Bicyclic copper complex formazan compounds having a fiber-reactive group of the vinyl sulfone series, containing a fiber-reactive group suitable as dyestuffs
Copper complex formazan compounds useful as dyestuffs and having fiber-reactive dyestuff properties, which are capable of providing fast, deep dyeings and prints on fiber materials, preferably of cellulose and polyamide fibers, have the following structural formula ##STR1## in which m and n are 1 or 2, A is a benzene ring or a naphthalene ring, either of which is necessarily substituted by the sulfo group in the ortho-position relative to the N-atom and which can optionally be further substituted with one to three substituents; B is phenyl or naphthyl, either of which can be substituted or unsubstituted; M is hydrogen or one equivalent of a metal; X is hydrogen or sulfo; Z is hydrogen or a group which confers water-solubility, one or both of which--besides the sulfo group necessarily required in the o-position relative to the N-atom of the hydrazone component A--are bonded to A on an aliphatic or aromatic carbon atom, Z.sup.1 is hydrogen or a group which confers water-solubility, one or both of which are bonded to B on an aliphatic or aromatic carbon atom of B, Z and Z.sup.1 together denoting not more than three sulfo groups if X is a sulfo group, and Y is the vinyl group or a group of the formula --CH.sub.2 --CH.sub.2 --E, in which E represents a substituent which can be removed under alkaline conditions.
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of my copending application Ser. No. 632,436, filed July 19, 1984, now abandoned.
Free radical heavy metal ions in water-soluble heavy metal complex dyestuffs are removed from the synthesis solution of the heavy metal complex dyestuff by means of a compound or several of the compounds mentioned below: (a) saturated and unsaturated fatty acids having about 8 to 18 carbon atoms and water-soluble salts thereof; (b) the monoesters and diesters of orthophosphoric acid and salts thereof corresponding to the general formula (1a) and (1b) ##STR1## in which R denotes a saturated or unsaturated aliphatic radical having about 8 to 18 carbon atoms and M stands for a hydrogen atom or a salt-forming, water-solubilizing metal; (c) aliphatic sulfonic acids and water-soluble salts thereof corresponding to the general formula (2) in which R and M have the abovementioned meanings; (d) aliphatic phosphonic acids and monoesters thereof and also water-soluble salts thereof corresponding to the general formulae (3a) and (3b) ##STR2## in which R and M have the abovementioned meanings; (e) malonic acid and water-soluble salts thereof; (f) trimercapto-s-triazine, 2-aminobenzoic acid, 8-hydroxyquinoline and water-soluble salts of these compounds; (g) water-soluble sulfides, in particular alkali metal sulfides; (h) functionalized water-insoluble polymers which react with metal ions by the ion-exchanger principle or form metal chelate complexes. Using these compounds, the excess heavy metal ions are precipitated out of the synthesis solution or separated off, without the heavy metal ions bound as a complex in the dye being attached.
The invention relates to dicyclic metal complex formazan dye derivatives and processes for producing compositions and for using them in dyeing processes.
The present invention provides reactive formazan dyestuffs of the general formula (I), ##STR1## Wherein A, B, D, Me, Q, R, and Z are defined in this document. The dyes according to the invention are distinguished by high fixation and a very good build-up. They are distinguished also by a low substantivity and a high exhaustion, and they have fiber-reactive properties and are very highly suitable for dyeing and printing of materials containing either cellulose fibers.
The invention is a dye composition containing two or more dyes of the vinyl sulfone type which can be used in combination to dye polyamide substrates. Preferably the dye compositions of the invention contain at least three dyes of different primary colors.
Water-soluble copper formazan compounds of the general formula ##STR1## in which: Y is vinyl or ethyl which is substituted by a substituent eliminatable under alkaline conditions; the benzene nucleus A can be substituted by further substituents; M is hydrogen or a metal; B is substituted or unsubstituted phenylene or naphthylene; Z.sup.1 is hydrogen or a water-solubilizing group, or --B--Z.sup.1 together denote hydrogen, carboxy, cyano or nitro; D is a substituted or unsubstituted benzene or naphthalene radical; and R is hydrogen or a group of the formula ##STR2## in which R* is hydrogen or a substituted or unsubstituted lower alkyl, n denotes the number zero or 1, and Y.sup.2 is defined in the same manner as Y. These copper formazan compounds possess fiber-reactive dye properties and dye particular cellulose fiber materials in deep reddish blue to greenish blue fast shades.
