GB1009911A - Highly polymeric dyestuffs and process for their manufacture - Google Patents

Abstract

Polymeric dyestuffs consist of a plurality of residues of an organic dyestuff bound chemically to amino and/or amino groups of a substance of high molecular weight which is not more than colloidally soluble in water or in alkaline aqueous medium and which consists of a synthetic polymer, or a polysaccharide containing amino and/or imino groups, or a protein other than animal fibres, the amount of organic dyestuff chemically bound being at least 7% by weight of the substance of high molecular weight. The polymeric dyestuffs may be made by reacting the high molecular weight substance, in aqueous medium in the presence of an acid-binding agent, with an organic dyestuff, or a dyestuff intermediate capable of forming a covalent bond by reaction with the amino and/or imino groups, the dyestuff intermediate then being converted to the polymeric dyestuff by condensation or coupling, or by diazotization and coupling. The polymeric dyestuffs may also be made by reacting the high molecular weight substance in aqueous medium and in presence of an acid-binding agent, with a compound which is capable of forming a covalent bond by reaction with the amino and/or imino groups but which is not a dyestuff or dyestuff intermediate, the resulting product then being condensed with a dyestuff, or a dyestuff intermediate which is then converted to a dyestuff as before. Reaction with the high molecular weight substance may be carried out at temperatures up to 100 DEG C. The proportion of bound dyestuff in the product may be 10-300% by weight. Suitable acid-binding agents are alkali-metal hydroxides, bicarbonates, carbonates or phosphates. Specified high molecular weight substance are polyaminostyrene, polyvinylamine, polyethylene-imine, chitosan, aminated starch or dextrin aminated cellulose derivatives, e.g. aminoethyl cellulose, zein, groundnut protein, "Ardein" (Registered Trade Mark) and casein. The dyestuff or dyestuff intermediate may be one of the oxazine-, triphenylmethane-, xanthene-, nitro-, acridone-, perinone-, azo-, anthraquinone- or phthalocyanine-series, containing as reactive groups epoxy, ethyleneimine, isothiocyanate, carbamic acid aryl ester, propiolic acid amide, acrylamino-, vinylsulphone, sulphonyl halide, or sulphonyloxy-groups or halogen atoms, present on an aliphatic acyl residue or in a pyrimidine, phthalazine or triazine ring. Specified compounds which, while reacting with the amino and/or imino groups, but which are not dyestuffs or dyestuff intermediates are halogeno - pyrimidines, halogeno - phthalazines, halogeno - quinazolines and halogeno - triazines. In examples, amino-cellulose and casein are reacted with copper phthalocyanine 3,31,311,3111 - tetrasulphochloride; amino-starch, amino-cellulose, casein, chitosan and polyethylene imine are reacted with a diazo coupling component, followed by condensation with diazotized amines; amino-cellulose and casein are reacted with azo dyes; and casein, chitosan and polyethylene imine are reacted with cyanuric chloride or tetrachloropyrimidine, followed by reaction with diazotizable amines and coupling components. The polymeric dyestuffs may be incorporated into spinning solutions for the spin-dyeing of viscose or synthetic resins, or may be used to dye pre-formed fibres. Specifications 734,134, 866,513 and 867,571 are referred to.