CS252594B1 - Grey till black 1 to 2 chromocompex azo-dye stuffs - Google Patents

Description

The invention relates to gray to black chromocomplex azo dyes.

In the dyeing and printing of wool and PAD, the assortment of acidic, sulfosubstituted 1: 2 metal-complex 0,0'-dihydroxyazo dyes has been emerging in recent years, characterized by high stability, high cold-solubility, excellent leveling and extensibility and universal use.

These are the coordination complexes 1 of the metal atom with the coordination number 6 (most often chromium or cobalt) with two identical or different o, O'-dihydroxy, o-hydroxy-o'-carboxy- or o-hydroxy-o'-aminoazo dyes.

The water solubility of these 1: 2 metal-complex azo dyes is enhanced by suitable substitution. 1: 2 metal-complex dyes solubilized by non-ionic hydrophilicity-increasing substituents such as sulfamoyl or methanesulfonyl groups are known. However, the production of these dyes is relatively expensive.

The same dyeing qualities were also achieved using dyes solubilized with sulfo groups. However, the incorporation of sulfo groups into the 1: 2 molecule of the metal complex dye is not without problems. While non-ionically substituted 1: 2 metal complexes are essentially monohydric acid salts, substitution with sulfo groups increases the negative charge of the color anion and, of course, can adversely affect its dyeing properties, especially dyeing and ductility.

Moreover, the dyeing behavior is influenced not only by the electric charge, but also by the substitution topography and the spatial arrangement of the color complex molecule.

Monosulfonated 1: 2 chromium complex dyes (I) are usually prepared by coordinating chromium of unsulfonated o, o- ^1- dihydroxyazo dye and 1: 1 hromocomplex o, o- ^1- dihydroxyazo dye containing one sulfo group per molecule. In this reaction, in addition to the desired asymmetric 1: 2 chromium complex dye, two symmetrical 1: 2 chromium complex dyes are formed to a small extent, both without a sulfo group and with two sulfo groups (II) per molecule.

We have now found a gray to black 1: 2 chromium complex dye consisting of a monosulfonated (I) and disulfonated (II) 1: 2 ohromcomplex according to the invention.

where

M = Na, K, NH ₄ both: _{χ χ} = SC> ₃ and Xj = ^NO 2 or both: Χ _χ = NO ₂ and X ₂ = SOjH

X = H, NHCOCH 3, γ _χ = h, no ₂ , with ₂ nh ₂ , with ₂ nhch ₃ . Cl

Y ₂ = H, NOj where:

Χ _χ = NO ₂ , SO ₂ NH ₂ , SO ₂ NHCH ₃ , Cl, Y ₂ = H, and if

Y ₂ = NO ₂ , is Υ _χ = H or

⁴ where Ζ _χ = NO ₂ and Z ₂ = SO ₃ H or Ζ _χ = SO 3 H and Z ₂ = NO ₂ in the ratio X: XI = 0.05 to 0.95: 0.95 to 0.05 and obtainable by coordinating chrome and a sulfonated o, o- ¹ -dihydroxyazo dye and a 1: 1 bromocomplex of o, o'-dihydroxyazo dye containing a single sulfo group per molecule or directly by wet mixing X and XI respectively. dry.

By increasing the content of disulfonated 1: 2 chromium complex (II), the dyeing properties of the monosulfonated 1: 2 chromium complex can be favorably influenced: dyes with a higher proportion of disulfonated component (II) show a marked improvement in cold solubility while maintaining other dyeing properties such as ductility and leveling; wool and PAD stain from a weakly acid to neutral bath, they can be well combined with other dyes of the same or even other metal-complex assortment, or with conventional acid dyes.

Example 1

49.2 g (0.1 mol) of chromium (III) 1: 1 monoazo dye complex 4-nitro-2-aminophenol-6-sulfoacid · 2-naphthol paste is added to a warm alkaline suspension of 70 ° C 17.2 g (0 0.5 mol) of the monoazo dye 2-aminophenol-4-sulfamide-2-naphthol and 19.4 g (0.05 mol) of the monoazo dye 4-nitro-2-aminophenol-6-sulfoacid → 2-naphthol. After a few hours of heating to 80-90 ° C, a mixed 1: 2 chromium complex solution was formed. Evaporation gave 120 g of a strong dye which stains wool and PAD with a gray shade.

Example 2

49.2 g (0.1 mol) of chromium (III) chromium 1: 1 monoazo dye complex 6-nitro-2-aminophenol-4-sulfoacid-1,2-naphthol in the form of a paste is introduced into a warm alkaline suspension of 22 g (0) 0.06 mol) 4-nitro-2-aminophenol-1,7-acetaminonaphthol monoazo dye and 15.6 g (0.04 mol) 6-nitro-2-aminophenol-4-sulfoacid-2-naphthol monoazo dye. After a few hours at 85-95 ° C, a 1: 2 chromium complex solution was formed. Evaporation gave 120 g of a strong dye which dyed wool and PAD with a gray to black shade.

Example 3

49.2 g (0.1 mol) of chromium 1: 1 monoazo dye complex 4-nitro-2-aminophenol-6-sulfoacid-R 2 -naphthol as a paste is added to 21.6 g (0.07 mol) of the monoazo dye 4,5-nitro-2-aminophenol-2-naphthol and 11.7 g (0.03 mol) of the monoazo dye 4-nitro-2-aminophenol-6-sulfo acid-1,2-naphthol 70 ° C warm alkaline suspensions. After a few hours of heating to 80-90 ° C, a mixed 1: 2 chromium complex solution was formed. Evaporation gave 120 g of a strong dye which stains wool and PAD with a gray shade.

EXAMPLE 4 g of ostalan gray S-G and 30 g of chromic 1: 2 monoazo dye complex 4-nitro-2-aminophenol-6-sulfoacid 2-naphthol were homogenized. 100 g of dye are obtained which stains wool and PAD with a gray shade.

Claims (2)

gray to black 1: 2 chromium complex dyes characterized by consisting of sulfonated (I) and disulfonated (II) 1: 2 chromocomplex 'where, θ 2ΝΓ M = Na, K, NH ₄ X = H, NHCOCH ₃ γ _χ = h, no ₂ , with ₂ nh ₂ , with ₂ nhch ₃ , Cl Y ₂ = H, NO ₂ where: Y ₃ = NO ₂ , SO ₂ NH ₂ , SO ₂ NHCH ₃ , Cl, Y ₂ = H and if both X ₃ = SO ₃ H and X ₂ = NO i both X ₃ = NO ₂ and X ₂ = SO ₃ from a mixture of mono3 or H or wherein Z = H, NO, wherein Z ₃ = NO ₂ and Z ₂ = SO ₃ H in a ratio of I: II = 0.05 to 0.95 to 0.05.