Patent GB-936071-A (GB)
Title: Improvements relating to reactive triazine dyestuffs and their use
IPC: C09B1/46
Filed: 1960-04-29
Abstract: The invention comprises reactive dyes of formula <FORM:0936071/IV(a)/1> where F is an azo, anthraquinone or phthalocyanine dye residue bound by means of an amino group and D is the residue of an organic amine bound by means of amino groups, the dye containing at least one acid salt-forming, water-solubilizing group.  The dyes may be made by reacting one mol. of an appropriate amino group containing dye in steps with 2 mols. of cyanuric chloride and 1 mol. of an organic diamine.  The dyes may also be made by reacting 1 mol. of the diamine with 1 mol. of cyanuric chloride, the product thus obtained with 1 mol. of amino dye and the resultant compound with 1 mol. of cyanuric chloride, or by reaching 1 mol. of the diamine with 2 mols. of cyanuric chloride and the product with 1 mol. of the amino-dye.  The azo dyes may be made by conventional diazotization and coupling processes.  D may be derived from aliphatic, araliphatic, cycloaliphatic, aromatic-isocyclic or heterocyclic compounds and, although advantageously uncoloured, may also be a dye .e.g. a diaminoazo compound.  D may be a polyamine and may contain secondary and/or primary amino groups which are capable of arylation.  Preferably one amino group reacts faster than the other.  Reactivity of the second amino group may be lessened by sterichindrance or because p  of a weakened basicity.  Thus, in the preferred diamines of the benzene, naphthalene, diphenyl and stilbene series, one amino group may be influenced by o-substitution especially by acid groups e.g. carboxylic, and particularly sulphonic acids. Specified diamines of this character are 1,3- and 1,4diaminobenzene-6-sulphonic acids.  Preferred are dyes of formula <FORM:0936071/IV(a)/2> where F is the residue of a monoazo or 1-amino-4-arylamino-anthraquinone dye, D is a 1,4-or 1,3-phenylene residue and n is 2 to 4.  Indicated as water-solubilizing groups are carboxylic and sulphonic acid, acylated sulphonamide, phosphoric acid and sulphate groups, sulphonic acid groups being preferred.  Azo dyes containing metallizable groupings may be used as starting-materials and are preferably metallised before reaction with cyanuric chloride. Copper, chromium, cobalt and nickel are indicated metals. Metal-free, or cobalt, nickel, titanium, tin and especially copper phthalocyanine dyes are mentioned, the cyanuric residues being advantageously bound to a benzo residue of the phthalocyanine structure via an external substituent e.g. a sulphonamide or sulphonic acid ester group. Likewise, when F is an anthraquinone residue, the cyanuric residue is indirectly attached to the anthraquinone residue, e.g. via a phenylamino, diphenylamino, phenoxy, phenoxyphenylamino, phenylthio or phenylthiophenylamino group.  Preferably the anthraquinone dyes are derived from 1,4-diaminoanthraquinones having at least one aromatically substituted amino group.  The dyes colour cellulosic materials being used in conjunction with acid-binding agents.  Examples are provided of the preparation of the dyes and their use in colouring cotton in a wide variety of colour shades. Representative of the azo dyes used, or obtained, in the examples and corresponding to F are 2-naphthalene-4,8-disulphonic acid --> 5-methyl2-methoxyaniline, 2-carboxyaniline-4-sulphonic acid --> 1-amino-3-carbomethoxyaminobenzene, 6-methyl-2-[41-aminophenyl]-benzthiazole317 -disulphonic acid --> 3-methylaniline, 3-nitro-aniline-6-sulphonic acid --> 1-(41-sulphophenyl)-3-methyl-5-pyrazolone (nitro group being reduced to amino group) and aniline-2-sulphonic acid --> 1-amino-8-naphthol-3,6-disulphonic acid (alkaline coupling). Representative of azo dyes used in the examples where equimolar quantities of a component of F and cyanuric chloride are used are 1-amino-3-(21,41-dichlorotriazinyl-(61)-amino) -benzene-6-sulphonic acid --> 1-(naphthyl-(21)-3-methyl-5 pyrazolone-51,71-disulphonic acid, 1-(31-sulphophenyl)-3-methyl-5-iminopyrazole, 2-naphthyl amine-6-sulphonic acid or acetacetic-o-anisidide sulphonic acid, 4-(21,41-dichlorotriazinyl-(61)-amino) -311-aminoazobenzene-411-sulphonic acid --> 2-naphthol-3,6-disulphonic acid, 4-methyaniline-2-sulphonic acid or 41-methyl-4-amino-azobenzene-3-sulphonic acid --> 1-(21,41-dichloro -11,31,51 -triazinyl -(61) -amino) -8-naphthol-3,6-disulphonic acid and 4-aminoazobenzene -3,41-disulphonic acid or 4-amino-2-carboxyphenol-6-sulphonic acid --> 2-(21,41-dichloro-11,31, 51-triazinyl-(61)-amino)-5-naphthol-sulpphonic acid. Representative of metal azo complexes used in the examples are 1-amino-2-phenol-3,5-disulphonic acid --> 2-amino-5-naphthol-7-sulphonic acid (coppered) and 1-amino-2-phenol-5-sulphonic acid --> 1-(41-aminophenyl)-3-methyl-5-pyrazolone (cobalted and chromed). Representative of anthraquinone dyes used in the examples are 1-amino-4-(41-aminophenylamino)-anthraquinone-2,6, 31-trisulphonic acid, 1-amino-4-(41-amino-diphenyl-amino)-anthraquinone-2,(mixed 5,8),31-trisulphonic acid, 1-amino-4-(41-aminophenylamino)-anthraquinone-2-carboxylic acid-31-sulphonic acid and 1-amino-4-(41-methylaminophenyllamino)-anthraquinone-2, 31-disulphonic acid.  Representative of the phthalocyanine dyes used in the examples are the condensation products of 1 mol. of copper phthalocyanine disulphonic acid, disulphonic acid chloride and 2 mols. of 4,41-diaminodiphenyl-2,21-disulphonic or 4,41-diaminostilbene-2,21-disulphonic acids and 3,31, 311,3111-copper phthalocyanine tetrasulphonic acid chloride condensed with 1-N-hydroxy-ethylamino-2-aminoethane or 1,3-diaminobenzene-4-sulphonic acid.  Representative of compounds used in the examples from which D is derived are 1,3- and 1,4-diaminobenzene-6-sulphonic acids, 4,41-diaminodiphenyl-3-sulphonic acid, 4,41-diaminostilbene-2,21-disulphonic acid, 1-methylamino-4-aniline-6-sulphonic acid and ethylene diamine.