Patent GB-498755-A (GB)
Title: Production of oxidation dyestuffs upon fibrous materials
IPC: D06P1/32
Filed: 1937-07-08
Abstract: Dyeings and printings are produced on fibrous materials by oxidizing thereon a compound containing one or more aromatic nuclei and one or more sulphamic acid groups or a salt of such a compound.  Specified compounds are phenyl-, tolyl-, naphthyl-, methoxyphenyl-, chlorophenyl- and phenylaminophenyl-, N-ethylphenyl-, N-(4-aminophenyl)-phenyl- and N-(41-aminophenyl)-4-hydroxyphenylmonosulphamic acids, 3 : 31-dimethoxydiphenyl-4 : 41-disulphamic acid and diphenylamine-4 : 41-disulphamic acid and specified oxidizing agents are chlorates, bromates, bichromates, nitrites and peroxides. The oxidation is preferably effected in presence of an acid or of a substance yielding acid under the treatment conditions, such as an ammonium salt, an ester, an amide, a fluorosulphonate, a nitrilosulphonate, an iminosulphonate or a hydroxylamine-di- or tri-sulphonate.  The colouration may be effected by (a) applying to the fibres a mixture of a salt of the sulphamic acid, the oxidizing agent and, if necessary, an oxidation catalyst and subjecting the goods to the action of an acid, (b) introducing the fibres, especially animal fibres, into a dyebath containing the sulphamate, the oxidizing agent, the oxidation catalyst (if necessary) and the acid or acid-forming substance, or (c) applying the sulphamate to the fibre and then treating it successively or simultaneously with the oxidizing agent and the acid.  The process may be used in conjunction with the use of "Rapidogen" (Registered Trade Mark) or Indigosol dyes.  In examples: (1) cotton goods are printed with an aqueous paste containing sodium phenylsulphamate, sodium chloride, sodium chlorate, vanadium chloride, potassium nitrilosulphonate and starch tragacanth thickening, dried, steamed in presence, if desired, of acetic acid vapour, washed, soaped, rinsed and dried to obtain an intense black print; (2) cotton goods are similarly printed with the use, as sulphamates, of sodium 2-methoxyphenyl, 4-chlorophenyl and 2 : 4-dimethylphenyl sulphamates to obtain brown, brown-violet and brown-yellow prints respectively; (3) cotton goods are similarly printed with the use, as sulphamate, of sodium N-ethylphenyl sulphamate to obtain a blue-black print; (4) cotton goods are similarly printed with the use, as sulphamates, of sodium 4-phenylaminophenyl sulphamate or N-(4-aminophenyl)-phenyl sulphamate to obtain an intense black print or of sodium N-(41-aminophenyl)-4 - hydroxyphenyl sulphamate to obtain a grey black; (5) cotton goods are printed with an aqueous paste containing sodium 4-phenylaminophenyl sulphamate, sodium chlorate, potassium ferrocyanide, potassium fluorosulphonate and starch tragacanth thickening, dried, steamed in presence of acetic acid vapour, washed and soaped to obtain an intense black print; (6) a cotton fabric is printed with an aqueous paste containing sodium 4 - phenylaminophenyl sulphamate, sodium chromate, potassium fluorosulphonate and starch tragacanth thickening and steamed in presence of acetic acid vapour to obtain a blue-black print; (7) a fabric or skein of cotton is padded with an aqueous liquor containing sodium 4-phenylaminophenyl sulphamate, sodium chlorate, vanadium chloride and gum tragacanth, dried, steamed in presence of acetic acid vapour, washed and soaped to obtain a black dyeing; (8) a cotton fabric is printed with an aqueous paste containing sodium 3 : 31-dimethoxy-4 : 41-diphenyl disulphamate, sodium chlorate, potassium fluorosulphonate, vanadium chloride and starch tragacanth thickening and further treated as in (7) to obtain a brown print; (9) cotton is printed with an aqueous paste containing sodium diphenylamine-4 : 41-disulphamate, sodium chlorate, vanadium chloride and starch tragacanth, thickening and further treated as in (7) to obtain a violet black print; (10) fabrics of viscose artificial silk, wool or natural silk are printed as in (9); (11) rabbit skins, preferably mordanted with iron, copper or chromium, are dyed various shades of grey, brown and green by treatment for 16 hours in an aqueous liquor at 30 DEG  C. containing sodium 4-phenylaminophenyl sulphamate and hydrogen peroxide with or without an addition of sulphuric or acetic acid.  The Specification as open to inspection under Sect. 91 comprises also an example in which wool is dyed an intense yellowish brown by treatment in a boiling aqueous liquor containing 4-phenylaminophenyl sulphamate, sodium sulphate and acetic acid with later addition of sulphuric acid and sodium bichromate.  This subject-matter does not appear in the Specification as accepted.  Sodium 2-methoxy, 2 : 4-dimethyl- and N-ethyl phenyl sulphamates are obtained by converting into the sodium salts the sulphamic acids obtained by the action of chlorosulphonic acid on the corresponding amines in presence of dimethylaniline.  Sodium 4-chloro- and 4-phenylamino-phenyl sulphamates are obtained by the action of sodium bisulphite on 4-chloronitrobenzene and 4-nitrodiphenylamine respectively.  Sodium N-(4-aminophenyl)-phenyl and N-(41-aminophenyl)-4-hydroxyphenyl sulphamates are obtained by converting into the sodium salts the sulphamic acids obtained by reducing the nitro groups in the products of the action of chlorosulphonic acid on 4-nitrodiphenylamine and 4-nitro-41-hydroxydiphenylamine respectively in presence of dimethylaniline.  Sodium 3 : 31-dimethoxy-4 : 41-diphenyl disulphamate and diphenylamine-4 : 41-disulphamate are obtained by converting into the sodium salts the sulphamic acids obtained by the action of chlorosulphonic acid on 3 : 31-dimethoxy-4 : 41-diaminodiphenyl and 4 : 41-diaminodiphenylamine respectively in presence of dimethylaniline.