Patent GB-942566-A (GB)
Title: New water-soluble dyes of the azo and anthraquinone series and containing methylene ether radicals
Inventor: BRAUN WILLY
IPC: D06P1/00
Filed: 1960-09-13
Abstract: 2 - (2 - hydroxybenzylideneamino) - 4:6 diamino - 1:3:5 - triazine is made by reacting melamine with salicylaldehyde in N-methylpyrrolidone.  2 - (8 - hydroxy - 3:6 - disulpho - 1 - naphthyl amino) - 4:6 - diamino - 1:3:5 - triazine, 2 (5 - hydroxy - 7 - sulpho - 2 - naphthylamino) - 4:6 - hydroxy - 1:3:5 - triazine, 2 - (4 - amino 3 - sulphophenylamino) - 4:6 - diamino 1:3:5 - triazine and 2 - (3 - amino - 4 - sulphophenylamino) -4:6 - diamino - 1:3:5 - triazine are made by reacting 2-chloro-4:6-diamino1:3:5-triazine with 1-amino-8-hydroxy-naphthalene - 3:6 - disulphonic acid, 2 - amino - 5 hydroxy-naphthalene - 7 sulphonic acid, pphenylene diamine sulphonic acid and 1:3diaminobenzene sulphonic acid respectively.  N - (8 - hydroxy - 6 - sulpho - 2 - naphthyl) glyoxal diureine and N - (4 - acetylaminophenyl) glyoxaldiureine are made by reacting glyoxalmonoureine dimethyl ether with 8-hydroxy-6sulphonaphthyl - (2) - urea and 4 - acetylamino phenyl urea respectively.  The 4-acetylamino derivative may be hydrolysed to yield N-(4amino - phenyl) - glyoxaldiureine.  n- (4-hydroxyphenyl) - glyoxal diureine is made by reacting 4-hydroxyphenyl urea wiwth glyoxalmonoureine. The corresponding methylol derivative is made by reacting the product with formaldehyde.  Methylol derivatives of 2-hydroxyphenyl urea, 2 - hydroxy - 3 - naphthoic acid amide, 5 - hydroxy 7 - sulpho - 2 - naphthyl urea and 1 - (3 - sulphonamidophenyl) - pyrazol - 5 - one - 3 - carboxylic acid amide are made by reacting these compounds with formaldehyde.ALSO:The invention comprises water-soluble azo and anthraquinone dyes containing one or two radicals of the formulae <FORM:0942566/C3/1> <FORM:0942566/C3/2> wherein the hydrogen atoms capable of reacting with formaldehyde are replaced by radicals of the formula -CH2OR in which R is the radical of an alcohol. The dyes are made by etherifying with an alcohol azo or anthraquinone dyes or diazo or coupling components which contain one or two of the radicals indicated above wherein the hydrogen atoms capable of reacting with formaldehyde are replaced by methylol radicals, and in the case of diazo and coupling components completing the dye by diazotization and coupling.  Dyes and diazo and coupling components wherein the hydrogen atoms in the above radicals are replaced by -CH2OR radicals where R has more than 3 carbon atoms may also be made by transetherification from similar dyes or components where R has 1 to 3 carbon atoms by heating with an alcohol of more than 3 carbon atoms in the presence of hydrogen chloride.  The dyes containing methylol groups may be made by reacting dyes containing one or two of the groups indicated above with formaldehyde or paraformaldehyde in an aqueous medium of pH 6 to 11. The azo dyes specified are monoazo dyes of the phenyl- or naphthyl-azo-benzene, -naphthalene or -pyrazolone type, metallized monoazo dyes and disazo dyes.  Examples are given. The dyes dye and print textile materials of wool, silk, synthetic linear polyamides and polyurethanes, polyvinyl alcohol, cellulose esters and cellulose. Specifications 842,802, 900,704, 900,950, 908,301 and 942,555 are referred to.ALSO:Textile materials of wool, silk, synthetic linear polyamides and polyurethanes, polyvinyl alcohol, cellulose esters and cellulose are dyed and printed, if desired in conjunction with a resin-finishing treatment, with water-soluble azo and anthraquinone dyes containing one or two radicals of the formulae:  -SO2NH2, -CONH2, -NHCONH2, -NHCSNH2, <FORM:0942566/D1-D2/1> , <FORM:0942566/D1-D2/2> and <FORM:0942566/D1-D2/3> wherein the hydrogen atoms capable of reacting with formaldehyde are replaced by radicals of the formula -CH2OR in which R is the radical of an alcohol.  The dyes may be applied to cellulose and wool in conjunction with a treatment with an acid-reacting substance.  The dyes may also be applied to textile materials together with acid-reacting substances and hardenable amino-plast-forming substances or precursors thereof and, if p desired, aldehydes, and the material then heated to an elevated temperature.  Acid-reacting substances specified are boric, phosphoric, formic, acetic, glycolic, tartaric, chloracetic, chloropropionic, citric and maleic acids, ammonium nitrate, ammonium chloride, mono-ammonium phosphate, zinc chloride, magnesium chloride and diethanolamine hydrochloride. Aminoplast-forming substances or precursors specified are dimethylolurea, dimethyl-dimethylol-urea, dimethyloldicyandiamide, methylolthiourea, dimethylolguanidine, trimethylolmelamine, diphenyldimethylolurea, methylol derivatives of mono- and diureines, carboxylic acid amides and diamides, urethanes and polyurethanes e.g. N:N-dimethylol glyoxalmonoureine and butanedioldiurethane and of hexahydroketotriazines, lactams, polyamides and ethylene ureas.  Aldehydes specified are formaldehyde, glyoxal and acetaldehyde; paraformaldehyde or hexamethylene tetramine may also be used.  In examples (1) bleached and mercerised cotton fabric is impregnated in a bath containing a dye of the above type, zinc chloride and monoammonium phosphate, dried and heated at 155 DEG C.; (2) a bleached rayon staple fabric is impregnated in a bath containing a dye of the above type, dimethyl-dimethylolurea, dimethylolbutane-diol-urethane, methylolcaprylic lactam, polyacrylamide, stearylethylene-imine-urea, polyglycol ether and ammonium nitrate, dried and heated at 150 DEG C.; and (19) a cotton fabric is padded with an aqueous solution containing a dye of the above type, N:N\sv-dimethylolglyoxalmonoureine and zinc chloride, dried and heated to 150-160 DEG C.  Specifications 842,802, 900,704, 900,950, 908,301, 942,555 are referred to.