Patent GB-968680-A (GB)
Title: Disperse dyestuffs bearing a mononuclear aromatic acyl radical with a halogenomethyl group, a process for their production, and their uses
Inventor: SENN OTTO
IPC: C08K5/00
Filed: 1960-09-19
Abstract: The invention comprises disperse dyes of the azo or nitro series which are free from SO3H or COOH groups and have at least one reactive group of formula <FORM:0968680/C4-C5/1> where x is H or an alkyl group of 1-4 C atoms, which may be substituted, y is CO or SO2 and Z is Hlg and A may have further substituents. The dyes may be made by condensing 1 mol. of a dye which has at least one amino group with an exchangeable hydrogen atom, or 1 mol. of an organic compound which has at least one amino group with an exchangeable hydrogen atom plus at least one group capable of forming an azo or nitro dye, with at least 1 mol. of a fractional derivative of an aromatic mononuclear acid which bears one halogenomethyl group, and, if an organic compound has been used, converting the product by coupling, or condensation, into an azo or nitro dye.  Preferably aromatic acid halides are used for the condensation.  Mono-and dis-azo dyes are mentioned and, when metallizable, they may be metallized with, e.g., Cr, Co, Ni or Cu yielding agents.  Metal-containing dyes may be used for the condensation. The metal dyes may be formed in substance or on the fibre.  The acylamino group may be in either the diazo, or the coupling, moiety of the dye molecule.  The dyes colour hydrophobic fibres, e.g. cellulose ether and ester, linear polyester, polyurethane, polyacrylonitrile, and acrylonitrile copolymer fibres but are preferably used on synthetic polyamide and basically modified polyacrylonitrile fibres (see Division D1). Examples are provided of the preparation of the dyes and their use in dyeing synthetic polyamide and secondary cellulose acetate fibres in yellow and red shades, representative of the dyes prepared being 2-hydroxy-5-methyl-41-amino - 1,11 - azobenzene, 4 - amino - 21,51 - dimethoxy - 41 - phenylazo - 1,11 - azobenzene, 3 - methyl - 4 - (41 - amino - 21 - nitro) - phenylaz - 5 - pyrazolone, 1 - [41 - (211 - amino) - ethyl-N - (21 - cyanoethyl) - amino] - phenylazo - 4 - methylsulphonylnaphthalene, 4 - amino - 21 - chloromethylsulphonyl - 1,11 - azobenzene and 1 - [41 - (211 - amino) - ethoxy] - phenylamino - 2 - nitrobenzene - 4 - sulphonic acid phenylamide, all of which are condensed with, e.g., 4 - chloromethylbenzene - 1 - carboxylic acid chloride, 4 - bromomethylbenzene - 1 - carboxylic acid bromide or 4-chloromethylbenzene sulphonic acid chloride and the dye 1-amino-2-chloro - 4 - methylsulphonylbenzene --> N - ethyl - N - [21 - 411 - chloromethylbenzenecarbonyl)-aminoethyl]-aniline.  Reference has been directed by the Comptroller to Specification 917,764.ALSO:Disperse dyes of the azo or nitro series which are free from SO3H or COOH groups and have at least one reactive group of formula <FORM:0968680/D1-D2/1> where X is H or an alkyl group of 1-4 C atoms, which may be substituted, Y is CO or SO2 and Z is halogen and A may have further substituents are used to colour hydrophobic fibres in yellow or red shades.  Fibres stated to be coloured by dyeing, padding or printing are those of cellulose ethers and esters, linear polyesters, polyurethanes polyacrylonitrile and acrylonitrile copolymers and especially those of synthetic polyamides and basically modified polyacrylonitriles.  Blends of fibres may be used. Conventional wetting, levelling, thickening and other textile auxiliary agents may be used the fibres being heat-treated either during, or after, the application of the dye, preferably in the presence of acid-binding agents.  Indicated dispersing agents are condensation products of naphthalene sulphonic acid and formaldehyde and of alkylphenols and ethylene oxide, esters of sulphosuccinic acid, Turkey red oil and soaps; they are used with or without, protective colloids such as dextrins, British gum, and water-soluble proteins.  Secondary cellulose acetate is dyed at 60-85 DEG C. and the triacetate at 95-100 DEG C.  Fully synthetic fibres are dyed at 60-100 DEG C. or under pressure at temperatures of over 100 DEG C. The printing pastes contain normal additions such as urea and thiourea.  Mono-and dis-azo dyes are mentioned and, when metallizable, complexes may be formed with e.g. Cr, Co, Ni or Cu yielding agents. Metallization may be affected in substance or on the fibre. Examples 1-13 illustrate the preparation of the dyes and their use in dyeing polyamide fibres from aqueous dispersion representative of the dyes used being 2-hydroxy-5-methyl-41-amino-1, 11-azobenzene, 4-amino-21,51-dimethoxy-41-phenylazo-1, 11 azobenzene, 3-methyl-4-(41-amino-21-nitro)-phenylazo-5-pyrazolone, 1-[41-(211-amino)-ethyl-N-(21-cyanoethyl) -amino]-phenylazo-4-methylsulphonyl-naphthalene, 4-amino-21-chloromethylsulphonyl-1, 11-azobenzene and 1-[41-(211-amino) -ethoxyl-phenylamino-2-nitrobenzene-4-sulphonic acid phenylamide all of which are condensed with e.g. 4-chloromethylbenzene-1-carboxylic acid chloride, 4-bromomethylbenzene-1-carboxylic acid bromide or 4-chloromethylbenzene sulphonyl chloride.  In addition secondary cellulose acetate is printed with a paste comprising an aqueous dispersion of the dye 1-[41-(211-amino) -ethoxy]-phenylamino-2-nitrobenzene-4-sulphonic acid phenylamide, condensed with 4-chloromethylbenzene-1-carboxylic and chloride, sulphonated pine and sperm oils, sodium-3-nitrobenzene-1-suphonate, sodium alginate and sodium bicarbonate.  The preparation of the dyes is in Division C4.  Reference has been directed by the Comptroller to Specification 917,764.