JPS6147174B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the formula In the above formula, R and R ₁ represent a hydrogen atom or a phenyl group which may be optionally substituted with chlorine or a C ₁ -C ₄ alkyl group, provided that at least one of the groups R ₁ or R represents hydrogen. ; Z is a chlorine atom or a nitro group, R ₂ and R ₃ are methyl, phenyl, or a carboxamide group, and groups X ₁ , X ₂ and X ₃ are hydrogen, a chlorine atom, a nitro group,
Methyl sulfone, sulfonamide, sulfonic acid mono- _C1 - _C4 alkylamide, sulfonic acid di-
The present invention relates to a novel chromium complex dye, which is a _C1 - _C4 alkylamide or a sulfonic acid phenylamide, and Me ⁺ is a cation. A novel chromium complex dye has the formula or is converted into a 1:1 chromium complex in a manner known per se by reaction with a chromium-donating reagent, and this complex is then reacted with an unmetallized dye of formula () or () to give 1 : produced by a method consisting of obtaining a 2Cr complex. Preferably, a 1:1 Cr complex of the dye of formula () is prepared and the dye of formula () is added thereto. The monoazo dye of the formula () is a diazotized 2-amino-1-hydroxy-4-sulfo-6-nitro- or 6-chloro-benzene of the formula (). obtained by known methods by coupling to pyrazolone, and monoazo dyes of formula () are of formula () The diazotized aminophenol of formula () It can be obtained by coupling with pyrazolone. However, in each of the above formulas, R, R ₃ , R ₂ and R ₁ have the meanings described above. Examples of suitable pyrazolones of formulas () and () are 3-methyl-5-pyrazolone, 3-phenyl-5-pyrazolone, 5-pyrazolone-3-carboxamide, 1-phenyl-3-methyl-5-pyrazolone, 1-(2'-, 3'- or 4'-chlorophenyl)-3-methyl-5-pyrazolone, 1-(2'-
5′-or 3′・4′-dichlorophenyl)-3-methyl-5-pyrazolone, 1-(2′・4′・6′-trichlorophenyl)-3-methyl-5-pyrazolone, 1-
(2'-chloro-6'-methylphenyl)-3-methyl-5-pyrazolone, 1-(4'-methyl-phenyl)-3-methyl-5-pyrazolone, 1-(2'-ethylphenyl)-3- Methyl-5-pyrazolone,
1-phenyl-3-aminocarbonyl-5-pyrazolone, 1,3-diphenyl-5-pyrazolone,
It is. Examples of possible diazo components of formula () are 2-amino-1-hydroxy-benzene, 4- or 5-chloro-2-amino-hydroxy-benzene, 4-
or 5-nitro-2-amino-hydroxy-benzene, 4,6-dichloro-2-amino-hydroxy-benzene, 4,6-dinitro-2-amino-
Hydroxy-benzene, 4-chloro-5-nitro-2-amino-hydroxy-benzene, 6-chloro-4-nitro-2-amino-hydroxy-benzene, 4-chloro-6-nitro-2-amino-hydroxy- benzene, 2-amino-1-hydroxy-4- or 5-(methylsulfone)-benzene,
2-amino-1-hydroxy-4- or 5-sulfonamido-benzene, 2-amino-1-hydroxy-4- or 5-sulfomethylamido-benzene, 2-amino-1-hydroxy-4- or 5-
Sulfodimethylamide-benzene and 2-amino-1-hydroxy-4- or 5-sulfanilide-
It's benzene. Dyes of formula () or () may be dyes such as chromium formate, chromium sulphate or chromium fluoride.
1:1 chromium complexes by reacting salts of valent chromium with metal-free dyes in an acidic medium at the boiling point or, if appropriate, at temperatures above 100° C., by conventional methods known per se. be done. It is also possible to form trivalent chromium from chromium compounds in the reaction mixture if a reducing agent such as glucose is added at the same time. This metallization can also be carried out in the presence of an organic solvent. Preferably, the reaction is carried out in an organic solvent such as an alcohol or ketone, with the exclusion of water as much as possible. The reaction of a 1:1 chromium complex of a dye of formula () or () with a metal-free dye of formula () or () can be carried out in an open or closed container in an alkaline to weakly acidic medium at room temperature or elevated temperature. , for example 50
It is suitably carried out at temperatures between 120°C and 120°C. The reaction can be carried out in organic solvents, such as alcohols or ketones, or in aqueous solution; in the case of aqueous solution, the reaction can be accelerated, if appropriate, by addition of a solvent such as, for example, alcohol or dimethylformamide. In general, it is recommended to react as much as possible equivalent amounts of chromium-containing 1:1 complex and metal-free dye, and the molar ratio of metal-free dye to 1:1 complex is at least 0.85:1 and at most 1 :0.85, and an excess of metal-containing dye is generally advantageous over an excess of metal-free dye. Generally, the closer this ratio is to 1:1, the more favorable the result. Instead of a single dye of formula () or (), it is also possible to use mixtures of suitable dyes.
Advantageous color tones are often obtained in this way. The novel chromium-containing mixed complexes obtainable by the above method are advantageously in the form of their salts, in particular alkali metal salts, especially sodium salts, ammonium salts or salts of organic amines with positively charged nitrogen atoms. It is isolated and suitable for dyeing and printing the most diverse materials, especially nitrogen-containing materials such as silk, leather, especially sheep, and synthetic fibers of polyamides or polyurethanes. They are particularly suitable for dyeing from weakly alkaline, neutral or slightly acidic baths, for example baths containing acetic acid. The dyeings thus obtained are uniform and have good fastness to light, washing, filling, hot pressing and carbonising. In the following examples, unless otherwise specified, parts are parts by weight, percentages are percentages by weight, and temperatures are given in degrees Celsius. Example 1 1:1Cr prepared by coupling diazotized 6-nitro-2-aminophenol-4-sulfonic acid to 1-phenyl-3-methyl-5-pyrazolone and then chromating the coupled product. 0.1 mol of the complex dye was mixed with diazotized 5-nitro-2-aminophenyl and 3-methyl-
Stir in 1.2 mol of water with 0.1 mol of monoazo dye prepared by coupling to 5-pyrazolone. The resulting suspension was heated to 90-95°C;
Adjust the pH to 8-8.5 with dilute sodium hydroxide solution. The suspension is stirred until no starting dye can be detected, then 260 g of sodium chloride are introduced, the pH is adjusted to 5 with a little acetic acid and the precipitated chromium mixed complex dye is separated off at 65.degree. After drying, a dark brown powder is obtained which can be dissolved in water to give a red solution and the wool and polyamide can be prepared from a weakly acidic bath to a red shade with good light fastness and good wet processing fastness. dye. Example 2 1 prepared by diazotizing 6-nitro-2-aminophenol-4-sulfonic acid, coupling the diazotized product to 3-methyl-5-pyrazolone, and chromating the coupled product. : 0.1 mol of 1Cr complex dye, 5-nitro-
Stirred in 1 mol of water with 0.1 mol of a dye prepared by diazotizing 2-aminophenol and coupling the diazotized product with 3-methyl-5-pyrozolone, the mixture was warmed to 80-85°C. Then adjust the pH to 9 with dilute sodium hydroxide solution. The mixture is stirred at this pH until no starting components are detected, 200 g of potassium chloride are introduced, the pH is adjusted to 6.5 with dilute acetic acid and the precipitate is separated off at 50.degree. When dry, the dye is a dark brown powder which dissolves in water and dyes wool and polyamide in clear red shades from weak acid baths. In the acid form, the dye has the formula corresponds to When using the monoazo dyes and monoazo dyes listed in the table, chromium mixed complex dyes having similar properties and dyeing wool and polyamides in orange to bluish red tones are likewise obtained.

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[Table] The λ _nax of wool and polyamide dyed with the chromium complex dye of the above example was as follows: Example number λ _nax 1 500nm 10 486nm 11 496nm 13 486nm 33 496nm 34 486nm

Claims (1)

[Claims] 1 formula In the above formula, R and _R1 represent a hydrogen atom or a phenyl group optionally substituted with chlorine or _C1 - _C4 alkyl, provided that at least one of the groups _R1 or R represents hydrogen; Z is a chlorine atom or a nitro group, R ₂ and R ₃ are methyl, phenyl, or carboxamide groups, and groups X ₁ , X ₂ and X ₃ are hydrogen, a chlorine atom, a nitro group,
Methyl sulfone, sulfonamide, sulfonic acid mono- _C1 - _C4 alkylamide, sulfonic acid di-
A chromium complex dye which is a _C1 - _C4 alkylamide or a sulfonic acid phenylamide, and Me ⁺ is a cation. 2. The dye according to claim 1, wherein X ₁ is NO ₂ , X ₃ is Cl, and X ₂ is H. 3. The dye according to claim 1 or 2, wherein R ₂ and R ₃ are CH ₃ or CONH ₂ . 4 R is H, and R ₁ is halogen or
The dye according to any one of claims 1 to 3, which is phenyl optionally substituted with _C1 - _C4 alkyl.