the final shade of the dyeing does not deveiop until com-pletion of the whole dyeing cycle and aftertreatments.
Chemical bonding of dye to fiber for fixation ~f dye was recognized as early as 1895. The reactive dye systems presently available require that the dyes contain a functional group capable o~ forming a covalent chemical bond with the fiber.
Fiber-reactive dyes are employed quite widely in coloring cellulosics and proteinaceous fibers. They, of course, exhibit excellent washfastness, resistance to rubbing, tinctorial powers, ease of application and leveling. The latter quality is a measure of uniformity a~d most important for long dye runs and color matching. The reaction of the dye with cellulosic fi~ers is basically an esterification or etherification reaction and is broadly represented as:
Dyc ~ ~ ~ Cl I Ce`l-OH ; Dyc ~ O l-O-Cc~
Cl Cl Dye-SO2C~2CH2oH + Cel -OH -~ ~ye-SO2CH2C~20-C21i (II) The triazine reactive group imparts oil solubility characteristics to the high molecular weight dye which hinder and interfere with an aqueous solubilizing group such as -SO3H. These dyes ar_ unstable and difficult to work with.
Most of the reactive dye systems are based upon chemistry where the reaction is effected in alkaline solutions. There are few present reactive dye systems which operate effectively at an acid p~. Such a system is desirable in the dyeing of mixed fabrics such as cotton blends with polyester, wool or nylon, the latter fibers being dyeable by acid dyes. ~owever, acid dyes,generally have no affinity for cellulose and usually only find use in dyeing of protelnaceous fibers. F~ther re, Qince the dye and fiber substrate are coreactive, complete dye-ing of the fabric will occur unless speclal precautions are prac ticed to localize the dye in areas of the fabric by printing, ;
stenciling or other graphic technique.
The American Cyanamid Company has published a book-let entitled "Cyanamide", which sets forth a considerable number of reactions of cy namide and dicyandi~mide. Page 32 of this booklet indicates that cyanæmide was long ~nown to be a dehydrating agent when warmed with anhy~rous formic acid and in the esterification o~ lactic or saLicylic acid in absolute ethanol. Note Pratorius-Seidler, G., J prakt. Chem. {2l 21, 129-50 (188Q); C.Z. L880, 245. A number of papers have inves-tigated the reaction of cyanamide with car~oxylic acids, and have ~roposed a mechanism wherein the acid is , converted to the anhydride ~y interaction with cyanamide, with for~ation of urea, and su~sequent acylation of the urea by the anhydride to produce a ureide, which at elevated temperatures interacts with the acid to produce an amide.
Cyanamide ~nd dialkylcyana~ides are also useful in the Synthesis o~ pyrophosphates. Kenner, G. W., Reese, C.B., and Todd, A.R., J. Chem. Soc. 1958, 546-51; ~.A. 52, 11072 (1958) indicates that a high energy phosphorus - oxygen bond is present in the presumed intermediate O-phosphoryl-pseudourea.
The use of cyanamide and phosphoric acid to impart flame retardant properties to cotton and other cellulosic fabrics is well known to the art. For instance, O'Brien "Cyanamide ~ased Durable ~lame-Retardant Finish for Cotton", Textile Research 3Ournal, March, 1968, pp. 256-266 indicates, at page 265, that the reaction of cyanamide and phosphoric acid with cellulose results in a cross-linking of cellulose molecules. From the properties of the resulting product, it is suggested that the cross-linked cellulose is some type of a dicellulose phosphate ester.
S~MARY OF THE INVENTION:
The present invention provides a dye system for dyeing hydroxy substituted substrates in which the reaction can be conducted in acidic to mildly alkaline solutions.
The dye system o~ the invention is a reactive system in which the reactive function is not self-contained in the dye molecule. Since the dye and fiber re~uire the presence of a condensation agent for reaction, certain dyes such as azo dyes, where the dye is formed by a sLmple coupling reaction, can be formed via an intermediate on the fabric which can be selectively color developed in discrete locations to form a pattern. The background areas can be fixed to expose or decompose the remaining precursor areas.
The dye system of the invention is further simplified in that a ~ingle group serves both as an aqueous s lubilizing group and as the potentially reactive coupling site to the fiber, thus providing a more simplified synthesis and a less complex and more stable dye molecule and dyed fabric.
m e present invention, in one aspect, resides in ., a method of forming a reactively dyed polymeric substrate, said method comprising:
~ a) contacting a polymeric substrate containing active hydrogen atoms present in the form of amino or thiol groups with a cyanamide compound selected from the group consisting of cyanamide, alkyl-substituted cyanamide, dicyandiamide, and alkyl-substituted dicyandiamide, wherein the alkyl groups each contain 1-6 carbon atoms, and with a coloring amount of a chromophore-substituted phosphorus acid of the formula:
(01 Rm ~ P - (OH3p (OR) B~4 wherein each R i~ a chromophore, m is 0, 1 or 2;
n is 0 or 1; p is 1 or 2; and ~ is 0 or 1; and m ~ p + ~= 3, at least one ~f m and ~ l~eing other than 0, at a pH of from about 1.5 to about 9, wherein the S equivalent ratio c)f said cyan~anide compound to each phosphorus acid ~unction of said chromophore-substituted phosphorus acid is at least about 2:1 and ~I heating the contacted substrate to a temper--ature of at least 200F for a time sufficient to fix said chromophore to said substrate.
This method is also disclosed, and is claimed, in Canadian Patent Application No. 219,183, filed January 31, 1975, (now Canadian Patent No. 1,090,054, granted November 25, 1980) of which the present application is a divisional.
In another aspect o~ the invention, there is provided a reactively dyed organic polymeric substrate of the formula:
()n m ~ \
(OH)z (OR~q where each R is a chromophore, said chromophore heing linked chemically to the P atom; Rl is the chain of a polymer having reactive groups with active hydrogen atoms selected from alcoholic hydroxyl groups, amino groups and thio groups;
m is 0, 1 or 2; n is 0 or 1; q is 0 or 1 and z is 0 or 1;
and m f p + q = 3, at least one of m and q being other than 0.
-7a-This aspect o~ the inYention is also disclosed, and is claimed, in Canadian Application No. 219,183, filed January 31, 1975, (now Canadian Patent No. 1,090,054, granted November 25, 1980) of wElich the present application is a divisional.
In our Canadian Patent 1,006,655, granted March 15, 1977, a related invention is disclosed and claimed. According to the invention described in that patent a reactively dyed hydroxy-substituted organic polymeric substrate is formed by the steps of:
cc)ntacting a substrate of the formula, RlCH, where Rl acids and amine or ammonium salts thereof and a water soluble carbodiimide in which the ratio equivalent of carbodiimide to acid is at least about 2:1. The invention to which said Canadian Patent 1,006,655 pertains is concerned particularly with the dyeing of cellulosic substrates.
The pre~ent invention, in a further aspect, resides in a dyestuff of the followinq formula:
o H ¦¦
,~=N~
/~ J~ SO3H PO(OH) 2 -The dye system of the present invention results in reactively dyed fabrics by immo~ilization of a dye as a cellulose phosphorus ester according to the following illustrative reaction:
(Il)n (~)n Rml-(0~)p + R'OH + CDI~ Rm-l + CDIX
(OR)q (OR) q where R is as defined above, R'OH is cellulose, CDI is a carbodiimide, CDIX is a CDI residue or by-product, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, q is 0 or 1 and z = p-l.
Thus, a chromophoric grouping (R) linked chemically to a phosphorus acid such as phosphonic, phosphonous, phosphinic or phcsphoric acid, reactively dyes cellulose (R'OH) with the aid of a carbodiLmide condensing agent (CDI).
Cyanamide which is a suitable carbodiimide, allows for a rapid esterification of phosphorus acids with alcohols. The by-product, CDIX, is urea. Thus, where R is a chromophore and R'OH is cellulose, a fiber reacted dye compound is formed is the chain of the polymer and OH is any h~droxyl group on the chain in the presence of a carbodiimlde with a chromophore substituted phDsp~orus acid of the formula:
CO~
n - P ~OH~p ~ORlq where R is the chromophore, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, and g is 0 or 1; and heating the contacted su~strate to a temperature of at least 200F for a time sufficient to react said acid with said hydroxyl to form a dyed substrate having a phosphorus ester linkage between said chromophore and chain and having the formula:
(~n Il ~ ORl R P
¦ (OH~
COR~
where z is p-l.
Also described and claimed in Canadian Patent 1,006,655 æ e reac~;vely dyed hydroxy-substituted organic polymeric substrate~a reacti~ely dyed hydroxy-substituted organic polymeric substrate of the formula:
r)n ¦¦ ~O
R_ P
¦ (OH~z (CR~
where R is a chromophore group, Rl is ~he chain of the polymer, m is C, 1 or 2, n is 0 or 1, a is 0 or 1 an~
z is 0 or 1; and compositions for reactively dyeing h~droxy-substituted organic polym~ric substrates comprising an aqueous solution containing at least 0.1~ ~y weight of a su~star.ce select^d from chromophore substitu~ed ~hosphorus _7~
111~844 with cellulose. This results is a substantial and washfast dyeing of cotton and other cellu7osic or hydroxy containing substrates. Cellulose esters of phosphonic acid dyes are found to be the most stable to heavy-duty alkaline detergents. The reaction of phosphonic acid dyes would proceed as follows:
O O
Il 11 R-P-OH + R'OH + CDI ~ R-P-OR' + CDIX
OH OH
The fabric or fiber system of the in~ention proceeds by forming an aqueous solution of a chromophore or precursor thereof linked chemically to a phosphorus contai~ing acld.
The solution general'y contains at least 0.1% of the dye and genera~ly no more than 10% by weight of the dye depending on the intensity of the chromophore and the shade desired. The dye concentration is generally between 0.1 and 5% by weight and the concentration of reacted dye on the fabric is believed to be in the range of 0.01 to 0.05 weight percent, although much greater concentrations of dye on the fabric can be employed, e.g., up to even 5.0 weight percent, or more; 10 4 to 10 2 mo~. percent.
The pH of the solution is generally about 3-4 but can be ~aried from about 1.5 to 9. Lower pH can be provided by addition to the impregnation bath of '%-5~ of an acid which is non-volatile at the cure temperature, and does not cause undue degradation of the substrate, such as a phos~horic acid, 'ower alkyl phosphonic acid or chloroacetic acid. This appears to im rove the efficiencv or^ t;~e aye im~obilizatior.
since less dye is found to wash out after cure. ~he amount of carbodiimide is usually increased in a ~ath containing added acid. ~igher pH baths mav be uti' zec cortaining s~'ts which are converted to the acid form during cure such as fugitive amine salts, or ammonium salts of the phosphorus acid chromophore. Higher pH baths may be necessary in certain situations which present corrosion problems, or have mixed fiber systems or fibers which would be excessively degraded at low pH.
Generally, in the bath the molar equivalent ratio of the diimide to each phosphorus acid function is at least about 2:1. Curing is generally conducted at a temperature of at least 200~F and generally below 400F. Preferably, the fabric may be preliminarily dried at a temperature below 200F before cure. The cure time can be varied from the order of seconds to hours depending on the temperature, dye concentration and fiber being colored.
~ he reacti~e dye system of the invention is general-ly applicable to substrates containing available hydroxyl groups such as cellulose, particularly cotton,and may ke practiced on fibers, films, yarns, cords, threads, paper, fabrics, non-woven or woven, knitted; or other types including pile fa'orics, velvet5~ knitted fabrics, corded webs or webs foDmed by a random webber.
The water-soluble condensation agent assists ln the formation of the phosphorus ester l nkzge be_~een the chromo-phore, R, and the cell~'ose substrate, R'OH. The agent is preferably a water-solubl~ carbodiimide such as ~yanamlde or dicyandiamide.
The impregnatins bath may also cont2in ~l~or ~mounts of conventi3r.al additives or assistants such as an~i-migralins agents, Glauber's salt, or ~ettin~ asents. Ccmpat_ble thic~-eners may also be present.
g The dyes that can be utilized in the dye immobiliza-tion process of the invention can be of diverse type and 3tructure. The dye may be an anthraquinone, phthalocyanine, mono-azo, polyazo, benza~throne, pyrazolone, naphthoquinone, triary~methane or cyanine type that is modified to contain a phosphorus acid group to impart water-solubility and to provide a reactive site for attachment to the hydroxyl groups on the substrate. The dyes may contain other aqueous solubilizing groups such as sulfonate and may contain other substituents that do not interfere with aqueous solubility characteristics or the dye immDbilization esterification reaction.
~ any of the phosphorus acid substituted dyes utilized in the process of the invention axe ~nown materials readily available m the art, and have been used to direct dye wool and other proteinaceouc fibers. Suitable dyes are di~closed in Belgium Patent No. 570,326, British Patent No. 455,092 and United States Patent Nos. 2,596,660 and 2,799,701. Analogues of many sulfonated dyes can readily be synthesized in the phosphono form by substituting the phosphono analog for the sulfono-containing compound during synthesi~.
The proces~ of the invention may be readily adapted SG
that it can be carried out in commercially available machinery used for dyeing or textile pr~nting processes and for continuous or non-continuous variations of 3uch processes. The fibrous or sheet material may be impresnated Wlt~ the dyestuff solution and then s~bjected to curing by heating, for example, ln a hot flue dryer, an oven or a stenter. The im~re~nation may be carried out for example by padding material ~th an aqueous solution cont2inir;g the dyestuff and curing agent. The dye treatment may also be car_ied out by textile printing ~ethods, 111~844 r for example, by locally treating the textile with a solution containing the dyestuff and condensation agent and thereafter subjecting the printed material to an elevated temperature for curing. Alternatively a phosphono-substituted primary agent may be coupled to the cellulose and thereafter coupled to an azo chromophore component.
The invention will now become better understood by reference to the following detailed description when considered in conjunction w~th the spocific examples of practice. It is to be understood that these examples are presented solely for purposes of illustration and not by way of limitation, and alternative materials may readily be substituted without depart-ing from either the spirit or scope of the in~e~tion.
DESCRIPTION OF THE PREFERRED EMBODTMENTS
The following example illustrates the synthesis of a phosphono analog of CI Acid Yellow No. 11, a pyrazolone dye:
8.7 grams of 3-amino~enzenephosphonic acid and 5.3g of Na2C03 were added to 100 ml of ~2 and cooled to 15C.
Dyes are retained in fibers by physical adsorption, salt or metal-complex formation, solution, mechanical retention, or the formation of covalent chemical bonds. Physical aasorp-tion and solution, in which the dye is partitioned between the fiber and the surrounding aqueous phase, are equilibrium reactions, and only by very careful selection of the dyes used, can good washfastness properties be achieved. Salt and metal complex formation are also equilibrium reactions and, though generally the retention of the dye is favored more than in physical adsorption, washfastness may still present a problem.
The dyes that are held ~y mechanical retention (azoics, vats and sulfurs) are virtually insoluble in water and show excellent fastness to washing, but have other disadvantages. They are, for example, difficult and expensive to apply; loose dye, which is not easily washed off, may be deposited on the sur-face, resulting in low fastness to rubbing (crockfastness), and the final shade of the dyeing does not deveiop until com-pletion of the whole dyeing cycle and aftertreatments.
Chemical bonding of dye to fiber for fixation ~f dye was recognized as early as 1895. The reactive dye systems presently available require that the dyes contain a functional group capable o~ forming a covalent chemical bond with the fiber.
Fiber-reactive dyes are employed quite widely in coloring cellulosics and proteinaceous fibers. They, of course, exhibit excellent washfastness, resistance to rubbing, tinctorial powers, ease of application and leveling. The latter quality is a measure of uniformity a~d most important for long dye runs and color matching. The reaction of the dye with cellulosic fi~ers is basically an esterification or etherification reaction and is broadly represented as:
Dyc ~ ~ ~ Cl I Ce`l-OH ; Dyc ~ O l-O-Cc~
Cl Cl Dye-SO2C~2CH2oH + Cel -OH -~ ~ye-SO2CH2C~20-C21i (II) The triazine reactive group imparts oil solubility characteristics to the high molecular weight dye which hinder and interfere with an aqueous solubilizing group such as -SO3H. These dyes ar_ unstable and difficult to work with.
Most of the reactive dye systems are based upon chemistry where the reaction is effected in alkaline solutions. There are few present reactive dye systems which operate effectively at an acid p~. Such a system is desirable in the dyeing of mixed fabrics such as cotton blends with polyester, wool or nylon, the latter fibers being dyeable by acid dyes. ~owever, acid dyes,generally have no affinity for cellulose and usually only find use in dyeing of protelnaceous fibers. F~ther re, Qince the dye and fiber substrate are coreactive, complete dye-ing of the fabric will occur unless speclal precautions are prac ticed to localize the dye in areas of the fabric by printing, ;
stenciling or other graphic technique.
The American Cyanamid Company has published a book-let entitled "Cyanamide", which sets forth a considerable number of reactions of cy namide and dicyandi~mide. Page 32 of this booklet indicates that cyanæmide was long ~nown to be a dehydrating agent when warmed with anhy~rous formic acid and in the esterification o~ lactic or saLicylic acid in absolute ethanol. Note Pratorius-Seidler, G., J prakt. Chem. {2l 21, 129-50 (188Q); C.Z. L880, 245. A number of papers have inves-tigated the reaction of cyanamide with car~oxylic acids, and have ~roposed a mechanism wherein the acid is , converted to the anhydride ~y interaction with cyanamide, with for~ation of urea, and su~sequent acylation of the urea by the anhydride to produce a ureide, which at elevated temperatures interacts with the acid to produce an amide.
Cyanamide ~nd dialkylcyana~ides are also useful in the Synthesis o~ pyrophosphates. Kenner, G. W., Reese, C.B., and Todd, A.R., J. Chem. Soc. 1958, 546-51; ~.A. 52, 11072 (1958) indicates that a high energy phosphorus - oxygen bond is present in the presumed intermediate O-phosphoryl-pseudourea.
The use of cyanamide and phosphoric acid to impart flame retardant properties to cotton and other cellulosic fabrics is well known to the art. For instance, O'Brien "Cyanamide ~ased Durable ~lame-Retardant Finish for Cotton", Textile Research 3Ournal, March, 1968, pp. 256-266 indicates, at page 265, that the reaction of cyanamide and phosphoric acid with cellulose results in a cross-linking of cellulose molecules. From the properties of the resulting product, it is suggested that the cross-linked cellulose is some type of a dicellulose phosphate ester.
S~MARY OF THE INVENTION:
The present invention provides a dye system for dyeing hydroxy substituted substrates in which the reaction can be conducted in acidic to mildly alkaline solutions.
The dye system o~ the invention is a reactive system in which the reactive function is not self-contained in the dye molecule. Since the dye and fiber re~uire the presence of a condensation agent for reaction, certain dyes such as azo dyes, where the dye is formed by a sLmple coupling reaction, can be formed via an intermediate on the fabric which can be selectively color developed in discrete locations to form a pattern. The background areas can be fixed to expose or decompose the remaining precursor areas.
The dye system of the invention is further simplified in that a ~ingle group serves both as an aqueous s lubilizing group and as the potentially reactive coupling site to the fiber, thus providing a more simplified synthesis and a less complex and more stable dye molecule and dyed fabric.
m e present invention, in one aspect, resides in ., a method of forming a reactively dyed polymeric substrate, said method comprising:
~ a) contacting a polymeric substrate containing active hydrogen atoms present in the form of amino or thiol groups with a cyanamide compound selected from the group consisting of cyanamide, alkyl-substituted cyanamide, dicyandiamide, and alkyl-substituted dicyandiamide, wherein the alkyl groups each contain 1-6 carbon atoms, and with a coloring amount of a chromophore-substituted phosphorus acid of the formula:
(01 Rm ~ P - (OH3p (OR) B~4 wherein each R i~ a chromophore, m is 0, 1 or 2;
n is 0 or 1; p is 1 or 2; and ~ is 0 or 1; and m ~ p + ~= 3, at least one ~f m and ~ l~eing other than 0, at a pH of from about 1.5 to about 9, wherein the S equivalent ratio c)f said cyan~anide compound to each phosphorus acid ~unction of said chromophore-substituted phosphorus acid is at least about 2:1 and ~I heating the contacted substrate to a temper--ature of at least 200F for a time sufficient to fix said chromophore to said substrate.
This method is also disclosed, and is claimed, in Canadian Patent Application No. 219,183, filed January 31, 1975, (now Canadian Patent No. 1,090,054, granted November 25, 1980) of which the present application is a divisional.
In another aspect o~ the invention, there is provided a reactively dyed organic polymeric substrate of the formula:
()n m ~ \
(OH)z (OR~q where each R is a chromophore, said chromophore heing linked chemically to the P atom; Rl is the chain of a polymer having reactive groups with active hydrogen atoms selected from alcoholic hydroxyl groups, amino groups and thio groups;
m is 0, 1 or 2; n is 0 or 1; q is 0 or 1 and z is 0 or 1;
and m f p + q = 3, at least one of m and q being other than 0.
-7a-This aspect o~ the inYention is also disclosed, and is claimed, in Canadian Application No. 219,183, filed January 31, 1975, (now Canadian Patent No. 1,090,054, granted November 25, 1980) of wElich the present application is a divisional.
In our Canadian Patent 1,006,655, granted March 15, 1977, a related invention is disclosed and claimed. According to the invention described in that patent a reactively dyed hydroxy-substituted organic polymeric substrate is formed by the steps of:
cc)ntacting a substrate of the formula, RlCH, where Rl acids and amine or ammonium salts thereof and a water soluble carbodiimide in which the ratio equivalent of carbodiimide to acid is at least about 2:1. The invention to which said Canadian Patent 1,006,655 pertains is concerned particularly with the dyeing of cellulosic substrates.
The pre~ent invention, in a further aspect, resides in a dyestuff of the followinq formula:
o H ¦¦
,~=N~
/~ J~ SO3H PO(OH) 2 -The dye system of the present invention results in reactively dyed fabrics by immo~ilization of a dye as a cellulose phosphorus ester according to the following illustrative reaction:
(Il)n (~)n Rml-(0~)p + R'OH + CDI~ Rm-l + CDIX
(OR)q (OR) q where R is as defined above, R'OH is cellulose, CDI is a carbodiimide, CDIX is a CDI residue or by-product, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, q is 0 or 1 and z = p-l.
Thus, a chromophoric grouping (R) linked chemically to a phosphorus acid such as phosphonic, phosphonous, phosphinic or phcsphoric acid, reactively dyes cellulose (R'OH) with the aid of a carbodiLmide condensing agent (CDI).
Cyanamide which is a suitable carbodiimide, allows for a rapid esterification of phosphorus acids with alcohols. The by-product, CDIX, is urea. Thus, where R is a chromophore and R'OH is cellulose, a fiber reacted dye compound is formed is the chain of the polymer and OH is any h~droxyl group on the chain in the presence of a carbodiimlde with a chromophore substituted phDsp~orus acid of the formula:
CO~
n - P ~OH~p ~ORlq where R is the chromophore, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, and g is 0 or 1; and heating the contacted su~strate to a temperature of at least 200F for a time sufficient to react said acid with said hydroxyl to form a dyed substrate having a phosphorus ester linkage between said chromophore and chain and having the formula:
(~n Il ~ ORl R P
¦ (OH~
COR~
where z is p-l.
Also described and claimed in Canadian Patent 1,006,655 æ e reac~;vely dyed hydroxy-substituted organic polymeric substrate~a reacti~ely dyed hydroxy-substituted organic polymeric substrate of the formula:
r)n ¦¦ ~O
R_ P
¦ (OH~z (CR~
where R is a chromophore group, Rl is ~he chain of the polymer, m is C, 1 or 2, n is 0 or 1, a is 0 or 1 an~
z is 0 or 1; and compositions for reactively dyeing h~droxy-substituted organic polym~ric substrates comprising an aqueous solution containing at least 0.1~ ~y weight of a su~star.ce select^d from chromophore substitu~ed ~hosphorus _7~
111~844 with cellulose. This results is a substantial and washfast dyeing of cotton and other cellu7osic or hydroxy containing substrates. Cellulose esters of phosphonic acid dyes are found to be the most stable to heavy-duty alkaline detergents. The reaction of phosphonic acid dyes would proceed as follows:
O O
Il 11 R-P-OH + R'OH + CDI ~ R-P-OR' + CDIX
OH OH
The fabric or fiber system of the in~ention proceeds by forming an aqueous solution of a chromophore or precursor thereof linked chemically to a phosphorus contai~ing acld.
The solution general'y contains at least 0.1% of the dye and genera~ly no more than 10% by weight of the dye depending on the intensity of the chromophore and the shade desired. The dye concentration is generally between 0.1 and 5% by weight and the concentration of reacted dye on the fabric is believed to be in the range of 0.01 to 0.05 weight percent, although much greater concentrations of dye on the fabric can be employed, e.g., up to even 5.0 weight percent, or more; 10 4 to 10 2 mo~. percent.
The pH of the solution is generally about 3-4 but can be ~aried from about 1.5 to 9. Lower pH can be provided by addition to the impregnation bath of '%-5~ of an acid which is non-volatile at the cure temperature, and does not cause undue degradation of the substrate, such as a phos~horic acid, 'ower alkyl phosphonic acid or chloroacetic acid. This appears to im rove the efficiencv or^ t;~e aye im~obilizatior.
since less dye is found to wash out after cure. ~he amount of carbodiimide is usually increased in a ~ath containing added acid. ~igher pH baths mav be uti' zec cortaining s~'ts which are converted to the acid form during cure such as fugitive amine salts, or ammonium salts of the phosphorus acid chromophore. Higher pH baths may be necessary in certain situations which present corrosion problems, or have mixed fiber systems or fibers which would be excessively degraded at low pH.
Generally, in the bath the molar equivalent ratio of the diimide to each phosphorus acid function is at least about 2:1. Curing is generally conducted at a temperature of at least 200~F and generally below 400F. Preferably, the fabric may be preliminarily dried at a temperature below 200F before cure. The cure time can be varied from the order of seconds to hours depending on the temperature, dye concentration and fiber being colored.
~ he reacti~e dye system of the invention is general-ly applicable to substrates containing available hydroxyl groups such as cellulose, particularly cotton,and may ke practiced on fibers, films, yarns, cords, threads, paper, fabrics, non-woven or woven, knitted; or other types including pile fa'orics, velvet5~ knitted fabrics, corded webs or webs foDmed by a random webber.
The water-soluble condensation agent assists ln the formation of the phosphorus ester l nkzge be_~een the chromo-phore, R, and the cell~'ose substrate, R'OH. The agent is preferably a water-solubl~ carbodiimide such as ~yanamlde or dicyandiamide.
The impregnatins bath may also cont2in ~l~or ~mounts of conventi3r.al additives or assistants such as an~i-migralins agents, Glauber's salt, or ~ettin~ asents. Ccmpat_ble thic~-eners may also be present.
g The dyes that can be utilized in the dye immobiliza-tion process of the invention can be of diverse type and 3tructure. The dye may be an anthraquinone, phthalocyanine, mono-azo, polyazo, benza~throne, pyrazolone, naphthoquinone, triary~methane or cyanine type that is modified to contain a phosphorus acid group to impart water-solubility and to provide a reactive site for attachment to the hydroxyl groups on the substrate. The dyes may contain other aqueous solubilizing groups such as sulfonate and may contain other substituents that do not interfere with aqueous solubility characteristics or the dye immDbilization esterification reaction.
~ any of the phosphorus acid substituted dyes utilized in the process of the invention axe ~nown materials readily available m the art, and have been used to direct dye wool and other proteinaceouc fibers. Suitable dyes are di~closed in Belgium Patent No. 570,326, British Patent No. 455,092 and United States Patent Nos. 2,596,660 and 2,799,701. Analogues of many sulfonated dyes can readily be synthesized in the phosphono form by substituting the phosphono analog for the sulfono-containing compound during synthesi~.
The proces~ of the invention may be readily adapted SG
that it can be carried out in commercially available machinery used for dyeing or textile pr~nting processes and for continuous or non-continuous variations of 3uch processes. The fibrous or sheet material may be impresnated Wlt~ the dyestuff solution and then s~bjected to curing by heating, for example, ln a hot flue dryer, an oven or a stenter. The im~re~nation may be carried out for example by padding material ~th an aqueous solution cont2inir;g the dyestuff and curing agent. The dye treatment may also be car_ied out by textile printing ~ethods, 111~844 r for example, by locally treating the textile with a solution containing the dyestuff and condensation agent and thereafter subjecting the printed material to an elevated temperature for curing. Alternatively a phosphono-substituted primary agent may be coupled to the cellulose and thereafter coupled to an azo chromophore component.
The invention will now become better understood by reference to the following detailed description when considered in conjunction w~th the spocific examples of practice. It is to be understood that these examples are presented solely for purposes of illustration and not by way of limitation, and alternative materials may readily be substituted without depart-ing from either the spirit or scope of the in~e~tion.
DESCRIPTION OF THE PREFERRED EMBODTMENTS
The following example illustrates the synthesis of a phosphono analog of CI Acid Yellow No. 11, a pyrazolone dye:
8.7 grams of 3-amino~enzenephosphonic acid and 5.3g of Na2C03 were added to 100 ml of ~2 and cooled to 15C.
3.7g of NaN02 in 10 ml of H20 were added to yield a brown solu-tion w~ich was slowly poured with stirring into 21 ml of concen-trated HCl containing 60g of ice. The mixture was stirred for 15 minutes and gave a positive response to the starch - KI test.
The diazotisation method is ~ased on Vogel, "Practical Organic Chemistry" (1951), p. 596, and follows the following reaction sequence:
MH2 N=NCl +~ 2 -t ~ICl ~C~3 _ ~ ~
~ (~-)2 ~ ~ (OH)2 j ~
8~4 Coupling of the diazotized intermediate (III) is based on British Patent No. 753,771. The solution containing the intermediate (III) was added to a solution containing 12.7g (1/20 mole) of 3-methyl-1-(p-sulfophenyl)-2-~yrazolin-5-one and 10g of sodium acetate in 100 ml of ~2 The pH of the second solution had been adjusted from 5.3 to 7.0 with NaO~. After stirring for 15 minutes the pH was 2.0 and there was no evidence of precipitation. On addition o~ isopropanol, a yellow powder was precipitated which after separation and drying in a vacuum oven yielded 13g. Coupling proceeded according to the following reaction:
- y=~ Cl ~'~ '.+
~ (~-)2 CH.~ ~ (Or.) 2 cr~.3 ,,~ . ' / \ ~ "
\ -Cç~;~S~3~la 3~ ~ -C6R4S03~a The following example illustrates the syntnesis of a bis pho~phono, bis-azo dye.
EXaMPLE 2 3-Aminobenzenephosphonic acid was diazotized accord-ing to the procedu_e of Exampie 1 usir.g 13 m~ of concentrated HCl. 18.0g (1/20 mole) of the mono-sodium salt of 8-amino-1--naphthol-3,6-disul~onic acid wa~ suspended in 50 ml of K2O
a~d the p~ was adjusted from 2.3 to 7 with NzOR. ~his solution was added to the diazotate to form a dar.k red solution h~ir.g a pH of 2.5.
Al.kaline coupling was racticed accordins to Vogel, supra, p. 597.
111~844 The red solution precipitated on standing and was adjusted to pH 7 with NaOH. 40 ml of a 10% NaOH solution was then added and cooled to 5C. A second preparation of diazo-tate was then added to form a blue solution having a pH of 7.4.
After 15 minutes the pH was adjusted to a pH of 2 with HCl.
The dye was precipitated with isopropanol to yield 40 grams of blac~ powder having the formula:
~_a~ N=N'- ~
O(O~)2 ~.2O3S -SO3`~ ~(~)2 The pyrazolone yellow dye of Example 1 was used to dye c~tton fabrics according to the following procedure.
A pad bath was prepared containing 5% o' the pyrazo-lone yellow dye, three molar ~quivalents of cyanamide (1.33 weigh_ percent) and 0,1% "Triton X 100*" (Rohm & Haas - octyl phenoxy polyethoxy ethanol - non-ionic wetting agent). The bath had a pH of 2.9. Samples of print cloth fabric were padded at 40 psi, and then oven dried for five mlnutes at 150F
except for one fabric that was air dried at room temperature.
One sample of fabric was cured for five minutes at 320F. An oven dried fabric was cut in half for color ccmparison. All but one one-hal~ of the ovan dried fabric were washed for eight minutes with heavy-d~ty detergen., dried and then ironed.
The air-dried fabric was colorless, the o~en dried 'abric was colorless, whereas the cured fa~ric had a bright lemon yellow color with some washoff by comparison with unwashed fabrics.
The colored fabrics were boiled for Gne hour in 3~ K2C~3 with some color lost. The fi~al color was a p2stel yellow shade of the orisinal bright yellow color.
*Trademark - 13 -111~844 Since the fabric subjected to air drying lost all color on washing, it is app~rent that the dye was not substan-tive. It is quite unexpected that the ester ~inkage of the fixed dye is sta~le to hot detergent alkaline medium since it would be expected that the phosphoru~ ester moiety would hydrolyze and rupture the dye attachment.
The blue dye of Example 2 was utilized to color cotton fabric according to the following procedure:
A pad bath was prepared containing 5% of the blue dye plus 6 molar equi~alents of cyanamide ~1.73%) and 0.1% of " ~1 Triton X 100. The pH of the bath was 2.6. Samples of cotton fabric were treated, dried and cured as in Example 3. After washing, the air-dried fabric was almost colorless. The oven-dried fabric was a very pale blue, whereas the cured fabric was a very dark navy blue. There was some sLight washoff by comp~rison with the unwashed fabric. The warp ~hrinkage was -3.75% whereas the fill shrinkage was +0.75%. After the fabric was boiled for one hour in 3% K2CO3, the final color was a darX pu~ple .
It was then attempted to fix the dye of Examp'e 1 on fabric using heat without the presence of a carbodiimide.
EX~MæL2 ;
A bath was prepared, containing 5% by weight of the pyrazolone yellow dye of ExamplP 1, 21us 0.1~ Triton X 100.
The p~ of the bath was 2.9. The bath did not contain any car~odiimide or equivalent mat2rial.
Samples of cotton fabric were ~added at 40 ?si, dried for fi~re minutPs at 150~ ar.d cured fcr five further minutes at 320~F, washed in hea~y-duty detergent 2nd ironed. The fabrics contained only a trace of yellow color. A dye and heatstep at curing temperature is not capable of fixing the dye on the fabric.
It was then attempted to fix on fabric the dye of Example 1 by means of a pad bath containing urea.
EXAMP~E 6 A bath w~s prepared containing 5~ by weight of the pyrazolone yellow dye of Example 1, 0.1~ Triton X 100 and 1.9 urea (3 mclar equivalents). The pH of the ~ath was 2.9.
Samples of cotton fabric were trated as in Example 5 and the samples xetained no more color than those of Example 5 showi~g that no dye immobilization occurred by this procedure.
It was then attempted to fix the dye of Example 2 on fabric using heat or urea in the a~sence of a carbodiimide.
Two baths were prepared, one containing 5% of the , ~
blue dye of Example 2 plus O.1% Triton X 100 and the other additionally containing 2.5% urea ~6 molar equivalents). The p~ of the first bath was 2.65 and that of the second bath with urea was 2.70. Samples of cotton fabric were padded at 40 psi, dr~ed for five mlnutes at 150F, cured for five minutes at 320F, washed in hea~y-duty detergent and ironed. Only a trace of blue remained in the fabrics. Colors were all about the same.
Th~ following example shows the use of polyvinyl alcohoL and phosphoric acid as adj~vants to ~e coloring bath:
A pad bath was prepared containing 1~ ~y weight of the blue dye of Example 2, 1~ E~PO4, 1.~% cyanamide ar.d 6 milliliters of 4~ Polyvinyl alcohol. ~To wet~ing aser.~ was _ 15 -' 1~11~
a~ded. The pad bath was used to treat 100~ cotton cloth and 50-50 cotton polyester cloth, according to the procedure of Exzmple 3. The cloths showed good color retention and sta-bility with very little washoff and very good resistance to boiling K2CO3. A similar bath containing 4% "Cellosize*" in place of poly~inyl alcohol gave a similar result and also imparted some blue color to glass cloth.
The following example illustrates the use of dicya~-diamide in place of cyanamide.
EXAMP~ 9 A pad bath was ~repared containing 1.5~ by weight of the yellow dye of Example 1 and 1% of dicyandiamide. ~0.8%
would be a molar ratio of 1:3). Samples of cotton cloth were treated according to the procedure of Example 3. After wash-ing, the dye i~mo~ilization was essentially the same as fhe cyanamide treated fabrics of Example 3.
The following example illustrates preparation of the benzyl phosphonic analog of the dye of Example 1.
p-Aminobenzyl phosphonic acid was coupled with the sulfophenyl pyrazolone utilized in Example 1 utilizlng 9.4 grams of the benzyl acid (0.1 mole) in place of 8.7 grams of the phenyl a~id. The pH was finally adjusted to 3.0 with HCl and the solid precipi~ated with isopropanol, presuma~ly as the monosodium salt having the structural formula:
*Trademark of Union Carbide Corporation for hydroxyethyl cellulose and/or carboxymethyl cellulose.
84~
C 3 l l N=N ~ CH2 P - OH
~=0 SO 3Na The dye exhibited similar behavior when utilized to color cotton fabric samples according to the procedure of Example 3.
The following experiment illustrates the preparation and use of the ammonium salt of the dye of Example 1 at higher pH.
An ammonium salt of the yellow dye of Example 1 was prepared by dis-Qoving the dye in an aqueous NH40H solution and evaporating the solution to dryness.
A pad bath was prepared containing 1% of the ammonium salt dye, 0.3~ cyanamide and 0.25% "Alipal CO 436*" (nonyl phenoxy polyethoxy-ethanol=sulfated, NH4 salt). The pH of the bath was 5.8. The bath was applied to fabric and cured as in Example 3. The dye immobilization was substantially the same as in Example 3.
An acid pad bath was prepared containing 1% of the sodium salt of the phenyl dye of Example 1, 0.25% of "Alipal**"
*Trade~ark **Trademar~ ~or a series of anionic surfactants containing alkylphenol and ethoxy groups in the molecule.
~' 1~118~4 and 3% of H3P~4 and 4.5% ~f cyanamide which represented a molar e~uivalent rati~ of 3:1 o~ the cyanamide to the combined dye ~;
and acid. The pH o~ the pad bath was 1.8.
-17a-Samples of fabric cloth impregnated, cured and washed according to the procedure of Example 3 showed very little washoff. U.V, analysis of the cloth indicated about 75% dye fixation.
Nethyl phosphonic acid ~MPA) was substituted for the H3PO4 of Example 12 and the cvanamide content was reduced by 1.3~ to adjust the MPA/cyanamide molar e~uivalent ratio to 1:2.
The p~ of the bath was 1.8. Samples of abric, Lmpregnated, cured a~d washed according to the procedure of Example 3 again demonstrated very little washoff, A sample of fabric which was air-dried before cure to minimi"e migration showed some-what improved color retention.
The following experiment shows the necessity of a phosphorus acid group in the dye molecule, A pyrazolone dye was prepared utilizing metanilic acid in place of the 3-aminobenzenephosphonlc acid of Example 1. A bath was prepared containing 1% of the sulfonated dye, 3% H3PO4, 0,25%1'Alipal*" and 4.5% cyanamide. The pH of the bath was 1,7~. Samples of fabric L~pregnated, cured and washed according to the procedure of Example 3 showed extreme washoff demonstrating that little or no dye was fixed.
Fixation and immobilization of dye by 'ormation of a phosphorus acid ester lin~age was further confirmed by the following experiment, A solution of 5% 3-aminobenzenephosphonic acid con-taining 3 molar e~uivalents of ~anamide was utilized to impregnate cotton cloth, The cloth was cured at 320F for *Trademar~ for a series of anionic surfactants containing alXyl~henol and ethoxy groups in the mo'ec~le.
111~8g4 five minutes to couple the ~mine base to the cellulose through the phosphono~ kage.
The cellulose-coupled amine base was then subiected to diazot~zation with the Na~O2-~Cl solution of ~xample l to form a diazonium salt. A portion of the cloth was exposed to light to decompose the diazonium salt. The fabric ~as then immersed in a solutton of the sulfophenyl pyraz~lone uti~zed in Example 1 and dried and washed. Color was only retained in the nonexposed areas, con4irming the phosphono-ester linkage as the immobilization mechanism.
A copper phthalocyanine substituted with phosphonic acid and sulfonic acid groups was prepared by heating an inti-, mate mixture of triammonium 4-sulfophthalic acid (llg), mono-potassium 4-phosphonophthalate (llg), urea (20g), cupric chloride dih~drate t3g), and ammonium molybdate (0.25g) at 250C, The product was purified by washing wl~h hydrochloric acid and drying in a vacu~m oYen at 60C.
A bath was prepared contai~ing 1% of this product, 20 ~ H3PO4, 4.4% cyanamide and 0.,25% Alipal. The p~ of the bath was ad~usted to 2.5 with t_iethanolamine. Samples of fabric impregnated, cured and washed according to the procedure of Ex~mple 3 were a green~sh-blue color.
The present in~ention pro~ides a no~el acid system for the fast dyeing of hydroxy fi~ers. The reactively dyed fibers exhi~it good color and are sta~le to hot basic media.
The dye system of the present invention provides 2 further zdvan~age since the dye can ~e recovered frcm ~he ~ath by precipitation on a calcium su~strate such as lime, CaC03 or 3a marb'e and can ~e regenerated by acid.
1~11844 The results obtained herein~bove indicate that the process of reactively dyeing textiles and otner substrates has broad applicability. The process of the present invention may be broadly applied to many substrates ha~ing an active hydrogen atam according to the well-known ~erewitinoff test (J. Am. Chem. Soc., 49, 3181 (1927)). Especially pre~erred are s~bstrates having alcoholic hydroxyl (non-phenolic) groups, amino groups, or thiol groups. That is, the re~cti~e site on the substrate may ha~e the formula -OH; -NH2~amino); -NH-L0 -(amino); or -SX. Thus the process of the present in~ention results in the fixation of phosphorus-containing dyestuffs on rayon. The fixation is obtained with wool but the depth of shade is not as good as with rayon. Fixation of the dyestuff is also o~tained with nylon, but the depth of shade is some-what inferior to that of wool. Of the ~ubstrates having Zerewitinof~-active hydrogen atoms, those compounds having hydroxyl groups are grea~ly preferred, especially organic poly-mers having hydroxyl groups. While the substrate may ~e in the form of cast or other massive articles, it is greatly preferred that the substrate be a textile fabric or a textile yarn, filament or fiber.
The results obtained with ~yanamide and dicyandiami~e ~uggest that cyanamide compounds of the genera' ~ormula X
/ N - C _ N
x2 wherei~ Xl a~d x2 are hydrogen, lower alkyl, or tcgether are ~(X3)2 = C
\N(~3)2 - 2~ -~y~
wherein each X3 is independently hydrogen or lower alkyl, can be used in the process of the present invention. Thus, methylcyanamide, dimethylcyanamide, ethylcyanamide, diethyl-cyanamide, butylcyanamide, dibutylcyanamide, and other cyanamide compound~ falling within the scope of the above formula dls-closed in the aforesaid American Cyanamid Company "Cyanamide"
booklet, may be used in place of cyanamide cr dicyandiamide.
Compounds of the above general formula may exist in tautomeric form and these tautomers are intended to be included in the general formula.
The dye, the fiber, and the cyanamide compound can be brought together in any particular order. Normally, the dye and the cyanamide compound, together with any con~entional additives or assistants, will be in the form of an aqueous solution, which is padded or otherwise applied to the substrate..
At least a coloring amount of the dye will be reacted onto the substrate.
As mentioned hereinabove, it is possible to form the dyestuff on the fabric essentially "in situ", by coupling a phosphono-substituted compound to the cellulose and thereafter coupling that c~mpound ~o an azo chromophore component or other chr~mophoric group. Alternatively, the pho~phorus~con-tainin~ dyestuff could be applied to a textile fabric which lS
- then subiected to an aftertreatment with the cya~amide compGuna.
Regar~less of the technique actually used, it is c~ea~ that the thrust of the present in~ention resides in contacting a poLy-meric sub~trate c~n~ai~in~ ~erewi~inof~-active hydrogen atoms, especially alcoho~lc hydroxyl, amino, or t~iol groups, with a cyanamide compound and wi~h a ~hromophore-substituted phos-phorus acid or a chromophore ~recursor-substituted phosphoru~
acid, and heating the contacted substrate to an elevated tem-perature to fix the chromophore or chromophore precursor to the substrate.
Mixtures of substrates, dyes, and/or cyanamide csmpound~ may be used if desired.
The addition of phosphoric acid to the impregnating bath appears to impro~e the efficiency of the dye Lmmo~iliza-t~on, ~ut can ha~e the undesirable effect of r~ducing the strength of the fabric by as much as about 50%. Dyes contain-ing two phospnonate groups or other phosphorus acid groups have been found to have an efficien¢y of qreater than 90~, when affixed to cotton or another suitable su~strata by the use of cyanamide or dicyandiamide, without using any phosphoric acid in the dyebath. Since no phosphoric acid is added to the dye-bath, the fabric essentially loses no strength duxing the dyeing process. Thus, where the strength of the textile fa~ric mu~t be maintained, and high c~upling efficiencies of the dye-stuff achieved, the use of the dyestuffs containing two or more pho~phorus acid substituents is often greatly preferred.
However, recent wor~ has established that monophos-phonate dyestuffs can produce excellent fix~tion on substrates, using the process of the present invention, at a pH of about 5.
To achieve this pH, it is preferred to add a~out 0.125 to a~out 0.25 weight percent of phosphoric acid ~ the "dyebath. Thus, broadly ~he amount of acid th~t can be used i~ the dye~ath ranges from about 0.1 to about 5 weight perc~nt.
Example 4 herei~above relates to using a di~phos-phorus acid)-substituted 2yestuff. Additional examles of using such dyestuffs are set forth ~e~ow.
11118~4 EXA~LE 1 7 H acid (81% pure, 43.5g, 0.1 mole) of the formula:
N~2 OH -SO~
was suspended ln 300 ml water and 100g ice and the pH adjusted to 6 with sodium hydroxide solution. Sodium acetate (39g, 0.3 mole) was added, followed by ~-chlorosuLfonylbenzenephos-phonic acid ~30g, 0.12 mole) in portions over 10 minutes, the temperature being mainta~ned at 10C and the p~ at 6. The solution was stirred for three hours ~n an ice bath, and then sodium car~onate (25g) was added.
To this solution was added a diazotized solt~tion of m-aminobenzenephosphonic acid. The combined solutions were stirred for 1 hour, then concentrated hydrochloric acid (400 ml) was added and the solution filtered to yield a red dye with the structure:
S
EXA~T E 18 ~his and ~he ~ollowing three exa~ples relate to the production o~ orang~ dyes, using, as the starting compour.d, J aci~ of Lhe ~or~ula:
~O~ R .
in place of the H acid. Example 17 was repeated, replacing the H acid with J acid, producing an orange dye o~ the formula: . O~
50~1~ Hs o,4 Eæ~l.E 1 9 Example 18 was repeated, but using the N-methyl deri~ati~e of the J ac~d, to p m duce an orange dy~ of the formula: o~
SO~ CJt, EXAMP~E 20 Example 18 was repeated, but th m-chlorosulfonyl-benzenephosphonic acid was replaced by benzoyl chloride, and the diazotized solution of m-aminobenzenephosphonic acld was replaced with a diazotized solution of o-amino-p-xylylenedi-phosphonic acid, to produce an oranse dye of the formula:
Cl~a Pof~ , OJ/
~,Po(o~O~JJ~:o~
- E~ ~ 21 Example 19 was repeated, but the m-chlorosulfonyl-benzenepnosphonic acid w~s deleted, ana the diazotized so~u-tion of m-aminobenzenephosphonic acic was repiaced ~ h a diazotized so~ ution of o-~mino-p-xyly' er~ed~ phosp~onic ac1 d, to produce an orange dye of the for~nula:
, po (OH~a 011 ; H C
c 1~, ro,~O~),, EXAM~LE 2Z
Following the procadure of Example 21, an orange dye was made by treating ~ -naphthol with diazotized o-amino--p-xylylenediphosphonic acid, and the resulting dye had the formula: -01~ CH, PO (0~1),.
~ C~J,,Po(o~
Example 22 was repeated, replacing the ~ -naphthol with F aci~, of the ~ormula:
-HO ~S
111~8~4 resulting ~n an orange dye Q:i' the forr~ula:
OH CH2PO(OH)2 ¢~N=N- ~
¦ ~) H2PO(OH)2 \~03H
Bromaminic acid (89.996 pure, 132 g, 0.315 mole), p-amino benzylphosphonic acid (65g, 0.345 mole), and cuprous chloride (:12 g~ were stirred in water 1800 ml) and ethyl alcohol (:200 mll, and sodium carbonate (160 g, 1.5 mole) added in portions. The solution was then heated to 50C, and stir-red at 45-50C for 18 hours. The reaction mixture was cooled and poured care~ully into concentrated hydrochloric acid (300 ml), and then :eiltered. The residue was recrystallized from aqueous hydrochloric acid to yield a blue dye of structure O NH
Il ~ 2 ~SO3H
O NH ~)-- CH2PO(~:)H)2 Example 24 was repeated, but the p-aminobenzyl-phosphonic acid was replaced by an equimolecular amount of ~c ~w 8~4 o-amino-p-xylylenediphosphonic acid, to produce a blue dye of the structure:
o NH
~ I ~ CH2PO(OH)2 O NH ~
CH2PO(OH)2 o-Amino-p-xylylenediphosphonic acid (28 g, 0.1 mole) was dissolved in water (150 ml) and sodium carbonate (21.2 g, 0.2 mole) added. Sodium nitrite (7.4 g, 0.107 mole) in water (40 ml) was added, and the solution was poured into a mixture of concentrated hydrochloric acid (50 ml) and ice (100 g). The solution was stirred at 5 for 20 minutes and then the excess nitrous acid destroyed with sulfamic acid. This solution was added to a solution of 3-methyl-1-(p-sulfophenyl)-2-pyrazoline-5-one (25.4 g, 0.1 mole) in water (300 ml3 containing sodium carbonate (50 g), and stirred for 1 hour at 5C. The solution was acidified with hydrochloric acid and from it was isolated the yellow dy~:
~CH2PO(OH32 N-N
HO
CH2PO(OH) so3 111~844 EX~MPLE 27 A pad bath was prepared containing 1% of the orange d~e of Example 23, 2% of dimethylcyanamide (about 15 molar equivalents~ and 0.1% "Triton X100". Samples of a multicomponent fabric containing discrete bands of wool, viscose rayon, silk, nylon, cotton, and "Dacron*" were padded at 40 psi, oven dried for 2 minutes at 180F and cured for 1.5 minutes at 390F. The fabrics were washed in detergent, rinsed and dried. Uhder these conditions, the wool was only slightly tinted and the "Dacron" unaffected. The rayon and cotton were dyed a bright orange, the nylon was dyed pink, and the silk was dyed a darker shade of orange than the cellulosic fibers.
An aqueous dye ~olution was made, with the solution containing 1~ by weight of the orange dye of Example 18, 1%
by weight of cyanamide, and 0.1% by weight of a surfactant ("Triton X100"~. Rayon, nylon and wool fabrics were immersed in the dye solution, dried for five minutes at 180F and cured for 90 seconds at 390F. After one home laundering the dyed samples showed significant dye fixation, with the rayon dyed the most strongly, followed, in order, by wool and nylon.
2~ Separate a~ueous dye solutions were prepared with each of the orange dyes of Examples 19, 20 and 23, each solution containing 1% by weight of the dye and 1% by weight of cyanamide. Separate cotton fabrics were then immersed in the respective dye solutions and then dried for five minutes at 180F and thereafter cured for ~0 seconds at 390 F.
*Trademark of DuPont for polyethylene terephthalate po'yester fiber.
After one home launderin~ all of the dyed samples showed excellent dye fixation.
An aqueous dye solution was made with the solution containin~ 1~ by weight of the yellow dye of Example 26 and 1%
by weight of cyanamide. Cotton fabrics were immersed in this dye solution, dried for fivé minutes at 180F and cured for 90 seconds at 3gOF. A~ter one home laundering the dyed samples were a bright yellow color and had excellent dye fix-ation.
An aqueous dye solution was made, containing 0.5 by weight of the blue dye of Example 25 and 3% by weight of dicyandiamide, this solution having pH of 2. Cotton fabrics were immersed in the dye solution, dried for five minutes at 180F and cured for 90 seconds at 390F. After one home laundering the fabrics were dyed a bright blue and the dye fixation was excellent.
An aqueous dye solution was made containing 0.5%
by weight of the blue dye of Example 25 and 1.25~ by weight of cyanamide, the pH of said solution then being adjusted to a level of 3 by the addition of ammonium hydroxide.
Cotton fabrics were immersed in the dye solution, dried for five minutes at 1~0F and cured for 90 seconds. After one home laundering the fabrics were dyed bright blue and the dye fixation was excellent.
In a fashion generally slmilar to that of Example 28 above, cotton swatches were dyed in aqueous dye soluticns pre-~' pared from each of the dyes of Example 21 (orange~, 22 (orange) and 24 (blue~. All of the dyed swatches showed excellent dye fixation after the home laundering.
COMPARATIVE EXAMPLE A
Example 28 was repeated, except the cyanamide was omitted. After one home laundering, the dyed fabrics were only tinted a very pale orange (an indication of little if any dye fixatlon).
~, ~111844 Additional classes of phosphorus-containing dyes can be readily prepared, following the procedures of Examples 17-21 and 23, but replacing the H, J a~d F acids with the dye intermediates disclosed in U.S. Patents:
2,a47,4s8 2,799,701 2,717,906 and 2,5~3,417 Additional phosphorus-containing dyes which may be used in the practice of the present invention are disclosed in the foll~wing patents:
Belgium 563,439 U.S. 2,326,047 U.S. 3,339,g99 U.S. 2,18~,998 U.S. 3,202,550 British 970,585 West German 1,042,523 Additional dyes whi~h can be produced following the procedure o Example 2~, but with different naphthylenic starting ~aterial~, are of the formulae.
pO (0~)~, ' .
, Cf~z t~
N03~
Po (f~')2, and - rO(o~2 ,~ '-' ' `~ `/Y~c~oc,~ -P~(O~JL
It is believed that the dyes of Exzmples 17, 18 and 19 are novel. The results obtained with the dyes of these examples suggest that a new dye family of the class R
I)ye--N-S02 ~1 ~Po(o~I)2 wherein R is hydrogen or lower alkyl, has been discovered.
These dyes, especially those containing two or more phos-phonate groups, wor~ very well in the process of the present invention, Of the various phosphorus-acid-substituted dyestuffs disclosed hereinabove, those dyestuffs substituted with more than one of said phosphorus acid radicals are particularly preferred, due to the excellent fixation obtained.
In the latter regard, the dyes co~tai~ing more than one phosphonate group have, as mentioned hereinabove, ~een found to ~e particularly preferred. ~he phosphonate 5ub-stituents may be loc~ted at any point on the dye molecule, at genera~ly pr~ximate positions or at positions further removed rom one another such as at the distal ends of the dye moiety.
Of the various phosphorus-acid-substitute~ dye-stuffs disclosed hereinabove, those dyestufCs substituted with one or more phosphonate radicals aIe parti~ularly ~11844 preferred, due to the ease of dyeing and excellent durabilityobtained .
The results obtained hereinabove i~dicate that chromophore-substituted phosphorus acids broadly of .he fo~mula:
tO) Il n R - P - (O~) ~OR)q wherein each R is a chromophore, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, and 5 is 0 or 1, and m + ~ ~ 5 = 3, and wherein at least one of m and q is other than 0, may be used in the process of the present invention. Chromophore-substituted phos-phorus acids having hydrocarbon substituents on the oxygen atom tin addition to the c~romophore) are not preferred, due to the decreased reactivity of these compounds, as well as the greater effort and expense in manufacturing same.
H~wever, it will be appreciated that such compounds may be used to replace part or all of the chromophore-substituted phosphonates or phosphates or similar compounds. Normally, only one chromophore will ~e attached to the phosphorus atom, either directly or indir~ctly (that is, it ia preferred that 2~ the sum of m and q is 1, for both the formula above and of page 7 hereinabove3, and it is preferred, as indicated hereinabove, that the chromophore carry two or more phosphorus acid grDups.
~ he present invention also includes novel xyl~lene diphospAonic acid dyestuffs of ~he general formula:
1~1184~
~2P03H2 Dye C~I2P03H~
wherein Dye represents a chromophore, preferably an azoic chromophore. Such dyestuffs offer two potentially reactive sites when used in the process described herein, a~d thus generally result in high levels of fixation of the dyestuff on the substrate.
In addition to the preferred azoic chromophore, it will be readily appreciated by those in the art that other chr~mophores may be utilized. For instance, Example 25 hereinabove relates to ~n anthraquinone chromophore. Clear-ly, any of tne other chromophores descrlbed hereinabove, or described in the references mentioned hereinabove, could be substituted for the chromophores disclosed herein in connection with the xylylene diphosphonic acid dyestuffs.
8~4 10 g of Procion Red NX2B (CI Reactive Red 1) were dissolved in 200-250 ml of water. One gram of m-aminobenzene phosphonic acid was dissolved in 50 ml ~f water, using a small amount of caustic to aid solubilization. Then the phosphonic acid solution was slowly added to the dye sol~tion with stirring. The i~itial pH of the dye solution was 6.5, and this p~ fell to 5.5 during the addition of the phosphonic acid. The pH was adjusted to 6.8 with 50% caustic, and then the solutio~ was warmed on a hot plate at 140F for ~0-30 minutes.
The resulting dye solution was cooled to room temperature and 15 g of phosphoric acid and 40 g of Cyanamide 50 (50% solution of cyanamide) were added, and the resulting solution was diluted to a total volume of 500 ml. The pH
of the final solution was 1.7.
The dye solution was then padded on 100~ cotton fabric at a pic~up of 70%. The padded fabric was dried for two minutes ~t 220F and cured for 45 seconds at 390F in a Benz u~it. The fabric was scoured with a nonionic detergent and soda ash, and then subjected to five home launderings.
Th~ retention of color on the fabric was very good.
It is belleved that the reaction betwe~n the Reactive ~ed l dyestu'' and the phosphonic acld was as ~ollows:
1~118~4 S03Na ~C~
N = N~ ~ ~ + ~ ( )2 NaOH
NaO3S I~lSQ3Na ~H2 H(N~3 P3H2 ~C
S03Na H ll 1~
/--\ HO p--C C~\ P03H
(~N = N~ N~ b,~ 2 NaO3S~903Na -- 3~i --.
A reduced dye solution was prepared of a convention-al monophosphate vat dye. A solution containing 5 grams per liter of the vat dye of the following formula:
~ 0~1 ~ .
~H
.
was reducsd ~y the addi~ion o~ 2 grams per liter of sodium nydrosulphite and, after the completion of the sodium hydro-sulphite addition, 2 sr~ms per liter of sodium hydroxide.
The addition of the sodium hydroxide was accompanied by a color change, which would be expected for vat dyes, as denoting reduction of the dye to its soluble leuco form.
Five grams per liter of a wetting agent (~Igepal CO-710*"), obtained from GAF) was also added to the solution.
Immediately after preparation of the above reduced dye solution, a sample was padded onto lQ0~ cotton, 3 ounce per yard sneeting, at a wet pickup of 75~. After padding, the sample was dried for 4~ seconds at 220GF.
A portion of the fabric sample was rinsed in hot water (at approximately 18~F) containing 10 grzms per liter of a scouring agent (Synthrapol ~SP o~tained _rom ICI).
A portion of the rinsed samp7e was th~n wasned 'ive times according to AATCC test meth~d 130-1970 II. The resul's are re~orted in Table 1 herei.~e~ow.
~Trademark of GA~ Cor~oration for nonyl~henoxy~oly~ethy'eneoxy~
ethanol; it is a nonionic surfac~n-.
i~ll844 Example 37 was repeated, up through the padding ofthe cotton sheeting with the reduced dye solution. The sample was then padded a second time through a 5 gram per liter solution each of acetic acid and hydrogen peroxide.
Aftsr the sacond padding step, the sample was dried for 45 seconds at 220F. After this oxidizing step, the sample exhibited a c~lor change, indicating that oxidation had occurred.
Portions of the sample were rinsed and washed by the procedure of Ex~m~le 37, with the results reported at Table 1 below.
EXA~PLE 39 Example 37 was repeated, through the drying step of the padded cotton sheeting. After the drying step, the sample was padded through an aqueous solution containing 80 grams per liter of cyanamide and 10 grams per liter of phosphoric acid. The sample was then dried for 90 seconds at 390F. This curing step a'lowed the reaction of the dye, the cyanamide and the cellulose to occur.
This sample was treated wi~h the rinsing and washing treatment described in ~xample 37. The results are reported in Table 1 below.
E~ample 3~ was repeated, but after th~ t~o ?addi~g steps and the d~ing step, the sample was ?added thrGuch the cyanamide-~hosphoric acid solution descrlbed in ~xampLe 39, and ~hen cured at 390F .or 90 seconds.
This samp'e ~as rinsed and ~ashed by the ?rccedure of Ex~ple 37, ~nd test resu'~s ~re re~Grted ir. Ta~'e 1 herei.~e'ow.
- ~8 -Example ~ Color After Rinse % Color After S Washe~
37 Pad 80.1 7.6 38 Pad ox. 40.6 10.7 39 Pad~pad 99.4 64.2 40 Pad/oxid/pad 99.2 73.5 As shown in Tab~e 1, there was some loss of color upon rinsing but the color loss was negligible for ~he samples of Examples 39 and 40. Washing resulted in even more dramatic differences between Examples 37 and 38, on the one hand, and 39 and 40, on the other. A definite difference in depth of shade of the samples was readily apparent. The samples of Examples 37 and 38 showed almost c~mplete loss of color. The samples of Examples 39 and 40, however, showed much less additional color loss after washing than the sa~ples from experiments which did not utilize the cyanamide treatment. There was no ~ubstantial increase in color yield of the ~ample of Example 40 over the sample of Example 39, indicating that the chemical oxidation step had little positive effect on increasing the retention of the dye in the cellulose, with the oxidation resulting in about a 9% increase in color retention.
Examples 37-40 indicate that the aftertreatment of a dyed fabric wi~h cyanamide, accompanied by a curing step, results in a more stable bond formation, and th~refore a high-.-er degree of fixation and dye retention n the fi~ar. The normal ~orces involved with vat dyes, inc~uding hydrogen bonding, van der Waals and other s~bstantive-t~pe bonds, werP
ins~fficient to retain suita~ie amounts o' the dye in the fi~er. In distinc~ contrast, the reaction between the dye, the cyan~mide and the cellulose created a bond which was s~fficiently strong to exhihit gocd dye ~etenticn.
Example 37 was repeated, using a correspondingamount of a monophosphonate dye of the following ~ormula:
~"C ~~P-O~
N~ ~
~H O
The results o~ evaluation of treated samples o~ this example are set ~orth in Table 2.
Example 38 was repeated, but using the mono-phosphonate dye of Example 41. The results of testing are set forth in Table 2 below.
Example 39 was repeated, but using the mono-phosphonate dye o~ Example 41. The results of testing are set forth in Table 2 below.
Example 40 was repeated, but using the mono-phosphonate dye of Example 41. The results of color retention testing are reported in Table 2 below.
Example ~ Color After Rinse% Color After 5 Washes 41 38.8* 9.6*
42 64.5 13.6 43 89.2 64.0 44 95.2 71.8 20 *Average of two samples The dyes used in Example 37 and in Example 41 were identical, except the phosphate group was replaced with the phosphonate group. The monophosphonate dye beha~ed in a similar mann~r to the monophosphate dye, with results almost identical.
~rl 8~4 The results lead to ~asically the same conclusions as for Table 1, and also lead to the conclusion that the phosphate and phosphonate dyes behave in a similar manner in their reaction with cyanamide and cotton.
Examples 37 - 40 were repeated, but using a monophosphate ~at dye of Example 13 of U. S. patent 3,339,999, which had the following formula:
~ ,,OC ~ CO N
Examples 45 - 48 had experimental results similar to Examples 37 - 40.
Examples 37 - 40 were repeated, but using a di phosphate vat dye of Example 2 of U. S. patent 3,339,999, having the following formula:
~C~
~N ~H O
NH O O NH o --P_o~/l~O ~l ~oll=o OH
84~
The results obtained for these examples were sLmilar to the results obtained for Examples 37-40.
Examples 37-40 were repeated, but using a diphosphate vat dye disclosed in Example 51 of U.S. Patent 3,339,999, and having the following formula:
~_ C~ ~C~
N~ O
,~3,C~ ~C_0~
0~1 . H O
The experi~ental results on dyed samples of these exa~ples were sLmilar to the results obtained for ~xamples 37-40.
m ese examples rPlate to 2yei~gs using a phosphate-containlng dye which ~s not a vat dye, and there.ore the necessity for having a reduction step ls eliminated. The dyestuff used in these examples had the 'ollowi~g s'ructure:
H3C \ N/ O
3 ~ 5O 2~ ~
O _ P OH
An a~ueous pad dye bath solution was made, contain-ing 0.5 weight percent of the above dye, 0.1 weight percent of wetting agent ("Igepal C0-710"), l.O~of phosphoric acid, and 7% by weight of cyanamlde, with all percentages based on the weight of the solution. Cotton samples were padded with the dye bath solution, using, in the case of Example 57, the dye bath solution described hereinabove, and, in the case of Example 58, the same solution but with the cyanamide and the phosphoric acid omitted.
The dyed samples of Example 57 (those containing the cyanamide and the phosphoric acid) had 73.7% color retention after rinsing, and 50.8~ color retention after five washes, using the pro~edure of Example 37. On the other hand, Example 58, which used no cyanamide, showed practically no fixation (less than 10~).
Examples ~7 - 58 were repeated, but using the phosphate-containing dye (which was not a ~at dye) of the formula:
~;
~ ~ ~,S3i'1 o ~30_ p-o~ ~
o~
The cyanamide dye bath solution contained only 5% by weight of cya~amide, based on the weight of the solution. ExEmple 59, which used the 5% by weight of cyanamide, and the phos-phoric acid~, resulted in 44.4% color retention after rinsing, a~d 39.3% color retention after five washes. On the other hand, Example 60, which corresponded to Example g8 in ~hat it had no cyanamide or pnosphoric acid, resulted in little or no dye fixation.
It will be appreciated from Examples ~7-56 herein-abo~e that a practical method has been developed for the application of phosphate vat dyes to cotton and cotton-cont~ ing fabrics, with good col~r fixation. The prior art to date was unable to use such vat dye~ commercia~ly on cotton, because of the problem of insufficient washfas~ness.
Usi~g the dye of Example 24, an a~ueous dye ~ath soiution was prepare~, having ~.2~ weight percent of the abo~e dye, 2 weight percent of dic zndlamide, ~.1 weight percent of surfactant (Tgepal CO 710~ and 0.125 weight perce~t of phospAoric acid. A l00~ cotton fabrlc ~as padded ~ith tn$s solution) passed through an otJen at 400F ~Jith an exposure t~me of 90 se~onds, and ther scoured using the pro-cedure of Exam.ple 37 and measured color~metrically ~or dye retention. .~bout 78% of the original color was retained after scourir.g.
111~844 EXAMpLE 62 Example 61 w~s repeated, except that the dye bath contained 8 weight percent, based on the weight of the bath, of a 50% aqueous solution o~ cyanamide in addition to the 2 weight percent of dicyandiamide. About 87% color retention was obtained.
Example 61 was repeated, except the dicyandiamide was eliminated ~rom the dyebath (that is, no dicyandiamide or cyanamide was in the dyebathl. The color retention after scouring was about 10~, and even more color was removed upon laundering.
A printing paste was prepared using 0.15 weight percent of the dye o Example 25, and 0.05 weight percent of the red dyestuf of the following formula:
H O
~ N - N - ~
~ PO(OH)2 O3 ~ SO3H
as well as 0.2 weight percent of wetting agent ("Igepal CO 710*~
(nonylpheno~ypoly(ethyleneoxy)ethanol having 10-11 ethyleneoxy units sold by 5AF), 0.1 weight percent o (NH4)2~PO4, 3.0 weight percent of dicyandiamide, 33 weight percent of 3%
"Keltex S*" (aqueous solution of sodium alginate, from Kelco Company), 33.0 weight percent o~ a 70% "~arsol**" emulsion, and the remainder water.
*Trademark **Trademark o~ Exxon Corporation ~or straight petroleum aliphatic sol~ents.
X
1i~11844 The resulting print paste, with pH adjusted to 8.6, was screen printed on 100% cotton fabric at an add-on of about S grams per square yard ~about a 100~ average add-on) The fabric was dried and fixed at 400F, at an exposure time of 60 seconds, to produce a printed cotton fabric having ~ood color retention.
Another printing paste was prepared, based on 0.2 weight percent of the blue dye of Example 2S, 0.05 weight percent of the red dye having a structure as shown in Example 64, 0.2 weight percent of wetting agent ("Igepal CO 710"), 3.0 weight percPnt of dicyandiamide, 48 weight percent of 3 "Superloid*" (ammonium alginate sold by Kelco Company), 15.~
weight percent of a 70~ "Varsol" emulsion, 2 weight percent of 50% "Carb~wax**" 4000 emulsion, and the rest water The printin paste had a pH of about 4.2. The paste was scre~n printed using the procedure of Example 4, with similar results.
As mentioned hereinabove, it is, i~ some i~stances, desirable to add an acid to the dyebath in order to adjust the pH to the desired level. Phosphoric acid is a convenient strong acid which is preferred for such p~ adiustment.
However, other compounds can be used, including methyl acid phoshate, ~mmonium phosphate, bor~c acid, formic acid, lactic acid, glycolic acid and s~lfuric acid.
*TrademarX
**Trademark. Car~owax is t~e trademar.~ for the 'amily of water-soluble polyethylene glycols and their derivatives made by the Chemicals nd Plastics Division of Union Car~ide Cor~oration.
The number following the name denotes the average molecular weight and thus the ethyleneoxy content.
"Car~owax" 4000 is polyethylene glycol; it is in the form of a white, free-flowing powder or creamy white 'lakes.
1~111~44 It is preferred that the dye bath contain no sol-vent or dye assistant, but in certain instances the use of such auxilliary chemicals may be useful. If an organic solvent is used to assist in ~ringing the reactants of the present invention together at the reaction temperature (that is, the dye, the cyanamide compound, and the substrate), such a solvent should contain no free alcoholic-type hydroxyl group, should have a boiling point higher than that of water, and pre~erably should be ~i~cible with water and the cyanamide compound. In such instances, suitable solvents might be "Carbowax*" 350, "Carbowax*" 750, "Carbowax*" 2000, triethylene glycol diacetate, diethylene glycol diacetate or urea.
While a wide variety of chromophores may be used in the practice of the present invention, it is generally pre-ferred that small dye molecules, compatible with color strength, be used. In general, long, linear dye molecules tend to position themselves along the cellulose polymer in such a manner that unreacted dye may be subjected to a slow release during subsequent washings, and not removed in adequate amounts during the production rinse.
Particularly preferred dyeing conditions for monophosphonic acid dyes include the use of about 0.2 weight percent sur~actant, 0.2 weight percent phosphoric acid, no organic solvent dyeing assistant, 4.0% cyanamide and 3.0 dicyandiamide. ~uch a dyebath, with proper amounts of dyestuff therein, can be padded onto 100% cotton at about 75% pickup, and ~ixed at a temperature of about 390 F fo~
about 90 seconds in a Benz unit. The color endurance of the dyed fabric runs about 75-90%, with less than 5~ strength loss in the ~a~ric tear strength and warp and fill tensile strengths.
*"Carbowax" 350, 750 and 2000 are methoxy polyethylene glycols.
-4g-The process of the present invention for the continuous dyeing of cotton equals or exceeds other reactive dyeing systems now in use. The present process involves a pad-predry-~ake-rinse-dry system which can be utilized on existing plant equipment. Most reactive dyeing systems are based upon alkallne dyeing environments, whereas the present system operates extsemely well on the acid side with a p~ of about 5, and thus is more compatible with the disperse dyes used in the thermosol dyeing of polyester-cotton fabrics.
Dye migration problems can be controlled by ~ormal adjust-ments in the padding and predrying steps in the operating plant, ana such adjustments are even easier on polyester-cotton blends. The dyeings are q~ite consistently level.
The strength loss of the cotton fabric is generally under 5%, which is ab~ut normal for reactive dyeing processing steps The dyebaths of the present in~ention do not exhibit tailing ~color strength loss) or ageing problems over a two-day period.
As mentioned above, the monophosphonic acid dyes used in the process of the present invention produce dyed fabrics having 70-90%, especial'y 75-90%, ~olor endurance.
This color enduranc~ can be defined as the ~ercent color retained, compared to initial unrinsed fa~ric, after a fu~' rinsing and fi~e standard AATC~ machlne launderinqs. In contrast, the color endurance for compe~ e reacti~e dyes a~erages abcut 60-70~.
The diazotisation method is ~ased on Vogel, "Practical Organic Chemistry" (1951), p. 596, and follows the following reaction sequence:
MH2 N=NCl +~ 2 -t ~ICl ~C~3 _ ~ ~
~ (~-)2 ~ ~ (OH)2 j ~
8~4 Coupling of the diazotized intermediate (III) is based on British Patent No. 753,771. The solution containing the intermediate (III) was added to a solution containing 12.7g (1/20 mole) of 3-methyl-1-(p-sulfophenyl)-2-~yrazolin-5-one and 10g of sodium acetate in 100 ml of ~2 The pH of the second solution had been adjusted from 5.3 to 7.0 with NaO~. After stirring for 15 minutes the pH was 2.0 and there was no evidence of precipitation. On addition o~ isopropanol, a yellow powder was precipitated which after separation and drying in a vacuum oven yielded 13g. Coupling proceeded according to the following reaction:
- y=~ Cl ~'~ '.+
~ (~-)2 CH.~ ~ (Or.) 2 cr~.3 ,,~ . ' / \ ~ "
\ -Cç~;~S~3~la 3~ ~ -C6R4S03~a The following example illustrates the syntnesis of a bis pho~phono, bis-azo dye.
EXaMPLE 2 3-Aminobenzenephosphonic acid was diazotized accord-ing to the procedu_e of Exampie 1 usir.g 13 m~ of concentrated HCl. 18.0g (1/20 mole) of the mono-sodium salt of 8-amino-1--naphthol-3,6-disul~onic acid wa~ suspended in 50 ml of K2O
a~d the p~ was adjusted from 2.3 to 7 with NzOR. ~his solution was added to the diazotate to form a dar.k red solution h~ir.g a pH of 2.5.
Al.kaline coupling was racticed accordins to Vogel, supra, p. 597.
111~844 The red solution precipitated on standing and was adjusted to pH 7 with NaOH. 40 ml of a 10% NaOH solution was then added and cooled to 5C. A second preparation of diazo-tate was then added to form a blue solution having a pH of 7.4.
After 15 minutes the pH was adjusted to a pH of 2 with HCl.
The dye was precipitated with isopropanol to yield 40 grams of blac~ powder having the formula:
~_a~ N=N'- ~
O(O~)2 ~.2O3S -SO3`~ ~(~)2 The pyrazolone yellow dye of Example 1 was used to dye c~tton fabrics according to the following procedure.
A pad bath was prepared containing 5% o' the pyrazo-lone yellow dye, three molar ~quivalents of cyanamide (1.33 weigh_ percent) and 0,1% "Triton X 100*" (Rohm & Haas - octyl phenoxy polyethoxy ethanol - non-ionic wetting agent). The bath had a pH of 2.9. Samples of print cloth fabric were padded at 40 psi, and then oven dried for five mlnutes at 150F
except for one fabric that was air dried at room temperature.
One sample of fabric was cured for five minutes at 320F. An oven dried fabric was cut in half for color ccmparison. All but one one-hal~ of the ovan dried fabric were washed for eight minutes with heavy-d~ty detergen., dried and then ironed.
The air-dried fabric was colorless, the o~en dried 'abric was colorless, whereas the cured fa~ric had a bright lemon yellow color with some washoff by comparison with unwashed fabrics.
The colored fabrics were boiled for Gne hour in 3~ K2C~3 with some color lost. The fi~al color was a p2stel yellow shade of the orisinal bright yellow color.
*Trademark - 13 -111~844 Since the fabric subjected to air drying lost all color on washing, it is app~rent that the dye was not substan-tive. It is quite unexpected that the ester ~inkage of the fixed dye is sta~le to hot detergent alkaline medium since it would be expected that the phosphoru~ ester moiety would hydrolyze and rupture the dye attachment.
The blue dye of Example 2 was utilized to color cotton fabric according to the following procedure:
A pad bath was prepared containing 5% of the blue dye plus 6 molar equi~alents of cyanamide ~1.73%) and 0.1% of " ~1 Triton X 100. The pH of the bath was 2.6. Samples of cotton fabric were treated, dried and cured as in Example 3. After washing, the air-dried fabric was almost colorless. The oven-dried fabric was a very pale blue, whereas the cured fabric was a very dark navy blue. There was some sLight washoff by comp~rison with the unwashed fabric. The warp ~hrinkage was -3.75% whereas the fill shrinkage was +0.75%. After the fabric was boiled for one hour in 3% K2CO3, the final color was a darX pu~ple .
It was then attempted to fix the dye of Examp'e 1 on fabric using heat without the presence of a carbodiimide.
EX~MæL2 ;
A bath was prepared, containing 5% by weight of the pyrazolone yellow dye of ExamplP 1, 21us 0.1~ Triton X 100.
The p~ of the bath was 2.9. The bath did not contain any car~odiimide or equivalent mat2rial.
Samples of cotton fabric were ~added at 40 ?si, dried for fi~re minutPs at 150~ ar.d cured fcr five further minutes at 320~F, washed in hea~y-duty detergent 2nd ironed. The fabrics contained only a trace of yellow color. A dye and heatstep at curing temperature is not capable of fixing the dye on the fabric.
It was then attempted to fix on fabric the dye of Example 1 by means of a pad bath containing urea.
EXAMP~E 6 A bath w~s prepared containing 5~ by weight of the pyrazolone yellow dye of Example 1, 0.1~ Triton X 100 and 1.9 urea (3 mclar equivalents). The pH of the ~ath was 2.9.
Samples of cotton fabric were trated as in Example 5 and the samples xetained no more color than those of Example 5 showi~g that no dye immobilization occurred by this procedure.
It was then attempted to fix the dye of Example 2 on fabric using heat or urea in the a~sence of a carbodiimide.
Two baths were prepared, one containing 5% of the , ~
blue dye of Example 2 plus O.1% Triton X 100 and the other additionally containing 2.5% urea ~6 molar equivalents). The p~ of the first bath was 2.65 and that of the second bath with urea was 2.70. Samples of cotton fabric were padded at 40 psi, dr~ed for five mlnutes at 150F, cured for five minutes at 320F, washed in hea~y-duty detergent and ironed. Only a trace of blue remained in the fabrics. Colors were all about the same.
Th~ following example shows the use of polyvinyl alcohoL and phosphoric acid as adj~vants to ~e coloring bath:
A pad bath was prepared containing 1~ ~y weight of the blue dye of Example 2, 1~ E~PO4, 1.~% cyanamide ar.d 6 milliliters of 4~ Polyvinyl alcohol. ~To wet~ing aser.~ was _ 15 -' 1~11~
a~ded. The pad bath was used to treat 100~ cotton cloth and 50-50 cotton polyester cloth, according to the procedure of Exzmple 3. The cloths showed good color retention and sta-bility with very little washoff and very good resistance to boiling K2CO3. A similar bath containing 4% "Cellosize*" in place of poly~inyl alcohol gave a similar result and also imparted some blue color to glass cloth.
The following example illustrates the use of dicya~-diamide in place of cyanamide.
EXAMP~ 9 A pad bath was ~repared containing 1.5~ by weight of the yellow dye of Example 1 and 1% of dicyandiamide. ~0.8%
would be a molar ratio of 1:3). Samples of cotton cloth were treated according to the procedure of Example 3. After wash-ing, the dye i~mo~ilization was essentially the same as fhe cyanamide treated fabrics of Example 3.
The following example illustrates preparation of the benzyl phosphonic analog of the dye of Example 1.
p-Aminobenzyl phosphonic acid was coupled with the sulfophenyl pyrazolone utilized in Example 1 utilizlng 9.4 grams of the benzyl acid (0.1 mole) in place of 8.7 grams of the phenyl a~id. The pH was finally adjusted to 3.0 with HCl and the solid precipi~ated with isopropanol, presuma~ly as the monosodium salt having the structural formula:
*Trademark of Union Carbide Corporation for hydroxyethyl cellulose and/or carboxymethyl cellulose.
84~
C 3 l l N=N ~ CH2 P - OH
~=0 SO 3Na The dye exhibited similar behavior when utilized to color cotton fabric samples according to the procedure of Example 3.
The following experiment illustrates the preparation and use of the ammonium salt of the dye of Example 1 at higher pH.
An ammonium salt of the yellow dye of Example 1 was prepared by dis-Qoving the dye in an aqueous NH40H solution and evaporating the solution to dryness.
A pad bath was prepared containing 1% of the ammonium salt dye, 0.3~ cyanamide and 0.25% "Alipal CO 436*" (nonyl phenoxy polyethoxy-ethanol=sulfated, NH4 salt). The pH of the bath was 5.8. The bath was applied to fabric and cured as in Example 3. The dye immobilization was substantially the same as in Example 3.
An acid pad bath was prepared containing 1% of the sodium salt of the phenyl dye of Example 1, 0.25% of "Alipal**"
*Trade~ark **Trademar~ ~or a series of anionic surfactants containing alkylphenol and ethoxy groups in the molecule.
~' 1~118~4 and 3% of H3P~4 and 4.5% ~f cyanamide which represented a molar e~uivalent rati~ of 3:1 o~ the cyanamide to the combined dye ~;
and acid. The pH o~ the pad bath was 1.8.
-17a-Samples of fabric cloth impregnated, cured and washed according to the procedure of Example 3 showed very little washoff. U.V, analysis of the cloth indicated about 75% dye fixation.
Nethyl phosphonic acid ~MPA) was substituted for the H3PO4 of Example 12 and the cvanamide content was reduced by 1.3~ to adjust the MPA/cyanamide molar e~uivalent ratio to 1:2.
The p~ of the bath was 1.8. Samples of abric, Lmpregnated, cured a~d washed according to the procedure of Example 3 again demonstrated very little washoff, A sample of fabric which was air-dried before cure to minimi"e migration showed some-what improved color retention.
The following experiment shows the necessity of a phosphorus acid group in the dye molecule, A pyrazolone dye was prepared utilizing metanilic acid in place of the 3-aminobenzenephosphonlc acid of Example 1. A bath was prepared containing 1% of the sulfonated dye, 3% H3PO4, 0,25%1'Alipal*" and 4.5% cyanamide. The pH of the bath was 1,7~. Samples of fabric L~pregnated, cured and washed according to the procedure of Example 3 showed extreme washoff demonstrating that little or no dye was fixed.
Fixation and immobilization of dye by 'ormation of a phosphorus acid ester lin~age was further confirmed by the following experiment, A solution of 5% 3-aminobenzenephosphonic acid con-taining 3 molar e~uivalents of ~anamide was utilized to impregnate cotton cloth, The cloth was cured at 320F for *Trademar~ for a series of anionic surfactants containing alXyl~henol and ethoxy groups in the mo'ec~le.
111~8g4 five minutes to couple the ~mine base to the cellulose through the phosphono~ kage.
The cellulose-coupled amine base was then subiected to diazot~zation with the Na~O2-~Cl solution of ~xample l to form a diazonium salt. A portion of the cloth was exposed to light to decompose the diazonium salt. The fabric ~as then immersed in a solutton of the sulfophenyl pyraz~lone uti~zed in Example 1 and dried and washed. Color was only retained in the nonexposed areas, con4irming the phosphono-ester linkage as the immobilization mechanism.
A copper phthalocyanine substituted with phosphonic acid and sulfonic acid groups was prepared by heating an inti-, mate mixture of triammonium 4-sulfophthalic acid (llg), mono-potassium 4-phosphonophthalate (llg), urea (20g), cupric chloride dih~drate t3g), and ammonium molybdate (0.25g) at 250C, The product was purified by washing wl~h hydrochloric acid and drying in a vacu~m oYen at 60C.
A bath was prepared contai~ing 1% of this product, 20 ~ H3PO4, 4.4% cyanamide and 0.,25% Alipal. The p~ of the bath was ad~usted to 2.5 with t_iethanolamine. Samples of fabric impregnated, cured and washed according to the procedure of Ex~mple 3 were a green~sh-blue color.
The present in~ention pro~ides a no~el acid system for the fast dyeing of hydroxy fi~ers. The reactively dyed fibers exhi~it good color and are sta~le to hot basic media.
The dye system of the present invention provides 2 further zdvan~age since the dye can ~e recovered frcm ~he ~ath by precipitation on a calcium su~strate such as lime, CaC03 or 3a marb'e and can ~e regenerated by acid.
1~11844 The results obtained herein~bove indicate that the process of reactively dyeing textiles and otner substrates has broad applicability. The process of the present invention may be broadly applied to many substrates ha~ing an active hydrogen atam according to the well-known ~erewitinoff test (J. Am. Chem. Soc., 49, 3181 (1927)). Especially pre~erred are s~bstrates having alcoholic hydroxyl (non-phenolic) groups, amino groups, or thiol groups. That is, the re~cti~e site on the substrate may ha~e the formula -OH; -NH2~amino); -NH-L0 -(amino); or -SX. Thus the process of the present in~ention results in the fixation of phosphorus-containing dyestuffs on rayon. The fixation is obtained with wool but the depth of shade is not as good as with rayon. Fixation of the dyestuff is also o~tained with nylon, but the depth of shade is some-what inferior to that of wool. Of the ~ubstrates having Zerewitinof~-active hydrogen atoms, those compounds having hydroxyl groups are grea~ly preferred, especially organic poly-mers having hydroxyl groups. While the substrate may ~e in the form of cast or other massive articles, it is greatly preferred that the substrate be a textile fabric or a textile yarn, filament or fiber.
The results obtained with ~yanamide and dicyandiami~e ~uggest that cyanamide compounds of the genera' ~ormula X
/ N - C _ N
x2 wherei~ Xl a~d x2 are hydrogen, lower alkyl, or tcgether are ~(X3)2 = C
\N(~3)2 - 2~ -~y~
wherein each X3 is independently hydrogen or lower alkyl, can be used in the process of the present invention. Thus, methylcyanamide, dimethylcyanamide, ethylcyanamide, diethyl-cyanamide, butylcyanamide, dibutylcyanamide, and other cyanamide compound~ falling within the scope of the above formula dls-closed in the aforesaid American Cyanamid Company "Cyanamide"
booklet, may be used in place of cyanamide cr dicyandiamide.
Compounds of the above general formula may exist in tautomeric form and these tautomers are intended to be included in the general formula.
The dye, the fiber, and the cyanamide compound can be brought together in any particular order. Normally, the dye and the cyanamide compound, together with any con~entional additives or assistants, will be in the form of an aqueous solution, which is padded or otherwise applied to the substrate..
At least a coloring amount of the dye will be reacted onto the substrate.
As mentioned hereinabove, it is possible to form the dyestuff on the fabric essentially "in situ", by coupling a phosphono-substituted compound to the cellulose and thereafter coupling that c~mpound ~o an azo chromophore component or other chr~mophoric group. Alternatively, the pho~phorus~con-tainin~ dyestuff could be applied to a textile fabric which lS
- then subiected to an aftertreatment with the cya~amide compGuna.
Regar~less of the technique actually used, it is c~ea~ that the thrust of the present in~ention resides in contacting a poLy-meric sub~trate c~n~ai~in~ ~erewi~inof~-active hydrogen atoms, especially alcoho~lc hydroxyl, amino, or t~iol groups, with a cyanamide compound and wi~h a ~hromophore-substituted phos-phorus acid or a chromophore ~recursor-substituted phosphoru~
acid, and heating the contacted substrate to an elevated tem-perature to fix the chromophore or chromophore precursor to the substrate.
Mixtures of substrates, dyes, and/or cyanamide csmpound~ may be used if desired.
The addition of phosphoric acid to the impregnating bath appears to impro~e the efficiency of the dye Lmmo~iliza-t~on, ~ut can ha~e the undesirable effect of r~ducing the strength of the fabric by as much as about 50%. Dyes contain-ing two phospnonate groups or other phosphorus acid groups have been found to have an efficien¢y of qreater than 90~, when affixed to cotton or another suitable su~strata by the use of cyanamide or dicyandiamide, without using any phosphoric acid in the dyebath. Since no phosphoric acid is added to the dye-bath, the fabric essentially loses no strength duxing the dyeing process. Thus, where the strength of the textile fa~ric mu~t be maintained, and high c~upling efficiencies of the dye-stuff achieved, the use of the dyestuffs containing two or more pho~phorus acid substituents is often greatly preferred.
However, recent wor~ has established that monophos-phonate dyestuffs can produce excellent fix~tion on substrates, using the process of the present invention, at a pH of about 5.
To achieve this pH, it is preferred to add a~out 0.125 to a~out 0.25 weight percent of phosphoric acid ~ the "dyebath. Thus, broadly ~he amount of acid th~t can be used i~ the dye~ath ranges from about 0.1 to about 5 weight perc~nt.
Example 4 herei~above relates to using a di~phos-phorus acid)-substituted 2yestuff. Additional examles of using such dyestuffs are set forth ~e~ow.
11118~4 EXA~LE 1 7 H acid (81% pure, 43.5g, 0.1 mole) of the formula:
N~2 OH -SO~
was suspended ln 300 ml water and 100g ice and the pH adjusted to 6 with sodium hydroxide solution. Sodium acetate (39g, 0.3 mole) was added, followed by ~-chlorosuLfonylbenzenephos-phonic acid ~30g, 0.12 mole) in portions over 10 minutes, the temperature being mainta~ned at 10C and the p~ at 6. The solution was stirred for three hours ~n an ice bath, and then sodium car~onate (25g) was added.
To this solution was added a diazotized solt~tion of m-aminobenzenephosphonic acid. The combined solutions were stirred for 1 hour, then concentrated hydrochloric acid (400 ml) was added and the solution filtered to yield a red dye with the structure:
S
EXA~T E 18 ~his and ~he ~ollowing three exa~ples relate to the production o~ orang~ dyes, using, as the starting compour.d, J aci~ of Lhe ~or~ula:
~O~ R .
in place of the H acid. Example 17 was repeated, replacing the H acid with J acid, producing an orange dye o~ the formula: . O~
50~1~ Hs o,4 Eæ~l.E 1 9 Example 18 was repeated, but using the N-methyl deri~ati~e of the J ac~d, to p m duce an orange dy~ of the formula: o~
SO~ CJt, EXAMP~E 20 Example 18 was repeated, but th m-chlorosulfonyl-benzenephosphonic acid was replaced by benzoyl chloride, and the diazotized solution of m-aminobenzenephosphonic acld was replaced with a diazotized solution of o-amino-p-xylylenedi-phosphonic acid, to produce an oranse dye of the formula:
Cl~a Pof~ , OJ/
~,Po(o~O~JJ~:o~
- E~ ~ 21 Example 19 was repeated, but the m-chlorosulfonyl-benzenepnosphonic acid w~s deleted, ana the diazotized so~u-tion of m-aminobenzenephosphonic acic was repiaced ~ h a diazotized so~ ution of o-~mino-p-xyly' er~ed~ phosp~onic ac1 d, to produce an orange dye of the for~nula:
, po (OH~a 011 ; H C
c 1~, ro,~O~),, EXAM~LE 2Z
Following the procadure of Example 21, an orange dye was made by treating ~ -naphthol with diazotized o-amino--p-xylylenediphosphonic acid, and the resulting dye had the formula: -01~ CH, PO (0~1),.
~ C~J,,Po(o~
Example 22 was repeated, replacing the ~ -naphthol with F aci~, of the ~ormula:
-HO ~S
111~8~4 resulting ~n an orange dye Q:i' the forr~ula:
OH CH2PO(OH)2 ¢~N=N- ~
¦ ~) H2PO(OH)2 \~03H
Bromaminic acid (89.996 pure, 132 g, 0.315 mole), p-amino benzylphosphonic acid (65g, 0.345 mole), and cuprous chloride (:12 g~ were stirred in water 1800 ml) and ethyl alcohol (:200 mll, and sodium carbonate (160 g, 1.5 mole) added in portions. The solution was then heated to 50C, and stir-red at 45-50C for 18 hours. The reaction mixture was cooled and poured care~ully into concentrated hydrochloric acid (300 ml), and then :eiltered. The residue was recrystallized from aqueous hydrochloric acid to yield a blue dye of structure O NH
Il ~ 2 ~SO3H
O NH ~)-- CH2PO(~:)H)2 Example 24 was repeated, but the p-aminobenzyl-phosphonic acid was replaced by an equimolecular amount of ~c ~w 8~4 o-amino-p-xylylenediphosphonic acid, to produce a blue dye of the structure:
o NH
~ I ~ CH2PO(OH)2 O NH ~
CH2PO(OH)2 o-Amino-p-xylylenediphosphonic acid (28 g, 0.1 mole) was dissolved in water (150 ml) and sodium carbonate (21.2 g, 0.2 mole) added. Sodium nitrite (7.4 g, 0.107 mole) in water (40 ml) was added, and the solution was poured into a mixture of concentrated hydrochloric acid (50 ml) and ice (100 g). The solution was stirred at 5 for 20 minutes and then the excess nitrous acid destroyed with sulfamic acid. This solution was added to a solution of 3-methyl-1-(p-sulfophenyl)-2-pyrazoline-5-one (25.4 g, 0.1 mole) in water (300 ml3 containing sodium carbonate (50 g), and stirred for 1 hour at 5C. The solution was acidified with hydrochloric acid and from it was isolated the yellow dy~:
~CH2PO(OH32 N-N
HO
CH2PO(OH) so3 111~844 EX~MPLE 27 A pad bath was prepared containing 1% of the orange d~e of Example 23, 2% of dimethylcyanamide (about 15 molar equivalents~ and 0.1% "Triton X100". Samples of a multicomponent fabric containing discrete bands of wool, viscose rayon, silk, nylon, cotton, and "Dacron*" were padded at 40 psi, oven dried for 2 minutes at 180F and cured for 1.5 minutes at 390F. The fabrics were washed in detergent, rinsed and dried. Uhder these conditions, the wool was only slightly tinted and the "Dacron" unaffected. The rayon and cotton were dyed a bright orange, the nylon was dyed pink, and the silk was dyed a darker shade of orange than the cellulosic fibers.
An aqueous dye ~olution was made, with the solution containing 1~ by weight of the orange dye of Example 18, 1%
by weight of cyanamide, and 0.1% by weight of a surfactant ("Triton X100"~. Rayon, nylon and wool fabrics were immersed in the dye solution, dried for five minutes at 180F and cured for 90 seconds at 390F. After one home laundering the dyed samples showed significant dye fixation, with the rayon dyed the most strongly, followed, in order, by wool and nylon.
2~ Separate a~ueous dye solutions were prepared with each of the orange dyes of Examples 19, 20 and 23, each solution containing 1% by weight of the dye and 1% by weight of cyanamide. Separate cotton fabrics were then immersed in the respective dye solutions and then dried for five minutes at 180F and thereafter cured for ~0 seconds at 390 F.
*Trademark of DuPont for polyethylene terephthalate po'yester fiber.
After one home launderin~ all of the dyed samples showed excellent dye fixation.
An aqueous dye solution was made with the solution containin~ 1~ by weight of the yellow dye of Example 26 and 1%
by weight of cyanamide. Cotton fabrics were immersed in this dye solution, dried for fivé minutes at 180F and cured for 90 seconds at 3gOF. A~ter one home laundering the dyed samples were a bright yellow color and had excellent dye fix-ation.
An aqueous dye solution was made, containing 0.5 by weight of the blue dye of Example 25 and 3% by weight of dicyandiamide, this solution having pH of 2. Cotton fabrics were immersed in the dye solution, dried for five minutes at 180F and cured for 90 seconds at 390F. After one home laundering the fabrics were dyed a bright blue and the dye fixation was excellent.
An aqueous dye solution was made containing 0.5%
by weight of the blue dye of Example 25 and 1.25~ by weight of cyanamide, the pH of said solution then being adjusted to a level of 3 by the addition of ammonium hydroxide.
Cotton fabrics were immersed in the dye solution, dried for five minutes at 1~0F and cured for 90 seconds. After one home laundering the fabrics were dyed bright blue and the dye fixation was excellent.
In a fashion generally slmilar to that of Example 28 above, cotton swatches were dyed in aqueous dye soluticns pre-~' pared from each of the dyes of Example 21 (orange~, 22 (orange) and 24 (blue~. All of the dyed swatches showed excellent dye fixation after the home laundering.
COMPARATIVE EXAMPLE A
Example 28 was repeated, except the cyanamide was omitted. After one home laundering, the dyed fabrics were only tinted a very pale orange (an indication of little if any dye fixatlon).
~, ~111844 Additional classes of phosphorus-containing dyes can be readily prepared, following the procedures of Examples 17-21 and 23, but replacing the H, J a~d F acids with the dye intermediates disclosed in U.S. Patents:
2,a47,4s8 2,799,701 2,717,906 and 2,5~3,417 Additional phosphorus-containing dyes which may be used in the practice of the present invention are disclosed in the foll~wing patents:
Belgium 563,439 U.S. 2,326,047 U.S. 3,339,g99 U.S. 2,18~,998 U.S. 3,202,550 British 970,585 West German 1,042,523 Additional dyes whi~h can be produced following the procedure o Example 2~, but with different naphthylenic starting ~aterial~, are of the formulae.
pO (0~)~, ' .
, Cf~z t~
N03~
Po (f~')2, and - rO(o~2 ,~ '-' ' `~ `/Y~c~oc,~ -P~(O~JL
It is believed that the dyes of Exzmples 17, 18 and 19 are novel. The results obtained with the dyes of these examples suggest that a new dye family of the class R
I)ye--N-S02 ~1 ~Po(o~I)2 wherein R is hydrogen or lower alkyl, has been discovered.
These dyes, especially those containing two or more phos-phonate groups, wor~ very well in the process of the present invention, Of the various phosphorus-acid-substituted dyestuffs disclosed hereinabove, those dyestuffs substituted with more than one of said phosphorus acid radicals are particularly preferred, due to the excellent fixation obtained.
In the latter regard, the dyes co~tai~ing more than one phosphonate group have, as mentioned hereinabove, ~een found to ~e particularly preferred. ~he phosphonate 5ub-stituents may be loc~ted at any point on the dye molecule, at genera~ly pr~ximate positions or at positions further removed rom one another such as at the distal ends of the dye moiety.
Of the various phosphorus-acid-substitute~ dye-stuffs disclosed hereinabove, those dyestufCs substituted with one or more phosphonate radicals aIe parti~ularly ~11844 preferred, due to the ease of dyeing and excellent durabilityobtained .
The results obtained hereinabove i~dicate that chromophore-substituted phosphorus acids broadly of .he fo~mula:
tO) Il n R - P - (O~) ~OR)q wherein each R is a chromophore, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, and 5 is 0 or 1, and m + ~ ~ 5 = 3, and wherein at least one of m and q is other than 0, may be used in the process of the present invention. Chromophore-substituted phos-phorus acids having hydrocarbon substituents on the oxygen atom tin addition to the c~romophore) are not preferred, due to the decreased reactivity of these compounds, as well as the greater effort and expense in manufacturing same.
H~wever, it will be appreciated that such compounds may be used to replace part or all of the chromophore-substituted phosphonates or phosphates or similar compounds. Normally, only one chromophore will ~e attached to the phosphorus atom, either directly or indir~ctly (that is, it ia preferred that 2~ the sum of m and q is 1, for both the formula above and of page 7 hereinabove3, and it is preferred, as indicated hereinabove, that the chromophore carry two or more phosphorus acid grDups.
~ he present invention also includes novel xyl~lene diphospAonic acid dyestuffs of ~he general formula:
1~1184~
~2P03H2 Dye C~I2P03H~
wherein Dye represents a chromophore, preferably an azoic chromophore. Such dyestuffs offer two potentially reactive sites when used in the process described herein, a~d thus generally result in high levels of fixation of the dyestuff on the substrate.
In addition to the preferred azoic chromophore, it will be readily appreciated by those in the art that other chr~mophores may be utilized. For instance, Example 25 hereinabove relates to ~n anthraquinone chromophore. Clear-ly, any of tne other chromophores descrlbed hereinabove, or described in the references mentioned hereinabove, could be substituted for the chromophores disclosed herein in connection with the xylylene diphosphonic acid dyestuffs.
8~4 10 g of Procion Red NX2B (CI Reactive Red 1) were dissolved in 200-250 ml of water. One gram of m-aminobenzene phosphonic acid was dissolved in 50 ml ~f water, using a small amount of caustic to aid solubilization. Then the phosphonic acid solution was slowly added to the dye sol~tion with stirring. The i~itial pH of the dye solution was 6.5, and this p~ fell to 5.5 during the addition of the phosphonic acid. The pH was adjusted to 6.8 with 50% caustic, and then the solutio~ was warmed on a hot plate at 140F for ~0-30 minutes.
The resulting dye solution was cooled to room temperature and 15 g of phosphoric acid and 40 g of Cyanamide 50 (50% solution of cyanamide) were added, and the resulting solution was diluted to a total volume of 500 ml. The pH
of the final solution was 1.7.
The dye solution was then padded on 100~ cotton fabric at a pic~up of 70%. The padded fabric was dried for two minutes ~t 220F and cured for 45 seconds at 390F in a Benz u~it. The fabric was scoured with a nonionic detergent and soda ash, and then subjected to five home launderings.
Th~ retention of color on the fabric was very good.
It is belleved that the reaction betwe~n the Reactive ~ed l dyestu'' and the phosphonic acld was as ~ollows:
1~118~4 S03Na ~C~
N = N~ ~ ~ + ~ ( )2 NaOH
NaO3S I~lSQ3Na ~H2 H(N~3 P3H2 ~C
S03Na H ll 1~
/--\ HO p--C C~\ P03H
(~N = N~ N~ b,~ 2 NaO3S~903Na -- 3~i --.
A reduced dye solution was prepared of a convention-al monophosphate vat dye. A solution containing 5 grams per liter of the vat dye of the following formula:
~ 0~1 ~ .
~H
.
was reducsd ~y the addi~ion o~ 2 grams per liter of sodium nydrosulphite and, after the completion of the sodium hydro-sulphite addition, 2 sr~ms per liter of sodium hydroxide.
The addition of the sodium hydroxide was accompanied by a color change, which would be expected for vat dyes, as denoting reduction of the dye to its soluble leuco form.
Five grams per liter of a wetting agent (~Igepal CO-710*"), obtained from GAF) was also added to the solution.
Immediately after preparation of the above reduced dye solution, a sample was padded onto lQ0~ cotton, 3 ounce per yard sneeting, at a wet pickup of 75~. After padding, the sample was dried for 4~ seconds at 220GF.
A portion of the fabric sample was rinsed in hot water (at approximately 18~F) containing 10 grzms per liter of a scouring agent (Synthrapol ~SP o~tained _rom ICI).
A portion of the rinsed samp7e was th~n wasned 'ive times according to AATCC test meth~d 130-1970 II. The resul's are re~orted in Table 1 herei.~e~ow.
~Trademark of GA~ Cor~oration for nonyl~henoxy~oly~ethy'eneoxy~
ethanol; it is a nonionic surfac~n-.
i~ll844 Example 37 was repeated, up through the padding ofthe cotton sheeting with the reduced dye solution. The sample was then padded a second time through a 5 gram per liter solution each of acetic acid and hydrogen peroxide.
Aftsr the sacond padding step, the sample was dried for 45 seconds at 220F. After this oxidizing step, the sample exhibited a c~lor change, indicating that oxidation had occurred.
Portions of the sample were rinsed and washed by the procedure of Ex~m~le 37, with the results reported at Table 1 below.
EXA~PLE 39 Example 37 was repeated, through the drying step of the padded cotton sheeting. After the drying step, the sample was padded through an aqueous solution containing 80 grams per liter of cyanamide and 10 grams per liter of phosphoric acid. The sample was then dried for 90 seconds at 390F. This curing step a'lowed the reaction of the dye, the cyanamide and the cellulose to occur.
This sample was treated wi~h the rinsing and washing treatment described in ~xample 37. The results are reported in Table 1 below.
E~ample 3~ was repeated, but after th~ t~o ?addi~g steps and the d~ing step, the sample was ?added thrGuch the cyanamide-~hosphoric acid solution descrlbed in ~xampLe 39, and ~hen cured at 390F .or 90 seconds.
This samp'e ~as rinsed and ~ashed by the ?rccedure of Ex~ple 37, ~nd test resu'~s ~re re~Grted ir. Ta~'e 1 herei.~e'ow.
- ~8 -Example ~ Color After Rinse % Color After S Washe~
37 Pad 80.1 7.6 38 Pad ox. 40.6 10.7 39 Pad~pad 99.4 64.2 40 Pad/oxid/pad 99.2 73.5 As shown in Tab~e 1, there was some loss of color upon rinsing but the color loss was negligible for ~he samples of Examples 39 and 40. Washing resulted in even more dramatic differences between Examples 37 and 38, on the one hand, and 39 and 40, on the other. A definite difference in depth of shade of the samples was readily apparent. The samples of Examples 37 and 38 showed almost c~mplete loss of color. The samples of Examples 39 and 40, however, showed much less additional color loss after washing than the sa~ples from experiments which did not utilize the cyanamide treatment. There was no ~ubstantial increase in color yield of the ~ample of Example 40 over the sample of Example 39, indicating that the chemical oxidation step had little positive effect on increasing the retention of the dye in the cellulose, with the oxidation resulting in about a 9% increase in color retention.
Examples 37-40 indicate that the aftertreatment of a dyed fabric wi~h cyanamide, accompanied by a curing step, results in a more stable bond formation, and th~refore a high-.-er degree of fixation and dye retention n the fi~ar. The normal ~orces involved with vat dyes, inc~uding hydrogen bonding, van der Waals and other s~bstantive-t~pe bonds, werP
ins~fficient to retain suita~ie amounts o' the dye in the fi~er. In distinc~ contrast, the reaction between the dye, the cyan~mide and the cellulose created a bond which was s~fficiently strong to exhihit gocd dye ~etenticn.
Example 37 was repeated, using a correspondingamount of a monophosphonate dye of the following ~ormula:
~"C ~~P-O~
N~ ~
~H O
The results o~ evaluation of treated samples o~ this example are set ~orth in Table 2.
Example 38 was repeated, but using the mono-phosphonate dye of Example 41. The results of testing are set forth in Table 2 below.
Example 39 was repeated, but using the mono-phosphonate dye o~ Example 41. The results of testing are set forth in Table 2 below.
Example 40 was repeated, but using the mono-phosphonate dye of Example 41. The results of color retention testing are reported in Table 2 below.
Example ~ Color After Rinse% Color After 5 Washes 41 38.8* 9.6*
42 64.5 13.6 43 89.2 64.0 44 95.2 71.8 20 *Average of two samples The dyes used in Example 37 and in Example 41 were identical, except the phosphate group was replaced with the phosphonate group. The monophosphonate dye beha~ed in a similar mann~r to the monophosphate dye, with results almost identical.
~rl 8~4 The results lead to ~asically the same conclusions as for Table 1, and also lead to the conclusion that the phosphate and phosphonate dyes behave in a similar manner in their reaction with cyanamide and cotton.
Examples 37 - 40 were repeated, but using a monophosphate ~at dye of Example 13 of U. S. patent 3,339,999, which had the following formula:
~ ,,OC ~ CO N
Examples 45 - 48 had experimental results similar to Examples 37 - 40.
Examples 37 - 40 were repeated, but using a di phosphate vat dye of Example 2 of U. S. patent 3,339,999, having the following formula:
~C~
~N ~H O
NH O O NH o --P_o~/l~O ~l ~oll=o OH
84~
The results obtained for these examples were sLmilar to the results obtained for Examples 37-40.
Examples 37-40 were repeated, but using a diphosphate vat dye disclosed in Example 51 of U.S. Patent 3,339,999, and having the following formula:
~_ C~ ~C~
N~ O
,~3,C~ ~C_0~
0~1 . H O
The experi~ental results on dyed samples of these exa~ples were sLmilar to the results obtained for ~xamples 37-40.
m ese examples rPlate to 2yei~gs using a phosphate-containlng dye which ~s not a vat dye, and there.ore the necessity for having a reduction step ls eliminated. The dyestuff used in these examples had the 'ollowi~g s'ructure:
H3C \ N/ O
3 ~ 5O 2~ ~
O _ P OH
An a~ueous pad dye bath solution was made, contain-ing 0.5 weight percent of the above dye, 0.1 weight percent of wetting agent ("Igepal C0-710"), l.O~of phosphoric acid, and 7% by weight of cyanamlde, with all percentages based on the weight of the solution. Cotton samples were padded with the dye bath solution, using, in the case of Example 57, the dye bath solution described hereinabove, and, in the case of Example 58, the same solution but with the cyanamide and the phosphoric acid omitted.
The dyed samples of Example 57 (those containing the cyanamide and the phosphoric acid) had 73.7% color retention after rinsing, and 50.8~ color retention after five washes, using the pro~edure of Example 37. On the other hand, Example 58, which used no cyanamide, showed practically no fixation (less than 10~).
Examples ~7 - 58 were repeated, but using the phosphate-containing dye (which was not a ~at dye) of the formula:
~;
~ ~ ~,S3i'1 o ~30_ p-o~ ~
o~
The cyanamide dye bath solution contained only 5% by weight of cya~amide, based on the weight of the solution. ExEmple 59, which used the 5% by weight of cyanamide, and the phos-phoric acid~, resulted in 44.4% color retention after rinsing, a~d 39.3% color retention after five washes. On the other hand, Example 60, which corresponded to Example g8 in ~hat it had no cyanamide or pnosphoric acid, resulted in little or no dye fixation.
It will be appreciated from Examples ~7-56 herein-abo~e that a practical method has been developed for the application of phosphate vat dyes to cotton and cotton-cont~ ing fabrics, with good col~r fixation. The prior art to date was unable to use such vat dye~ commercia~ly on cotton, because of the problem of insufficient washfas~ness.
Usi~g the dye of Example 24, an a~ueous dye ~ath soiution was prepare~, having ~.2~ weight percent of the abo~e dye, 2 weight percent of dic zndlamide, ~.1 weight percent of surfactant (Tgepal CO 710~ and 0.125 weight perce~t of phospAoric acid. A l00~ cotton fabrlc ~as padded ~ith tn$s solution) passed through an otJen at 400F ~Jith an exposure t~me of 90 se~onds, and ther scoured using the pro-cedure of Exam.ple 37 and measured color~metrically ~or dye retention. .~bout 78% of the original color was retained after scourir.g.
111~844 EXAMpLE 62 Example 61 w~s repeated, except that the dye bath contained 8 weight percent, based on the weight of the bath, of a 50% aqueous solution o~ cyanamide in addition to the 2 weight percent of dicyandiamide. About 87% color retention was obtained.
Example 61 was repeated, except the dicyandiamide was eliminated ~rom the dyebath (that is, no dicyandiamide or cyanamide was in the dyebathl. The color retention after scouring was about 10~, and even more color was removed upon laundering.
A printing paste was prepared using 0.15 weight percent of the dye o Example 25, and 0.05 weight percent of the red dyestuf of the following formula:
H O
~ N - N - ~
~ PO(OH)2 O3 ~ SO3H
as well as 0.2 weight percent of wetting agent ("Igepal CO 710*~
(nonylpheno~ypoly(ethyleneoxy)ethanol having 10-11 ethyleneoxy units sold by 5AF), 0.1 weight percent o (NH4)2~PO4, 3.0 weight percent of dicyandiamide, 33 weight percent of 3%
"Keltex S*" (aqueous solution of sodium alginate, from Kelco Company), 33.0 weight percent o~ a 70% "~arsol**" emulsion, and the remainder water.
*Trademark **Trademark o~ Exxon Corporation ~or straight petroleum aliphatic sol~ents.
X
1i~11844 The resulting print paste, with pH adjusted to 8.6, was screen printed on 100% cotton fabric at an add-on of about S grams per square yard ~about a 100~ average add-on) The fabric was dried and fixed at 400F, at an exposure time of 60 seconds, to produce a printed cotton fabric having ~ood color retention.
Another printing paste was prepared, based on 0.2 weight percent of the blue dye of Example 2S, 0.05 weight percent of the red dye having a structure as shown in Example 64, 0.2 weight percent of wetting agent ("Igepal CO 710"), 3.0 weight percPnt of dicyandiamide, 48 weight percent of 3 "Superloid*" (ammonium alginate sold by Kelco Company), 15.~
weight percent of a 70~ "Varsol" emulsion, 2 weight percent of 50% "Carb~wax**" 4000 emulsion, and the rest water The printin paste had a pH of about 4.2. The paste was scre~n printed using the procedure of Example 4, with similar results.
As mentioned hereinabove, it is, i~ some i~stances, desirable to add an acid to the dyebath in order to adjust the pH to the desired level. Phosphoric acid is a convenient strong acid which is preferred for such p~ adiustment.
However, other compounds can be used, including methyl acid phoshate, ~mmonium phosphate, bor~c acid, formic acid, lactic acid, glycolic acid and s~lfuric acid.
*TrademarX
**Trademark. Car~owax is t~e trademar.~ for the 'amily of water-soluble polyethylene glycols and their derivatives made by the Chemicals nd Plastics Division of Union Car~ide Cor~oration.
The number following the name denotes the average molecular weight and thus the ethyleneoxy content.
"Car~owax" 4000 is polyethylene glycol; it is in the form of a white, free-flowing powder or creamy white 'lakes.
1~111~44 It is preferred that the dye bath contain no sol-vent or dye assistant, but in certain instances the use of such auxilliary chemicals may be useful. If an organic solvent is used to assist in ~ringing the reactants of the present invention together at the reaction temperature (that is, the dye, the cyanamide compound, and the substrate), such a solvent should contain no free alcoholic-type hydroxyl group, should have a boiling point higher than that of water, and pre~erably should be ~i~cible with water and the cyanamide compound. In such instances, suitable solvents might be "Carbowax*" 350, "Carbowax*" 750, "Carbowax*" 2000, triethylene glycol diacetate, diethylene glycol diacetate or urea.
While a wide variety of chromophores may be used in the practice of the present invention, it is generally pre-ferred that small dye molecules, compatible with color strength, be used. In general, long, linear dye molecules tend to position themselves along the cellulose polymer in such a manner that unreacted dye may be subjected to a slow release during subsequent washings, and not removed in adequate amounts during the production rinse.
Particularly preferred dyeing conditions for monophosphonic acid dyes include the use of about 0.2 weight percent sur~actant, 0.2 weight percent phosphoric acid, no organic solvent dyeing assistant, 4.0% cyanamide and 3.0 dicyandiamide. ~uch a dyebath, with proper amounts of dyestuff therein, can be padded onto 100% cotton at about 75% pickup, and ~ixed at a temperature of about 390 F fo~
about 90 seconds in a Benz unit. The color endurance of the dyed fabric runs about 75-90%, with less than 5~ strength loss in the ~a~ric tear strength and warp and fill tensile strengths.
*"Carbowax" 350, 750 and 2000 are methoxy polyethylene glycols.
-4g-The process of the present invention for the continuous dyeing of cotton equals or exceeds other reactive dyeing systems now in use. The present process involves a pad-predry-~ake-rinse-dry system which can be utilized on existing plant equipment. Most reactive dyeing systems are based upon alkallne dyeing environments, whereas the present system operates extsemely well on the acid side with a p~ of about 5, and thus is more compatible with the disperse dyes used in the thermosol dyeing of polyester-cotton fabrics.
Dye migration problems can be controlled by ~ormal adjust-ments in the padding and predrying steps in the operating plant, ana such adjustments are even easier on polyester-cotton blends. The dyeings are q~ite consistently level.
The strength loss of the cotton fabric is generally under 5%, which is ab~ut normal for reactive dyeing processing steps The dyebaths of the present in~ention do not exhibit tailing ~color strength loss) or ageing problems over a two-day period.
As mentioned above, the monophosphonic acid dyes used in the process of the present invention produce dyed fabrics having 70-90%, especial'y 75-90%, ~olor endurance.
This color enduranc~ can be defined as the ~ercent color retained, compared to initial unrinsed fa~ric, after a fu~' rinsing and fi~e standard AATC~ machlne launderinqs. In contrast, the color endurance for compe~ e reacti~e dyes a~erages abcut 60-70~.
- 4~ -1~118~4 Previous attempts by the æ t to develop an acid-side reacti~e dye system have been characterized by poor resistance to acid perspiration, whereas the fabrics dyed according to the present process showed litt'e or no change in color, and little or no staining of a multifibered t~st fabric when teste~ accord~ng to AATCC Test ~ethod 15-1975~ In laundering, color lo-~s resistance is excellent, with the results from 10-25 washes looking very fa~ora~le. The light fastness of the dyed f~brics of the present in~ention is at least compa-titive to other reactive dyes based on similar chromophores, and the same is true of similar tests, such as dry cleaning.
Another ma~or advantage of the dye system of the present inYention is that the present dyes are not sub~ect to hydrolysis during storage, in distinct contrast to the reactive dyestuffs which are n~w on the market, which ha~e a restricted shelf life. The dyes of the present invention should last indefinitely under storage conditions, and this is basically because the present dyestufCs are stable to moist~re attac~, as c~mpared to the commercially available reactive dyestuffs.
In other words, the dyes of the present inYention axe, in their original, unreacted stat~, simple acid dyes which are chemically unaffected by maisture or water in any form. Thus, they will last with full efficiency for years, ar.d this is in distLnct contrast to reactive dyestu,Cfs designed for alkaline-side dyeings.
8~4 Another maior advantage of the dye systems of the present invention is the high percPnt fixation of the dye on the fiber which can be obtained. Normally, the alka}ine-side reactive dyes have about 70~ fixation or so, while fixations as high as 85% can be readily obtainable with the procesq of the present invention.
It is to be understood that only preferred embodi-ments of the invention have been described and that numerous alternati~es, substitutions and modifications are all permissible without departing fr~m the spirit or scope of the i~vention as defined in the following claims~
~UPPLEMENTARY DISCLQSIRE
In Example 64 (page 461 of the Principal Disclosure herein there is disclosed a novel red dyestuff having the following structural formula O H
Il i , ~ N-N _ ~
HO S ~ SO H PO(OH)2 chemically named l-hydroxy-3,6-disulfo-8-acetamido-2-(3'-phosphonophenylazo)naphthalene.
The inventive embodiment there disclosed, it has been found, embraces, in addition to the above-depicted compound the alkali metal and ammonium salts thereof. These novel bright red azo dyes exhibit properties improved over known materials, i.e., good lightfastness and color strength, they are convenient to use in commercial dyeing operations, reasonably soluble in aqueous solutions (with or without surface active agents, organic solvents or the like) and convenient to synthesize.
We have found, for instance, that these novel dyes are lightfast and are more efficient than other commonly used materials. As an example, where one pound of the novel 2~ dye compound is re~uired to dye a given quantity of substrate (such as 100% cotton or another fiber) a greater amount, up to about l.65 pounds, of another higher molecular weight dye is required to dye the same quantity of material.
~;
1~11844 The above-recited dyes, while useful as general dye-stuff materials, are particularly suitable for reactive dyeing, that is in a process where the dye is reactively linked to callulose fibers of the substrate to be dyed by means of a phosphorus ester link produced in the presence of a carbodiimide such as cyanamide. This procedure is described in detail in our German Offen. Publication ~o.
2,505,497 of August 14, 1975.
Although formulated herein in its frea-acid form, the acid dye of the invention may also be made and used in its alkali metal or ammcntum salt forms. It preferably is used in free-acid form, more preferably in the ammonium or an acid ammonium salt form. Salts of the dye with amines which are volatile under cure conditions may also be used. The ammonium and acid ammonium salts are conveniently made by adding ammonium hydroxide to solutions of the free-acid dye.
Correspondin~ly, upward adjustments of pH in the dyebath are preferably made with ammonia, less preferably with a volatile amine such as dimethylamine. Downward adjustments of pH, if needed, preferably are made with hydrochloric acid or other acid volatile undex curing conditions When used at low pH, as exemplified hereinafter, the novel free-acid dye of the invention is used in aqueous solution. At higher p~, the nature of the ammoni~n or aIkali metal salt of the dye in solution ~ill depend upon the ammonia or alkali metal content of the solution 35 measured by the pH. The ammonium salts are usual'y the tri-or tetra-ammonium salts, or mixtures ther_of, ~ithin ~he general p~ range employed. ~.ixtures of ammoniIm an alkali metal salts may also be use~.
~:~118~4 Co~pounds of our invention are produced by reacting N-acetyl H-acid with dtazotized m-aminobenzene-phosphonic acid in the presence of suitable ajuncts. The preparation of N-acetyl H-acid is described in Fierz-David, "Fundamental Processes of Dye Chemistry", Interscience Publishers, 1949, at pp. 263-264. The general reaction of certain naphthol sulfonic acids with 3-aminobenzenephosphonic acid is described in Example 1 o~ ~7. S. Patent No. 3,202,550 to Grossmann et al.
EXAM~LE 66 H acid (eastman produced purified by reprecipita-tion, 175 g. 0.5 mold), sodium carbonate ~30 g), and water (750 ml) were mixed and heated to 50C to dissolve. Acetic anhydride (85 g, 0.83 mole) was added dropwise over 15 minutes and the solution then stirred ~or 1 hour at 50C. Sodium carbonate (75 g) was then added and the solution heated for 1 hour at 95C to reverse any acylation of the hydroxyl group.
The solution was then cooled in ice.
m-Aminophenylphosphonic acid (86.5 g, 0.5 moles) and sodium carbonate (53 g, 0.5 mole) were dissolved in water (500 ml). Sodium nitrite (37 g. 0.54 mole) in water (1~0 ml) was added, and the solution cooled to 1~C. The solution was added to concentrated hydrochloric acid (125 ml) and ice (500 g.). The solution was added all at once to the solution of acetyl H acid, and the solution stirred for 1 hour. Concentrated hydrochloric acid ~500 ml) was then added (pH = 0.5) and the solution filtered. The precipitated solid was washed with glacial acetic acid and dried under vacuum at 50C.
Further purification to the free acid was effected by dissolving the dye in aqueous methanol and passing the -~D54-111~844 solution through an acid ion exchange resl~. Removal of the solvent yielded a dye which was, by titration, a tetrabasic acid of greater than 95% purity, thus confirming the structure illustrated above.
As a further means of analysis, the free acid was reacted in solution to make the tri-potassium salt and the solution evaporated to dryness giving the heptahydrated potassium salt having the empirical formula:
C18Hl30llN3s2pK3 7H2 Results of elemental analysis are:
.
Theory: C 27.5 N 5.4 S 8.1 P 3.9 H:2O 16.0 Molecular r~eight 785 Found: C 26.9 N 5.8 S 7.7 P 3.5 H2O 15.5 Molecular Weight 789 .
A printing paste was prepared using 0.05 weight percent of the dye of the formula:
0 3jI
~ , ,1 ~O3S 3 PO(OH)2 and 0.i5 weight percent of a blue dye of the struc~ure:
-SD5,-~1118~4 o NH2 PO(0~)2 CH2PO(OE)2 This dye iq prepared by reacting bromaminic acid with o-amino-p-xylylenediphosphonic acid as described in Example 25 of our German Offen. P 25 05 497.1.
The print paste also included 0.2 weight percent of a r~ ~' wetting agent (IgepalCO-710"* nonylphenoxypoly(ethyleneoxy)-ethanol having 10-11 ethyleneoxy units, sold by GAF), 0.1 weight percént (NH4)2HP04, 3.0 weight percent of dicyan-diamide, 1,O weight percent of sodium alginate, 33.0 weight percent of 70% Varsol emulsion and the remalnder water, The resulting print paste was adjusted to a pH of 8.6 with ammonium hydroxide.
The print paste so prepared was screen printed on 100% cotton fabric at an add-on of a~out ~ grams per square yard (about a 100~ average add-on). The fabric was dried and fixed at 400~F, at an exposure time of ~0 seconds, to produce a printed cotton fabric having a good color fixation.
(This example corresponds in substance to Example 64 of the Principal Disclosure.) In the following Examples 68-70, all percentages are expressed on the weight of the bath.
*Trademar~
A dye bath containing the ~ollowing ingredients was prepared:
.
1.0~ Red dye o~ Example 66 3~0% H3P04 (85~) 8.0% "Cyanamide AC-50" (50%) 2.0~ "Car~owax 350"
0.25% "Igepal C0-710"
pH 1.5 The above bath was padded on 100% cotton at 70% pick-up, dried at 220F, and cured for 60 seconds at 390F. The cloth was rinsed; practically no color was removed.
A bath containinq the following ingredients was prepared:
0.5% Red dye of Example 66
Another ma~or advantage of the dye system of the present inYention is that the present dyes are not sub~ect to hydrolysis during storage, in distinct contrast to the reactive dyestuffs which are n~w on the market, which ha~e a restricted shelf life. The dyes of the present invention should last indefinitely under storage conditions, and this is basically because the present dyestufCs are stable to moist~re attac~, as c~mpared to the commercially available reactive dyestuffs.
In other words, the dyes of the present inYention axe, in their original, unreacted stat~, simple acid dyes which are chemically unaffected by maisture or water in any form. Thus, they will last with full efficiency for years, ar.d this is in distLnct contrast to reactive dyestu,Cfs designed for alkaline-side dyeings.
8~4 Another maior advantage of the dye systems of the present invention is the high percPnt fixation of the dye on the fiber which can be obtained. Normally, the alka}ine-side reactive dyes have about 70~ fixation or so, while fixations as high as 85% can be readily obtainable with the procesq of the present invention.
It is to be understood that only preferred embodi-ments of the invention have been described and that numerous alternati~es, substitutions and modifications are all permissible without departing fr~m the spirit or scope of the i~vention as defined in the following claims~
~UPPLEMENTARY DISCLQSIRE
In Example 64 (page 461 of the Principal Disclosure herein there is disclosed a novel red dyestuff having the following structural formula O H
Il i , ~ N-N _ ~
HO S ~ SO H PO(OH)2 chemically named l-hydroxy-3,6-disulfo-8-acetamido-2-(3'-phosphonophenylazo)naphthalene.
The inventive embodiment there disclosed, it has been found, embraces, in addition to the above-depicted compound the alkali metal and ammonium salts thereof. These novel bright red azo dyes exhibit properties improved over known materials, i.e., good lightfastness and color strength, they are convenient to use in commercial dyeing operations, reasonably soluble in aqueous solutions (with or without surface active agents, organic solvents or the like) and convenient to synthesize.
We have found, for instance, that these novel dyes are lightfast and are more efficient than other commonly used materials. As an example, where one pound of the novel 2~ dye compound is re~uired to dye a given quantity of substrate (such as 100% cotton or another fiber) a greater amount, up to about l.65 pounds, of another higher molecular weight dye is required to dye the same quantity of material.
~;
1~11844 The above-recited dyes, while useful as general dye-stuff materials, are particularly suitable for reactive dyeing, that is in a process where the dye is reactively linked to callulose fibers of the substrate to be dyed by means of a phosphorus ester link produced in the presence of a carbodiimide such as cyanamide. This procedure is described in detail in our German Offen. Publication ~o.
2,505,497 of August 14, 1975.
Although formulated herein in its frea-acid form, the acid dye of the invention may also be made and used in its alkali metal or ammcntum salt forms. It preferably is used in free-acid form, more preferably in the ammonium or an acid ammonium salt form. Salts of the dye with amines which are volatile under cure conditions may also be used. The ammonium and acid ammonium salts are conveniently made by adding ammonium hydroxide to solutions of the free-acid dye.
Correspondin~ly, upward adjustments of pH in the dyebath are preferably made with ammonia, less preferably with a volatile amine such as dimethylamine. Downward adjustments of pH, if needed, preferably are made with hydrochloric acid or other acid volatile undex curing conditions When used at low pH, as exemplified hereinafter, the novel free-acid dye of the invention is used in aqueous solution. At higher p~, the nature of the ammoni~n or aIkali metal salt of the dye in solution ~ill depend upon the ammonia or alkali metal content of the solution 35 measured by the pH. The ammonium salts are usual'y the tri-or tetra-ammonium salts, or mixtures ther_of, ~ithin ~he general p~ range employed. ~.ixtures of ammoniIm an alkali metal salts may also be use~.
~:~118~4 Co~pounds of our invention are produced by reacting N-acetyl H-acid with dtazotized m-aminobenzene-phosphonic acid in the presence of suitable ajuncts. The preparation of N-acetyl H-acid is described in Fierz-David, "Fundamental Processes of Dye Chemistry", Interscience Publishers, 1949, at pp. 263-264. The general reaction of certain naphthol sulfonic acids with 3-aminobenzenephosphonic acid is described in Example 1 o~ ~7. S. Patent No. 3,202,550 to Grossmann et al.
EXAM~LE 66 H acid (eastman produced purified by reprecipita-tion, 175 g. 0.5 mold), sodium carbonate ~30 g), and water (750 ml) were mixed and heated to 50C to dissolve. Acetic anhydride (85 g, 0.83 mole) was added dropwise over 15 minutes and the solution then stirred ~or 1 hour at 50C. Sodium carbonate (75 g) was then added and the solution heated for 1 hour at 95C to reverse any acylation of the hydroxyl group.
The solution was then cooled in ice.
m-Aminophenylphosphonic acid (86.5 g, 0.5 moles) and sodium carbonate (53 g, 0.5 mole) were dissolved in water (500 ml). Sodium nitrite (37 g. 0.54 mole) in water (1~0 ml) was added, and the solution cooled to 1~C. The solution was added to concentrated hydrochloric acid (125 ml) and ice (500 g.). The solution was added all at once to the solution of acetyl H acid, and the solution stirred for 1 hour. Concentrated hydrochloric acid ~500 ml) was then added (pH = 0.5) and the solution filtered. The precipitated solid was washed with glacial acetic acid and dried under vacuum at 50C.
Further purification to the free acid was effected by dissolving the dye in aqueous methanol and passing the -~D54-111~844 solution through an acid ion exchange resl~. Removal of the solvent yielded a dye which was, by titration, a tetrabasic acid of greater than 95% purity, thus confirming the structure illustrated above.
As a further means of analysis, the free acid was reacted in solution to make the tri-potassium salt and the solution evaporated to dryness giving the heptahydrated potassium salt having the empirical formula:
C18Hl30llN3s2pK3 7H2 Results of elemental analysis are:
.
Theory: C 27.5 N 5.4 S 8.1 P 3.9 H:2O 16.0 Molecular r~eight 785 Found: C 26.9 N 5.8 S 7.7 P 3.5 H2O 15.5 Molecular Weight 789 .
A printing paste was prepared using 0.05 weight percent of the dye of the formula:
0 3jI
~ , ,1 ~O3S 3 PO(OH)2 and 0.i5 weight percent of a blue dye of the struc~ure:
-SD5,-~1118~4 o NH2 PO(0~)2 CH2PO(OE)2 This dye iq prepared by reacting bromaminic acid with o-amino-p-xylylenediphosphonic acid as described in Example 25 of our German Offen. P 25 05 497.1.
The print paste also included 0.2 weight percent of a r~ ~' wetting agent (IgepalCO-710"* nonylphenoxypoly(ethyleneoxy)-ethanol having 10-11 ethyleneoxy units, sold by GAF), 0.1 weight percént (NH4)2HP04, 3.0 weight percent of dicyan-diamide, 1,O weight percent of sodium alginate, 33.0 weight percent of 70% Varsol emulsion and the remalnder water, The resulting print paste was adjusted to a pH of 8.6 with ammonium hydroxide.
The print paste so prepared was screen printed on 100% cotton fabric at an add-on of a~out ~ grams per square yard (about a 100~ average add-on). The fabric was dried and fixed at 400~F, at an exposure time of ~0 seconds, to produce a printed cotton fabric having a good color fixation.
(This example corresponds in substance to Example 64 of the Principal Disclosure.) In the following Examples 68-70, all percentages are expressed on the weight of the bath.
*Trademar~
A dye bath containing the ~ollowing ingredients was prepared:
.
1.0~ Red dye o~ Example 66 3~0% H3P04 (85~) 8.0% "Cyanamide AC-50" (50%) 2.0~ "Car~owax 350"
0.25% "Igepal C0-710"
pH 1.5 The above bath was padded on 100% cotton at 70% pick-up, dried at 220F, and cured for 60 seconds at 390F. The cloth was rinsed; practically no color was removed.
A bath containinq the following ingredients was prepared:
0.5% Red dye of Example 66
5.0% "Cyanamide AC-50" (50%) O.S~ "Igepal C0-710"
0 34 H3P04 l85%) pH Adjusted to 5 with NH40H
.
This bath was padded on 1004 cotton, steamed for 1 minute at 220 F and then cured 45 seconds at 390F. When the cloth was scoured with 1.7 g/l soda ash and 1.5 g/l "Synthrapol SP"
at the boil for 2 mlnutes, a fixation of B0~ was obtained.
Fixation is defined herein as that percentage of the color retained on the cloth after scouring, based on the color as it comes from the curing o~en, both color measurements being taken on a Bechman DBG Spectrophotometer.
~r The following bath was prepared:
-2.0% Red dye of Example 66 4 . 0% Dicyandiamide 0.1% Igepal CO-71Q
0.125% 3 4 ( 5%
pH 5 This bath was padded on a 50/50 blend of polyester (T54)/
cotton at 60% pick-up, infrared pre-dried and cured 75 seconds at 400F. After scouring as in Example 69, color fixation was 70~.
As noted above, the novel dyes of the invention are usually efficient, by which it is meant that the color yield per unit of dye weight is exceptional for a dye which is washfast on cellulosic fabrics and yarns. The exceptional efficiency stems from the fact that the dyes give inherently intens~ bright red dyeings, coupled with the fact that their molecular weights are very low by comparison with the large-molecule direct dyes which are substantive to cellulosics. Hence each molecule, which is to say, each low molecular weight of it, provides a high yleld of color on a pound-for-pound basis.
The low molecular weight, or expressed otherwise, the general simplicity and smallness of the molecule, provide yet another advantage to the dyes of the invention.
Especially when a dye is permanently fixed to a substrate by chemical reaction, it is highly desirable that any of the dye which has failed to become reactively bound should be readily washed away during process rinsing, to provide -S~58-easy washoff, and reduce subs~quent "washdown" during use.I~ the dyes of the invention, the same phosphonic acid group which provides a site for reaction also serves as a strong water-solubilizing group for aiding removal of any dye molecules which are not fixed, thereby insuring efficient removal of unfixed dye during process rinsing, and reducing or even eliminating subsequent drawn-out washdown during customer use. The red dyes of the invention are believed to be easier to wash off in process rinsing than any red dye being used in commercial continuous dyeing today.
The acetyl group is provided in the dyes as the smallest group capable of overcoming the inherent susceptibility to light of H-acid dyes. Other groups will furnish lightfastness properties, but no other so efficiently as the acetyl. In other words, the acetyl group supplies lightfastness in conjunction with minimum effect on the high redness per pound of the dye~ of the in~ention.
The dyes of the invention have a distinct advantage, compared to conventional reactive dyes which are applied under strongly alkaline conditisns, that they mostly are applied under acidic conditions and thus may be applied together with disperse dyes in the same dyebath. Alkaline conditions lead to floccu}ation of the majority of disperse dyes, which fact drastically ~imits the possibilities for simultaneous dyeings of polyester and cotton with disperse and conventional reactive dyes. In contrast, the acid fixing conditions used ~ith the phosphonic dyes of the invention have no adv~rse effect on disperse dyes, and the two types of dyes can be used together without difCicul y.
0 34 H3P04 l85%) pH Adjusted to 5 with NH40H
.
This bath was padded on 1004 cotton, steamed for 1 minute at 220 F and then cured 45 seconds at 390F. When the cloth was scoured with 1.7 g/l soda ash and 1.5 g/l "Synthrapol SP"
at the boil for 2 mlnutes, a fixation of B0~ was obtained.
Fixation is defined herein as that percentage of the color retained on the cloth after scouring, based on the color as it comes from the curing o~en, both color measurements being taken on a Bechman DBG Spectrophotometer.
~r The following bath was prepared:
-2.0% Red dye of Example 66 4 . 0% Dicyandiamide 0.1% Igepal CO-71Q
0.125% 3 4 ( 5%
pH 5 This bath was padded on a 50/50 blend of polyester (T54)/
cotton at 60% pick-up, infrared pre-dried and cured 75 seconds at 400F. After scouring as in Example 69, color fixation was 70~.
As noted above, the novel dyes of the invention are usually efficient, by which it is meant that the color yield per unit of dye weight is exceptional for a dye which is washfast on cellulosic fabrics and yarns. The exceptional efficiency stems from the fact that the dyes give inherently intens~ bright red dyeings, coupled with the fact that their molecular weights are very low by comparison with the large-molecule direct dyes which are substantive to cellulosics. Hence each molecule, which is to say, each low molecular weight of it, provides a high yleld of color on a pound-for-pound basis.
The low molecular weight, or expressed otherwise, the general simplicity and smallness of the molecule, provide yet another advantage to the dyes of the invention.
Especially when a dye is permanently fixed to a substrate by chemical reaction, it is highly desirable that any of the dye which has failed to become reactively bound should be readily washed away during process rinsing, to provide -S~58-easy washoff, and reduce subs~quent "washdown" during use.I~ the dyes of the invention, the same phosphonic acid group which provides a site for reaction also serves as a strong water-solubilizing group for aiding removal of any dye molecules which are not fixed, thereby insuring efficient removal of unfixed dye during process rinsing, and reducing or even eliminating subsequent drawn-out washdown during customer use. The red dyes of the invention are believed to be easier to wash off in process rinsing than any red dye being used in commercial continuous dyeing today.
The acetyl group is provided in the dyes as the smallest group capable of overcoming the inherent susceptibility to light of H-acid dyes. Other groups will furnish lightfastness properties, but no other so efficiently as the acetyl. In other words, the acetyl group supplies lightfastness in conjunction with minimum effect on the high redness per pound of the dye~ of the in~ention.
The dyes of the invention have a distinct advantage, compared to conventional reactive dyes which are applied under strongly alkaline conditisns, that they mostly are applied under acidic conditions and thus may be applied together with disperse dyes in the same dyebath. Alkaline conditions lead to floccu}ation of the majority of disperse dyes, which fact drastically ~imits the possibilities for simultaneous dyeings of polyester and cotton with disperse and conventional reactive dyes. In contrast, the acid fixing conditions used ~ith the phosphonic dyes of the invention have no adv~rse effect on disperse dyes, and the two types of dyes can be used together without difCicul y.
Claims
1. A dyestuff of the following formula:
.
.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US44139374A | 1974-02-11 | 1974-02-11 | |
US441,393 | 1974-02-11 | ||
US53434974A | 1974-12-18 | 1974-12-18 | |
US534,349 | 1974-12-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1111844A true CA1111844A (en) | 1981-11-03 |
Family
ID=27032798
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA219,183A Expired CA1090054A (en) | 1974-02-11 | 1975-01-31 | Reactive dyeing system and xylylene diphosphonic acid dyes |
CA356,595A Expired CA1111844A (en) | 1974-02-11 | 1978-12-27 | Reactive dyeing system and xylylene diphosphonic acid dyes |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA219,183A Expired CA1090054A (en) | 1974-02-11 | 1975-01-31 | Reactive dyeing system and xylylene diphosphonic acid dyes |
Country Status (9)
Country | Link |
---|---|
JP (1) | JPS50157466A (en) |
AU (1) | AU7797075A (en) |
BE (1) | BE836496R (en) |
BR (1) | BR7500846A (en) |
CA (2) | CA1090054A (en) |
CH (2) | CH609998A5 (en) |
DE (2) | DE2505497C3 (en) |
GB (2) | GB1497344A (en) |
IT (1) | IT1032233B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3504964A1 (en) * | 1984-07-13 | 1986-01-23 | Bayer Ag, 5090 Leverkusen | DYE SOLUTIONS |
JPH01230673A (en) * | 1988-03-10 | 1989-09-14 | Osaka Prefecture | Anthraquinone compound, dye and dyeing of leather |
CN103422368B (en) * | 2012-05-22 | 2015-06-17 | 江南大学 | Dyeing method of cotton product reduced dye with low bath ratio |
-
1975
- 1975-01-31 CA CA219,183A patent/CA1090054A/en not_active Expired
- 1975-02-05 CH CH1032576A patent/CH609998A5/en not_active IP Right Cessation
- 1975-02-05 CH CH135975A patent/CH616292GA3/en unknown
- 1975-02-06 AU AU77970/75A patent/AU7797075A/en not_active Expired
- 1975-02-07 BR BR846/75A patent/BR7500846A/en unknown
- 1975-02-10 GB GB5576/75A patent/GB1497344A/en not_active Expired
- 1975-02-10 JP JP50016360A patent/JPS50157466A/ja active Pending
- 1975-02-10 DE DE2505497A patent/DE2505497C3/en not_active Expired
- 1975-02-10 GB GB42092/76A patent/GB1497345A/en not_active Expired
- 1975-02-10 IT IT48085/75A patent/IT1032233B/en active
- 1975-02-10 DE DE2559540A patent/DE2559540C3/en not_active Expired
- 1975-12-10 BE BE162626A patent/BE836496R/en not_active IP Right Cessation
-
1978
- 1978-12-27 CA CA356,595A patent/CA1111844A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE2559540A1 (en) | 1977-02-10 |
AU7797075A (en) | 1976-08-12 |
JPS50157466A (en) | 1975-12-19 |
DE2505497B2 (en) | 1979-04-26 |
BR7500846A (en) | 1975-12-02 |
DE2505497A1 (en) | 1975-08-14 |
DE2505497C3 (en) | 1979-12-20 |
GB1497345A (en) | 1978-01-05 |
CA1090054A (en) | 1980-11-25 |
DE2559540C3 (en) | 1980-06-04 |
CH616292B (en) | |
GB1497344A (en) | 1978-01-05 |
BE836496R (en) | 1976-04-01 |
DE2559540B2 (en) | 1979-09-20 |
CH609998A5 (en) | 1979-03-30 |
CH616292GA3 (en) | 1980-03-31 |
IT1032233B (en) | 1979-05-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR880001614B1 (en) | Cellulose fabric pr those mixed spinning dyeing method | |
GB2076006A (en) | Reactive disazo compounds | |
US3531459A (en) | Monoazo-dyestuffs containing fiber-reactive and water solubilizing radicals | |
US4134722A (en) | Reactive dyeing system using phosphorus acid dyes with a cyanamide compound | |
US2892671A (en) | Coloring process | |
US4150020A (en) | Reactive xylylene diphosphonic acid dyes | |
US4150021A (en) | Esters of cellulose with phosphonic acid dyes having a sulfonamide bridge | |
CA1111844A (en) | Reactive dyeing system and xylylene diphosphonic acid dyes | |
KR910000526B1 (en) | Method for dyeing and finishing cellulose fiber material | |
US4111648A (en) | Reactive dyeing systems using dyes with carboxylic acid groups | |
US3148933A (en) | Process for coloring fibers with fiber reactive phthalocyanine dyestuffs and products obtained thereby | |
US4378970A (en) | Red monoazo sulphonic acid dyestuffs for polyamide | |
US3294778A (en) | Fiber-reactive dyestuffs | |
US3232927A (en) | Water soluble organic dyestuffs | |
US4474696A (en) | Reactive disazo dyestuffs containing triazines | |
EP0203567B1 (en) | Disazo dyes and dyeing method using the same | |
US4394129A (en) | Process for the finishing of fibrous materials: sulfonyl- or carbonyl-cyanamides of dyestuffs | |
KR20010067352A (en) | Blue monoazo disperse dyestuff | |
US6319290B1 (en) | Fiber-reactive disazo dyestuffs | |
KR890001784B1 (en) | Process for the manufacture of monoazo compounds | |
GB2255981A (en) | Dry leuco sulphur dyes | |
US4699626A (en) | Mixtures of copper complexes of disazo compounds: 4,4'-(3,3'-dihydroxybiphenylene) tetrazo component and disulfonaphthol and 3-sulfo-6-(2'-chloro-4'-chloro or hydroxy-1,3,5-triazin-6'-ylamino)-naphth-1-ol coupling component | |
US3232926A (en) | 5,5'-methylene-bis(halopyrimidine) dyestuffs | |
US3301846A (en) | Dyestuffs containing chloromethyl or bromomethyl groups | |
CA1085386A (en) | Water-soluble brown l:2-chromium-mixed complex dyestuffs, process for their manufacture and their use for the dyeing of natural or synthetic polyamide fibers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |