Patent GB-493883-A (GB)
Title: Manufacture of complex metal compounds of mordant azo-dyestuffs
IPC: C09B45/16
Filed: 1937-04-20
Abstract: Complex metal compounds of mordant o-hydroxymonoazo dyestuffs are manufactured by coupling a diazo-compound of an o-aminophenol or a substitution product thereof, particularly a sulphonated derivative, in an alkaline medium with a 1 : 8-aminonaphtholsulphonic acid, in which one hydrogen atom of the amino group is substituted by an -SO2-aryl-o-hydroxycarboxylic acid residue and the other is unsubstituted, particularly a condensation product of 1 : 8-aminonaphtholsulphonic acid with a salicylic acid sulphochloride, and treating the resulting monoazo dyestuff with at least one agent yielding metal, e.g. an agent yielding a bivalent or trivalent metal such as iron or chromium, e.g. by the process described in Specification 26460/12.  The products, which may be completely or partially metallized and may also contain several different metals simultaneously, are suitable for application by the customary methods of dyeing and printing with mordant dyestuffs, e.g. by the processes described in Specifications 26460/12, 318,469, 319,457, [all in Class 15 (ii)], and 435,701, to various fibres, e.g. cotton, regenerated cellulose artificial silk or natural silk.  In examples: (1) 1-hydroxy - 2 - amino - 4 - chlorobenzene - 6 sulphonic acid is diazotized and coupled with the condensation product from 1-hydroxy-2-carboxybenzene-4-sulphochloride and 1 : 8 : 3 : 6-acid, and the product is treated with a substance yielding chromium, e.g. chromium lactate; silk is dyed with the product in combination with a chromium mordant from an acid bath blue shades; by treating the original dyestuff with copper sulphate, there is obtained the copper compound, which is suitable for chrome printing on cotton, preferably with addition of urea, yielding violet shades; violet shades are also obtained on viscose artificial silk or natural silk by printing with the dyestuff, chromium lactate and tragacanth or gum thickening and steaming; the copper compound, or the corresponding nickel compound, may be further treated with a chromium salt; (2) the sodium salt of picramic acid is diazotized and coupled with the coupling component of (1), and the product is treated with a substance yielding chromium, e.g. chromium acetate; the product can be printed on cotton with chromium acetate, yielding greenish grey prints; (3) 1-amino-2-hydroxy-3-nitro-5-chlorobenzene is diazotized and coupled with the coupling component of (1), and the product is treated with a substance yielding chromium or with a copper salt; the products dye silk with the aid of a chromium mordant greenish blue and violet shades respectively; the copper compound is also suitable for chrome printing on cotton; (4) 1-hydroxy-2-amino - 6 - carboxybenzene - 4 - sulphonic acid is diazotized and coupled with the coupling component of (1), and the product is treated with a compound yielding copper; the product yields reddish violet prints on cotton with the aid of chromium acetate; (5) 5-nitro-3-amino - 4 - hydroxy - 1 - methylbenzene is diazotized and coupled with the coupling component of (1), and the product is converted into its chromium compound, which yields grey-blue shades in chrome printing on cotton; (6) 1 - hydroxy - 2 - amino - 4 - chlorobenzene-6-sulphonic acid is diazotized and coupled with the condensation product from 1-hydroxy-2 - carboxybenzene - 4 - sulphochloride and 1 : 8 : 4 : 6-acid, and the product is converted into its copper compound, which yields red violet prints on cotton with the aid of chromium acetate.  Samples have been furnished under Sect. 2 (5) of the chromium and copper compounds of the following dyestuffs; 1 - hydroxy - 2-amino - 4 - chlorobenzene - 6 - sulphonic acid --> the condensation product from 1-hydroxy2 - carboxybenzene - 4 - sulphochloride and 1 : 8 : 4-acid; 1 - hydroxy - 2 - amino - 4-nitrobenzene-6-sulphonic acid --> the same coupling component; 1 - hydroxy - 2 - amino-4 - chlorobenzene - 6 - sulphonic acid --> the condensation product from 1-hydroxy-2-carboxybenzene-4-sulphonic acid and 1 - 8 : 6-acid.  The Specification as open to inspection under Sect. 91 comprises also the manufacture of the dyestuffs free from metal.  It contains additional examples describing the preparation of the following dyestuffs and their chromium and copper compounds: (a) 5-nitro-3-amino-2 - hydroxy - 1 - methylbenzene --> the condensation product from salicylic acid sulphochloride and 1 : 8 : 3 : 6-acid; (b) 4-nitro-6 - chloro - 2 - aminophenol --> the same coupling component.  Reference is made in a table to the dyestuffs obtained by coupling this condensation product with the diazo compounds of p-chloro-o-aminosalicylic acid, 4-chloro - 2 - aminophenol, 5 - nitro - 2 - aminophenol, 5 - nitro - 4 - chloro - 2 - aminophenol and 4 - nitro - 2 - aminophenol - 6 - sulphonic acid.  The coupling components of the examples may be replaced by the condensation product of salicylic acid sulphochloride with 1 : 8 : 4-acid.  All the metal-free dyestuffs of the examples are described as suitable for chrome printing on cotton, and those of examples (1) and (4) above for dyeing silk with the aid of a chromium mordant.  This subject-matter does not appear in the Specification as accepted.