US2785040A - Process for dyeing cellulosic materials - Google Patents
Process for dyeing cellulosic materials Download PDFInfo
- Publication number
- US2785040A US2785040A US2785040DA US2785040A US 2785040 A US2785040 A US 2785040A US 2785040D A US2785040D A US 2785040DA US 2785040 A US2785040 A US 2785040A
- Authority
- US
- United States
- Prior art keywords
- pyrophosphate
- sodium
- parts
- dyeing
- copper
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 80
- 238000004043 dyeing Methods 0.000 title claims description 74
- 239000000463 material Substances 0.000 title claims description 48
- 239000002184 metal Substances 0.000 claims description 96
- 229910052751 metal Inorganic materials 0.000 claims description 96
- 239000003795 chemical substances by application Substances 0.000 claims description 78
- 238000001465 metallisation Methods 0.000 claims description 38
- 230000001264 neutralization Effects 0.000 claims description 30
- 150000001412 amines Chemical class 0.000 claims description 26
- 150000001450 anions Chemical class 0.000 claims description 22
- 239000000975 dye Substances 0.000 claims description 16
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 235000011180 diphosphates Nutrition 0.000 description 38
- 229940048084 Pyrophosphate Drugs 0.000 description 34
- 239000010949 copper Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 34
- 229910052802 copper Inorganic materials 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- XPPKVPWEQAFLFU-UHFFFAOYSA-J Pyrophosphate Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 24
- -1 for example Chemical compound 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- XAOURURONSTUPU-UHFFFAOYSA-K [O-]P([O-])(=O)OP(=O)([O-])O.[Cu+2].[Na+] Chemical compound [O-]P([O-])(=O)OP(=O)([O-])O.[Cu+2].[Na+] XAOURURONSTUPU-UHFFFAOYSA-K 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 238000009835 boiling Methods 0.000 description 20
- FQENQNTWSFEDLI-UHFFFAOYSA-J Tetrasodium pyrophosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 18
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 18
- 239000003513 alkali Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 12
- 229910000365 copper sulfate Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229920000742 Cotton Polymers 0.000 description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L Nickel(II) sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 10
- XPPKVPWEQAFLFU-UHFFFAOYSA-N Pyrophosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 229940053662 nickel sulfate Drugs 0.000 description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- 235000019832 sodium triphosphate Nutrition 0.000 description 10
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 10
- 229940083608 Sodium Hydroxide Drugs 0.000 description 8
- 150000001447 alkali salts Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229940005657 pyrophosphoric acid Drugs 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 229940048086 sodium pyrophosphate Drugs 0.000 description 8
- SXFNQFWXCGYOLY-UHFFFAOYSA-J [Cu+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Cu+4].[O-]P([O-])(=O)OP([O-])([O-])=O SXFNQFWXCGYOLY-UHFFFAOYSA-J 0.000 description 6
- LSFRJVCYHFCAKA-UHFFFAOYSA-K [O-]P([O-])(=O)OP(=O)([O-])O.[Ni+2].[Na+] Chemical compound [O-]P([O-])(=O)OP(=O)([O-])O.[Ni+2].[Na+] LSFRJVCYHFCAKA-UHFFFAOYSA-K 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- SZGVJLCXTSBVKL-UHFFFAOYSA-H 2,4,6,8,10,12-hexaoxido-1,3,5,7,9,11-hexaoxa-2$l^{5},4$l^{5},6$l^{5},8$l^{5},10$l^{5},12$l^{5}-hexaphosphacyclododecane 2,4,6,8,10,12-hexaoxide Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)O1 SZGVJLCXTSBVKL-UHFFFAOYSA-H 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- 238000009967 direct dyeing Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 229940005740 hexametaphosphate Drugs 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241000006460 Cyana Species 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N D-sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 241000658540 Ora Species 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H Sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 229960004793 Sucrose Drugs 0.000 description 2
- FPBMTPLRBAEUMV-UHFFFAOYSA-N [Na][Ni] Chemical compound [Na][Ni] FPBMTPLRBAEUMV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- SQSPRWMERUQXNE-UHFFFAOYSA-N diaminomethylideneurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 2
- 235000013681 dietary sucrose Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 229960003540 oxyquinoline Drugs 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 150000003385 sodium Chemical class 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000001187 sodium carbonate Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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
- D06P1/32—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 oxidation dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
-
- 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
- D06P3/66—Natural or regenerated cellulose using reactive dyes
Definitions
- the dyestuffs used in the present process contain as metallizable groups, for example, ortho-hydroxy-carboxylic acid (salicylic acid), ortho:ortho-dihydroxy-azoor ortho hydroxy ortho' carboxy azo-groupings or 8-hydroxyquinoline radicals.
- ortho-hydroxy-carboxylic acid salicylic acid
- ortho:ortho-dihydroxy-azoor ortho hydroxy ortho' carboxy azo-groupings or 8-hydroxyquinoline radicals.
- direct dyestuffs that is to say, dyestufis suitable for dyeing cellulose-containing materials by the usual direct dyeing methods, of which the complex nickel or copper compounds prepared in substance are so sparingly soluble in water themselves and in the form of their alkali salts that they cannot be used for dyeing by the usual methods from an alkaline bath without special assistants.
- metallizable dyestuffs are advantageously used in the present process in the form of their alkali salts.
- an alkali for example, an alkali carbonate or alkali hydroxide.
- a large excess of an alkali hydroxide is, however, preferably avoided as it may have a disadvantageous effect.
- agent yielding metal there come into consideration agents yielding nickel and especially those yielding copper.
- the agent yielding metal is added to the dyebath after or at the earliest simultaneously with the addition of the compound providing anions of a polyphosphoric acid.
- agents yielding metal there may he used, for example, simple water-soluble salts of nickel or copper, that is to say, those which do not contain the metal in complex union, such as nickel sulfate or copper sulfate.
- tetra-alkali pyrophosphates for example, tetra-sodium pyrophosphate (NaePzOmlOI-lzO).
- alkali pyrophosphates may be added to the dyebath at the outset, if desired, as an alkaline addition for dissolving the dyestufi (see above), or after the material to be dyed has been entered in the dyebath, but at the, latest simultaneously with the agent yielding metal.
- a procedure that is especially advantageous in many cases is to use as the agent yielding metal an alkali-nickel pyrophosphate or alkali-copper pyrophosphate, for example, sodium-copper pyrophosphate (3N84P207.CU2P207).
- alkali-nickel pyrophosphate or alkali-copper pyrophosphate for example, sodium-copper pyrophosphate (3N84P207.CU2P207).
- these compounds contain, in addition to the metal forming the complex, the residue of pyrophosphoric acid, the
- the quantity of the polyphosphoric acid ions in the dyebath has a certain influence on the result.
- the dyebath should contain at least 2 mols of pyrophosphate ions per gram-atom of copper (which corresponds to the constitution of the sodium-copper pyrophosphate mentioned above).
- the excess of the agent yielding copper calculated on the quantity of dyestutf used, is not inordinately high and amounts, for example, to about 100 percent, it is desirable to make up the dyebath so that it contains at most 8 mols of pyrophosphate ions per gram-atom of copper. A higher content of pyrophosphate ions may lead to incomplete metallization.
- the dyestuff In dyeing cellulose-containing materials with direct dyestufls the dyestuff, as is generally known, is not fixed on the goods to the extent of 100 percent, but a certain residue, which in some cases is quite small, always remains unused dissolved in the dyebath, although the dyeing process appears to be practically complete.
- the metallization of the invention can generally be brought about, that is to say, the agent yielding copper may be added.
- the agent yielding copper may be added.
- the agent yielding metal depends mainly on the constitution of the-dyestuff and in part on the concentration of the bath. With some dyestuffs it is possible to add the agent yielding metal when the dyestuff is only partially fixed on the fiber. In the case of a number of dyestuffs the dyeing may be carried out by adding the agent yielding metal at the outset, for example, it may be added to the dyebath before the material to be dyed is entered.
- the dyestuffs are advantageously used in the form of their alkali salts. This applies also to the examples of the process given above, although in the examples the dyestuffs, as is usual, are formulated in the form of the free acids.
- the dyestuffs can be made up to the desired strength with the usual agents each, for example, as sodium sulfate, sodium carbonate, urea, saccharose or dextrin.
- after-treat dyeings produced by the present process with agems which enhance their properties of wet fastness.
- agems which enhance their properties of wet fastness.
- after-treatment agents which are prepared without tormaldehyde.
- the present processg it ishardly possible with the known methods to produce useful dyeings when the agent yielding metal is added before the greater part of the dyestuil V has been absorbed.
- the present process possesses quite generally the surprising advantage that aliphatic hydroxycarboxylic acids are not required, and the much more Ireadily accessible polyphosphates can be used with at least equal success.
- Dyestufi of the formula ggg g OH HO OH HO Cu Blue.
- HsN SOsH HOaS NH Ni: Reddish blue.
- the resulting copper pyrophosphate is introduced into a boiling solution of 134 parts of crystalline sodium pyrophosphate in 150 parts of water, and boiling is continued until dissolution is complete.
- the deep blue, clear solution is evaporated in vacuo, and the easily water-soluble sodium-copper pyrophosphate (3Na4P2O7.Cu2P2O7.3H2O) is obtained in the form of a pale powder.
- Sodium nickel pyrophosphate is prepared in the same manner with the corresponding equimolecular quantities of nickel sulfate and sodium pyrophosphate.
- a similar result is obtained by using, instead of sodiumcopper pyrophosphate, sodium nickel pyrophosphate or an equimolecular mixture of nickel sulfate and tetrasodium pyrophosphate.
- Example 3 p 1 part of the dyestufi of the formula CH3 CH: -OH (J-OH do I E do 00011 OOH 111K ITTH and 0.1 part of sodium hydroxide solution of 30 percent strength are covered with parts of Water, and the mixture is boiled. A dyebath prepared by diluting the resulting stock solution with 2900 parts of water having a temperature of about 60 C; i
- a similar result is obtained by using, instead of sodiumcopper pyrophosphate, sodium-nickel pyrophosphate or a mixture of solution of equimolecular quantities of nickel sulfate and sodium pyrophosphate.
- the dyestufi used in this example can be metallized, instead of with the derivatives of pyrophosphoric acid, with sodium-copper tripolyphosphate, hexasodinrn-copper tetrapolyphosphate and also with sodium-copper hexametaphosphate, or with mixtures-which yield these compounds, of copper sulfate -and sodium-tripolyphosphate, sodium tetrapolyphospliate or sodium hexametaphosphate.
- Sodium-copper tripolyphosphate is prepared as follows:
- Process for dyeing cellulosic materials with metallizable direct dyestuffs, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of non-metallized dyestuff comprises adding to the dyebath an agent yielding a metal having an atomic num her from 28 to 29 and carrying out the metallization in a neutral to alkaline medium in the presence of anions of a polyphosphoric acid and in the absence of amines.
- Process for dyeing cellulosic materials with metallizable direct dyestufis, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of non-metallized dyestufi which process comprises adding to the dyebath an agent yielding a metal having an atomic number from 28 to 29 and carrying out the metallization in a neutral to alkaline medium in the presence of anions of pyrophosphoric acid and in the absence of amines.
- Process for dyeing cellulosic materials with metallizable direct dyestufis, which form sparingly soluble metal complexes by adding an agent yielding metal toa bath containing at least a small quantity of non-' metallized dyestufif, which process comprises adding to r the dyebath an agent yielding ametal having an atomic number from 28 to 29 and carrying out the metallization in a neutral to alkaline medium in the presence of anions of hexametaphosphoric acid and in the absence of amines.
- Process for dyeing cellulosic materials with metallizable direct dyestufis, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of non metallized dyestufl which process comprises adding to the dyebath an agent yielding copper and carrying out the metallization in a neutral to alkaline medium and in the presence of anions of pyrophosphoric acid provided by the addition of an alkali pyrophosphate and in the absence of amines.
- Process for dyeing cellulosic materials with metallizable direct dyestuffs, which form sparingly soluble metal'complexes, by adding an agent yielding metal to a bath containing at least a small quantity of nonmetallized dyestufi comprises adding to the dyebath an alkali-nickel pyrophosphate and carrying out the metallization in a neutral to alkaline medium and in the absence of amines.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
United tates PROCESS FOR DYEING (ZELLULOSIC MATE WITH METALLIZABLE DRECT DYESTUFFS AND ANIONS OF A POLYPHOSPHORIQ ACE No Drawing. Application December 12, 1952,
Serial No. 325,716
Claims priority, application Switzerland December 14, 1951 '14 Claims. (Cl. 8-42) This invention is based on the observation that cellulose-containing materials can be dyed in an advantageous manner with metallizable direct dyestuffs, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing a small quantity of non-metallized dyestuff, if there is used as an agent yielding metal an agent yielding nickel or copper and the metallization is carried out in a neutral to alkaline medium in the presence of anions of a polyphosphoric acid.
The dyestuffs used in the present process contain as metallizable groups, for example, ortho-hydroxy-carboxylic acid (salicylic acid), ortho:ortho-dihydroxy-azoor ortho hydroxy ortho' carboxy azo-groupings or 8-hydroxyquinoline radicals. There come into consideration exclusively those direct dyestuffs, that is to say, dyestufis suitable for dyeing cellulose-containing materials by the usual direct dyeing methods, of which the complex nickel or copper compounds prepared in substance are so sparingly soluble in water themselves and in the form of their alkali salts that they cannot be used for dyeing by the usual methods from an alkaline bath without special assistants. These metallizable dyestuffs are advantageously used in the present process in the form of their alkali salts. In some cases it is desirable to dissolve the dyestufi with the addition of an alkali, for example, an alkali carbonate or alkali hydroxide. A large excess of an alkali hydroxide is, however, preferably avoided as it may have a disadvantageous effect.
As agent yielding metal there come into consideration agents yielding nickel and especially those yielding copper. The agent yielding metal is added to the dyebath after or at the earliest simultaneously with the addition of the compound providing anions of a polyphosphoric acid.
As agents yielding metal there may he used, for example, simple water-soluble salts of nickel or copper, that is to say, those which do not contain the metal in complex union, such as nickel sulfate or copper sulfate. In this form of the process there are advantageously used as compounds providing the anions of a polyphosphoric acid, alkali salts of polyphosphoric acids of the formula Hm+2PmO3m+1 in which m represents a whole number greater than one. Especially valuable are tetra-alkali pyrophosphates, for example, tetra-sodium pyrophosphate (NaePzOmlOI-lzO). These alkali pyrophosphates may be added to the dyebath at the outset, if desired, as an alkaline addition for dissolving the dyestufi (see above), or after the material to be dyed has been entered in the dyebath, but at the, latest simultaneously with the agent yielding metal.
A procedure that is especially advantageous in many cases is to use as the agent yielding metal an alkali-nickel pyrophosphate or alkali-copper pyrophosphate, for example, sodium-copper pyrophosphate (3N84P207.CU2P207). As these compounds contain, in addition to the metal forming the complex, the residue of pyrophosphoric acid, the
' atent further addition of a phosphorus compound of the above kind is unnecessary.
In order to utilize the improvement in tinctorial properties brought about by the metallization of the dyestutf and to ensure always producing the same tint with the same dyestuff, there is used at least the theoretical quantity of the agent yielding metal required for complete metallization, and advantageously an amount in excess of this quantity, for example, a total amount of up to twice the theoretical quantity.
The quantity of the polyphosphoric acid ions in the dyebath has a certain influence on the result. In order to avoid the precipitation of insoluble copper compounds, the dyebath should contain at least 2 mols of pyrophosphate ions per gram-atom of copper (which corresponds to the constitution of the sodium-copper pyrophosphate mentioned above). Provided that the excess of the agent yielding copper, calculated on the quantity of dyestutf used, is not inordinately high and amounts, for example, to about 100 percent, it is desirable to make up the dyebath so that it contains at most 8 mols of pyrophosphate ions per gram-atom of copper. A higher content of pyrophosphate ions may lead to incomplete metallization. From this fact, and from the observation that with a large excess of pyrophosphate ions but with the same quantitative ratio of copper to pyrophosphate ions the incomplete metallization occurring under the usual conditions can be considerably improved by a substantial increase in the quantity of the agent yielding copper (and a corresponding increase in the amount of pyrophosphate), calculated on the quantity of dyestufi it can be concluded that a kind of equilibrium reaction is involved.
In dyeing cellulose-containing materials with direct dyestufls the dyestuff, as is generally known, is not fixed on the goods to the extent of 100 percent, but a certain residue, which in some cases is quite small, always remains unused dissolved in the dyebath, although the dyeing process appears to be practically complete. At this stage of the dyeing process the metallization of the invention can generally be brought about, that is to say, the agent yielding copper may be added. Whether it is possible without disadvantage, or may even be of advantage, to add the agent yielding metal beforehand, depends mainly on the constitution of the-dyestuff and in part on the concentration of the bath. With some dyestuffs it is possible to add the agent yielding metal when the dyestuff is only partially fixed on the fiber. In the case of a number of dyestuffs the dyeing may be carried out by adding the agent yielding metal at the outset, for example, it may be added to the dyebath before the material to be dyed is entered.
As has been briefly mentioned above, the dyestuffs are advantageously used in the form of their alkali salts. This applies also to the examples of the process given above, although in the examples the dyestuffs, as is usual, are formulated in the form of the free acids. The dyestuffs can be made up to the desired strength with the usual agents each, for example, as sodium sulfate, sodium carbonate, urea, saccharose or dextrin. If this standardization to a predetermined strength is carried out with a sufiicient quantity of an alkali pyrophosphate, no further pyrophosphate need be added for dyeing, and the metallization can be carried out merely by adding at the appropriate moment a simple metal salt such, for example, as copper sulfate, without any other addition.
in other respects the dyeing carried out by one of the methods known for direct dyeing dyestuffs at a raised temperature, for example, in a boiling bath or near the boiling point, and advantageously with the addition of one of the usual salts, such as sodium sulfate.
In certain cases it may be of advantage to after-treat dyeings produced by the present process with agems which enhance their properties of wet fastness. In this connection there may be mentioned, for example, treatment with a reaction product of formaldehyde with a pompound such as .cyana'mide, dicyanarnide, 'dicyandiamidine or melamine. There may also be mentioned after-treatment agents which are prepared without tormaldehyde.
' the present processg it ishardly possible with the known methods to produce useful dyeings when the agent yielding metal is added before the greater part of the dyestuil V has been absorbed. The present process possesses quite generally the surprising advantage that aliphatic hydroxycarboxylic acids are not required, and the much more Ireadily accessible polyphosphates can be used with at least equal success. r
The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated,.and the relationship between parts by weight and parts by volume being that of the kilogram to the liter:
. p Exa mple'v I 1 part of the dyestuif of the formula and 0.1 part of sodium-hydroxide solution of 3.0 percent mixture is raised to the boil. A dyebath is prepared by diluting the resulting stock solution with 2900 parts of 7 in parts by volume '10 parts of sodium-copper pyrophosphate are added to the dyebath. 100 parts of previously Wetted cotton are then entered, and vthe bath temperature is raised to the boil: in the course of A: hour. Boiling is carried on for hour, during which 2% parts of crystalline sodium sulfate are addedafter '10 minutes and a further 20 parts thereof-after 20 minutes. At the end of this period the dyebath is well exhausted. The dyeing is rinsed in the cold/centrifuged and dried. There is obtained a deep blue dyeing of good fastness to light and washing.
A similar result is obtained if the sodium-copper pyrophosphate is added duringrthe exhaustion of the dyebath or only at the end of the exhaustion.
By using, instead-of the aforesaid sodium-copper pyrophosphate solutionythe same quantityof a'solutionof an equivalent quantity'of a mixture of nickel sulfate and tetrasodium pyrophosphate.
Instead of dyeing with the dyestufi ofthe above formula OH HO H038 NH- S 0311 V O O H V H O cotton may be dyed in the same manner with the following dyestuffs:
Dyestufi of the formula Tint of dyeing 7 H038 .HNG' V Cu: Reddish grey. 1 H0: NA Ni: Reddish grey.
7. SOsH 7 no=s BIN-G Cm Grey. 2.-.... H0 N== N=N N=N Ni: Navy blue.
doon no SOaH V V N\ H300 Hots NH-o C-NH SOsH CH3 I ll Cu: Reddlsh HO N=N N=N N N N=N N=N 0 g I p I Ni: Violet. oon on no. H V cm "000B 1 r NH:
' 'COdH r Cu: Brown. 4 no HO3S- NH-(fl) o-Nrr-G-u: 0H 7 3mm N N r a some";
Dyestufi of the formula ggg g OH HO OH HO Cu: Blue. HsN SOsH HOaS NH: Ni: Reddish blue.
OH H? OH HO N=N N=N e my 1H Ems NH iii iiii i (I JH: H: CH: CH: 6H 0E The sodium-copper pyrophosphate is prepared as follows:
44.6 parts of crystalline sodium pyrophosphate are dissolved in 300 parts of hot water, and the solution is added to a solution of 51 parts of crystalline copper sulfate (CuSO4.5HzO) in 200 parts of water. There is formed immediately a White precipitate of copper pyrophosphate, which is filtered off and Washed with water.
The resulting copper pyrophosphate is introduced into a boiling solution of 134 parts of crystalline sodium pyrophosphate in 150 parts of water, and boiling is continued until dissolution is complete. The deep blue, clear solution is evaporated in vacuo, and the easily water-soluble sodium-copper pyrophosphate (3Na4P2O7.Cu2P2O7.3H2O) is obtained in the form of a pale powder.
Sodium nickel pyrophosphate is prepared in the same manner with the corresponding equimolecular quantities of nickel sulfate and sodium pyrophosphate.
Example 2 1 part of the dyestutf, obtained by reducing the nitrodisazo-dyestutf of the formula HOaS N=N OH with glucose in sodium hydroxide solution, and 0.1 part of sodium hydroxide solution of 30 percent strength are covered with 100 parts of water, and the mixture is boiled. By diluting the resulting stock solution with 2900'parts of Water having a temperature of about 60 C. a dyebath is prepared.
100 parts of previously wetted cotton are entered and the bath temperature is raised in the course of /2 hour to 100 C. Boiling is continued for hour, during which 20 parts of crystalline sodium sulfate are added after minutes and a further parts thereof after 20 minutes. At the end of this period there are added to the dyebath 20 parts by volume of an aqueous solution containing in 100 parts by volume 10 parts of sodium-copper pyrophosphate, and the treatment is continued for a further 30 minutes. Thedyebath is well exhausted. The dyeing is rinsed in the cold, centrifuged and dried. There is obtained a grey dyeing of good fastness to light and Washing.
A similar result is obtained by adding the sodiumcopper pyrophosphate to the dyebath at the beginning of the dyeing operation.
I SO10 copper pyrophosphate, the same quantity of a solution of 4.28 parts of crystalline copper sulfate and 15.4 parts of By using, instead of the aforesaid solution of sodiumcrystalline tetrasodium pyrophosphate in parts of water, the dyeing process gives a similar result.
A similar result is obtained by using, instead of sodiumcopper pyrophosphate, sodium nickel pyrophosphate or an equimolecular mixture of nickel sulfate and tetrasodium pyrophosphate.
Example 3 p 1 part of the dyestufi of the formula CH3 CH: -OH (J-OH do I E do 00011 OOH 111K ITTH and 0.1 part of sodium hydroxide solution of 30 percent strength are covered with parts of Water, and the mixture is boiled. A dyebath prepared by diluting the resulting stock solution with 2900 parts of water having a temperature of about 60 C; i
100 parts of previously wetted cotton are entered and the temperature of the bath is raised to 100 C. in the course of A2 hour. Boiling is continued for hour, during which 20 parts of crystalline sodium sulfate are added after 10 minutes and a further 20 parts thereof after 20 minutes. At the end of this period there are added to the dyebath 20 parts by volume of an aqueous solution containing in 100 parts by volume 10 parts of sodium-copper pyrophosphate, and the treatment is continued for 30 minutes. The dyebath is then Well exhausted. The dyeing is n'nsed in the cold, centrifuged and dried. There is obtained an orange-yellow dyeing of good fastness to light and washing.
By using instead of the aforesaid sodium-copper pyrophosphate solution the same quantity of a solution of 4.28 parts of crystalline copper sulfate and 15.4 parts of crystalline tetrasodium pyrophosphate in 90 parts of Water, the dyeing process gives a similar result.
A similar result is obtained by using, instead of sodiumcopper pyrophosphate, sodium-nickel pyrophosphate or a mixture of solution of equimolecular quantities of nickel sulfate and sodium pyrophosphate.
The dyestufi used in this example can be metallized, instead of with the derivatives of pyrophosphoric acid, with sodium-copper tripolyphosphate, hexasodinrn-copper tetrapolyphosphate and also with sodium-copper hexametaphosphate, or with mixtures-which yield these compounds, of copper sulfate -and sodium-tripolyphosphate, sodium tetrapolyphospliate or sodium hexametaphosphate.
Sodium-copper tripolyphosphate is prepared as follows:
3618 parts of anhydrous sodium tripolyphosphate ar dissolved -in 200 parts -of hot water, end -the solution is equimolecular quantity' of hexasodium tetrapolyphos- Sodium copperthexametaphosphate is prepared assfoladded to a solution of 25 parts of crystalline coppersul- 5 lows: V y t fate (CUSOILSHZO) in 100 parts of Water. There is y l g g f f l immediately formed a White precipitate of copper tripoly- 2 3 1 5 5 fi i i 6 unon phosphate, Which is filtered off and washed Withwa'ter. a e O a so H 1.011 S -g me Upper 7 Th 01 h sohatersoyobtainadfiis int-mducsd fate (CuS94.5I-I2O) 1n 160 parts or Water. The blue r c 2 2 O E 36 8 H M71, I 7 19 clear solution is then evaporated in vacuo, and the easily f a 01 ng P H 0 Pa 5 i fj s soluble sodium-copper hexametaphosphate is obtained as P yP P pafts of Waten and me mutate a blue tpowder. Instead of the above mentioned sodium is boiled until dissolution is complete. The blue clear salts of thesaidjhosporioacid th cgn'esponding potas solution is evaporated in vacuo, and the easilysoluhle siumjcan bfi used. 7 pp tripolypho'sphate Obtained blue 15 Instead of using the dyestutfof the above formula, the powder. V following dyestuffs maybe used for dyeing cotton, linen By using, instead of sodium tripolyphosphate an or rayon in the manner described in this example:'
7 Dyestufl of the formula Tint of dyeing V 9 H038. NH-CO-NH 7 $03K H Q V assess.
l I e I V VYHOOCIJ CH3 HO 7 7 OH 7 OCH! COOH H300 HOaS- NH- S0311 00H, 7
H0O): (BB; 113) OH 7 H: OOH
oo'on olN OH=OH N-N CH=CH N----N c 5 r n e- 0 \O/ Q O v {Nl.Ora ge. 03H SOaH son: 802K 0 V 7 OH r a OH OOH SOVIVNHL V nooo. 7 7
I V v CuzBordeaux.
' on No,
' H018 N=N CO'OH on OK coon (EQOH 11038 7 NH 0311 00011 on 0H t r Cu: Reddish Ni l i ddish v (|3=N I N=c 1 :0 0H; $11, 0
1. Process for dyeing cellulosic materials with metallizable direct dyestuffs, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of non-metallized dyestuff, which process comprises adding to the dyebath an agent yielding a metal having an atomic num her from 28 to 29 and carrying out the metallization in a neutral to alkaline medium in the presence of anions of a polyphosphoric acid and in the absence of amines.
2. Process for dyeing cellulosic materials with metallizable direct dyestuffs, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of non-metallized dyestufl, which process comprises adding to the dyebath an agent yielding a metal having an atomic number from 28 to 29 and carrying out the metallization in a neutral to alkaline medium in the presence of anions of a polyphosphoric'acid of the formula in which m represents a Whole number greater than 1 and in the absence of amines.
3. Process for dyeing cellulosic materials with metallizable direct dyestufis,, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of non-metallized dyestufi, which process comprises adding to the dyebath an agent yielding a metal having an atomic number from 28 to 29 and carrying out the metallization in a neutral to alkaline medium in the presence of anions of pyrophosphoric acid and in the absence of amines.
4. Process for dyeing cellulosic materials with metallizable direct dyestufis, which form sparingly soluble metal complexes, by adding an agent yielding metal toa bath containing at least a small quantity of non-' metallized dyestufif, which process comprises adding to r the dyebath an agent yielding ametal having an atomic number from 28 to 29 and carrying out the metallization in a neutral to alkaline medium in the presence of anions of hexametaphosphoric acid and in the absence of amines.
5. Process for dyeing cellulosic materials with metallizable direct dyestuffs, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of nonmetallized dyestufi, which process comprises adding to the dyebath an agent yielding a metal having an atomic number from 28 to 29 and carrying out the metallization H035 HOC N=N N: N=N
00 on no in a neutral to alkaline medium and in the presence of anions of pyrophosphoric acid provided by the addition of an alkali pyrophosphate and in the absence of amines.
6. Process for dyeing cellulosic materials with metallizable direct dyestufis, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of nonthe dyebath an alkali-Me pyrophosphate, Merepresent ing a metal having an atomic number from 28 to 29 and carrying out the metallization in a neutral to alkaline medium and in the absence of amines.
7. Process for dyeing cellulosic materials with metallizable direct dyestufis, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of non metallized dyestufl", which process comprises adding to the dyebath an agent yielding copper and carrying out the metallization in a neutral to alkaline medium and in the presence of anions of pyrophosphoric acid provided by the addition of an alkali pyrophosphate and in the absence of amines.
8. Process for dyeing cellulosic materials with metallizable direct dyestuffs, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of nonmetallized dyestuif, which process comprises adding to the dyebath an alkali-copper pyrophosphate and carrying out the metallization in a neutral to alkaline medium and in the absence of amines.
9. Process for dyeing cellulosic materials with metallizable direct dyestuffs, which form sparingly soluble metal'complexes, by adding an agent yielding metal to a bath containing at least a small quantity of nonmetallized dyestufi, which process comprises adding to the dyebath an alkali-nickel pyrophosphate and carrying out the metallization in a neutral to alkaline medium and in the absence of amines.
10. Process for dyeing cellulosic materials with metallizable direct dyestuffs, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of nonmetallized dyestufii, which process comprises adding to the dyebath wherein the dyestufi of the formula COOH 7 SOaH is for the most part fixed on the material to be dyed,
and the dissolved dyestufi of the formula and carrying out the metallization in a neutral to alkaline medium and in the absence of amines.
12. Process for dyeing cellulosic materials with metallizable direct dyestufls, which form sparingly soluble metal complexes, by adding an agent yielding metal to a bath containing at least a small quantity of nonmetallized dyestuff, which process comprises adding metallized dyestuif, which process comprises adding to 75 sodium-copper pyrophosphate to the dyebath before the material to be dyed is entered Which dyebath contains theidissolyed dyestuft-pt the formula V and carrying ontjthe metalliz ati onin a neutral to alkaline um-and n t e bs ce of a ines. j 13. {Process for dyeing cellnlosic materials withvmetallizable direct dyestuffs, which form sparingly soluble metal pomplexes, by addinganage'ntyielding metal to a bath containing atleast a small qnantity of non-- metalli zed,dyestuif, which4process comprises adding 7 sodium-popper pyrophosphate to thedyebath before the S OzNH:
material to be'dyedis entered, which dyebath contains the dissolveddyestufl? of the formula 12 and carrying out the metalli z ation in a neutral to alkaline medium and in the absence of amines.
14. Process for dyeing cellulosic materials with metallizable direct dyestuffs, which form sparingly soluble metal complexes, by adding an agent yieldin'grmetal to a bath containing at least a small quantity of "non-v metallized dyestufi; which process comprises addingv sodium-nickel pyr-ophospha te to the dyebatli before the material to be dyed is entered, which dyebathcontains the dissolved dyestufi of the formul'a END 1 and carrying out the. metallization in a neutral to alkaline medium and in the absence of amines;
References Cited in the file of this patent UNITED STATES PATENTS y 7 OTHER REFERENCES v Ind, and-Eng. Chem., for November 1951, p. 5A (advertisement) American Dyestufir Reporter, fol-January 28, 1935;
pp, 40 to .47.
Claims (1)
1. PROCESS FOR DYEING CELLULOSE MATERIALS WITH METALLIZABLE DIRECT DYESTUFFS, WHICH FORM SPARINGLY SOLUBLE METAL COMPLEXES, BY ADDING AN AGENT YIELDING METAL TO A BATH CONTAINING AT LEAST A SMALL QUANTITY OF NON-METALLIZED DYESTUFF, WHICH PROCESS COMPRISES ADDING TO THE DYEBATH AN AGENT YIELDING A METAL HAVING AN ATOMIC NUMBER FROM 28 TO 29 AND CARRYING OUT THE METALLIZATION IN A NEUTRAL TO ALKALINE MEDIUM IN THE PRESENCE OF ANIONS OF A POLYPHOSPHORIC ACID AND IN THE ABSENCE OF AMINES.
Publications (1)
Publication Number | Publication Date |
---|---|
US2785040A true US2785040A (en) | 1957-03-12 |
Family
ID=3446394
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US2785040D Expired - Lifetime US2785040A (en) | Process for dyeing cellulosic materials |
Country Status (1)
Country | Link |
---|---|
US (1) | US2785040A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4248593A (en) * | 1977-08-13 | 1981-02-03 | Hoechst Aktiengesellschaft | Process for obtaining fast colorations and prints on materials consisting of cellulosic fibers or of blends thereof with synthetic fibers |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB445466A (en) * | 1932-12-07 | 1936-04-14 | Hall Lab Inc | Improvements in or relating to the dyeing or printing of textile materials |
US2148659A (en) * | 1935-04-06 | 1939-02-28 | Soc Of Chemical Ind | Process for the production of fast tints on cellulosic fibers |
US2185905A (en) * | 1940-01-02 | Process for the production of fast | ||
US2243020A (en) * | 1938-07-25 | 1941-05-20 | Soc Of Chemical Ind | Process for producing fast tints on cellulose fibers |
-
0
- US US2785040D patent/US2785040A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2185905A (en) * | 1940-01-02 | Process for the production of fast | ||
GB445466A (en) * | 1932-12-07 | 1936-04-14 | Hall Lab Inc | Improvements in or relating to the dyeing or printing of textile materials |
US2148659A (en) * | 1935-04-06 | 1939-02-28 | Soc Of Chemical Ind | Process for the production of fast tints on cellulosic fibers |
US2243020A (en) * | 1938-07-25 | 1941-05-20 | Soc Of Chemical Ind | Process for producing fast tints on cellulose fibers |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4248593A (en) * | 1977-08-13 | 1981-02-03 | Hoechst Aktiengesellschaft | Process for obtaining fast colorations and prints on materials consisting of cellulosic fibers or of blends thereof with synthetic fibers |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2785040A (en) | Process for dyeing cellulosic materials | |
US2860128A (en) | Triazine disazo-dyestuffs | |
GB369991A (en) | Manufacture of azo-dyestuffs containing chromium | |
US3288777A (en) | Metallized monoazodyestuffs containing a dihalopyrimidyl group | |
US4618673A (en) | Salts of the 1:2 chromium complex of 4-(5'-chloro-2'-hydroxy-3'-sulfophenylazo)-3-methyl-1-phenylpyrazol-5-one and 4-(3', 5'-dichloro-2'-hydroxyphenylazo)-3-methyl-1-phenylpyrazol-5-one | |
US2400092A (en) | Process for preparing coppercontaining azo dyestuffs | |
US2938895A (en) | Metalliferous disazo dyestuffs containing heavy metal in complex union and a reactive triazine nucleus | |
US2594803A (en) | Method of dyeing cellulosic fibers | |
US2714588A (en) | Copper-containing disazo dyestuffs | |
US2109806A (en) | Metalliferous azo-dyestuffs and process of making same | |
US2305747A (en) | Complex chromium compounds of ortho-hydroxyazo dyestuffs and process of making same | |
US2583519A (en) | Azo-dyestuffs | |
US2777840A (en) | Asymmetrical urea derivatives of monoazo-dyestuffs | |
US1888516A (en) | Azo-dyestuffs containing chromium and process of making same | |
US2749207A (en) | Hoxchi | |
US3399187A (en) | Copper-containing disazo dyestuffs | |
US2749206A (en) | Process for dyeing or printing cellu- | |
US2732372A (en) | Chromable monoazo dyestuffs | |
US1856796A (en) | Azo-dyestuffs containing chromium and process of making same | |
US2676958A (en) | Azo-dyestuffs | |
US1885641A (en) | Dyestuffs containing metals and process of making same | |
US3030352A (en) | New cupriferous trisazo dyestuffs and a proces for their preparation | |
US2941991A (en) | Metal-containing polyazo dyestuffs | |
US2769806A (en) | Disazo-dyestuffs | |
US2662806A (en) | Process for the dyeing of cellulosic materials and dyestuff preparations suitable for this purpose |