JPS5832180B2 - Hybrid chromium complex dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention, in the form of a free acid, has the formula Methyl, phenyl or -〇〇NH2, R4 is hydrogen, chlorine or nitro, R5 is hydrogen or nitro, R6 is hydrogen, chlorine, nitro, methyl, -802NH2, -8O2NH-C6H5, -8O2C
H3 or -N(CH3)5O2CH3, and R7 and R8 are hydrogen, chlorine, nitro, cyanomethyl, methoxy,
-CO■2, -NHCOCH3,502NI (2, -8
O2CH3 or -8o2NHC6H5, R9 and Rlo are hydrogen, chlorine, nitro or methyl, and M is a cation.

Novel hybrid ROM complex dyes are prepared by treating an azo dye of the formula or an azomethine dye of the formula with a chromium donor to convert it into a 1:l chromium complex, which is then converted into a non-metallized dye 5)
It can also be produced by combining it by reaction with 6) to form a 1:2 hybrid ROM complex.

Preferably the l:l chromium complex is prepared from an azo dye of formula (5) containing a sulfonic acid group and the complex is prepared from an azo dye of formula (6) containing a sulfonic acid group.
) is subjected to addition reaction with azomethine dye.

To carry out this reaction, it is not necessary to react the isolated azomethine complex of formula (6) with the 1:1 chromium complex.

In order to produce a 1:2 hybrid ROM complex of formula (1),
It is sufficient to react a mixture of an 0-aminophenol of formula (7), and an 0-hydroxyaldehyde of formula (8), into a l:l chromium complex.

The azo dye and azomethine dye necessary for producing the 1:2 hybrid ROM complex of the present invention can be produced according to conventional methods.

For example, an azo dye of formula (5) can be obtained by combining a diazonium salt of an amine of hydrochloric acid with a coupling component of formula aω.

The azomethine dye of Tsukasa 6) can be obtained by a condensation reaction between amine (7) and 0-hydroxyaldehyde (8).

Suitable amines (7) are selected, for example, from among the following: 4- or 5-chloro-2-amino-1-hydroxybenzene, 4,6-dichloro-2-amino-1-hydroxybenzene, 4-5 - or 6-nitro-2-amino-1-hydroxybenzene, 4-chloro-5- or -
6-nitro-2-amino-1-hydroxybenzene, 4
-Nitro-6-chloro/L/-2-amino-1-hydroxybenzene 6-nitro-4-methyl-2-amino-1
-Hydroxybenzene, 4-nitro-6-acetylamino-2-amino-1-hydroxybenzene, 6-nitro-4-acetylamino-2-amino-1-hydroxybenzene, 4,6-sinitro 2-7mi/ -1-hydroxybenzene, 4-nitro-6-methyl-2-amino-1
-Hydroxybenzene, 2-aminophenol, 2-aminophenyl-4- or -5-sulfonamide, 2-aminephenol-4- or -5-alkylsulfonamide having 1 to 4 C atoms in the alkyl group, alkyl 2-Aminephenol-4 having 1 to 4 C atoms in the group
- or -5-dialkylsulfonamides, 2-aminophenyl-4- or -5-alkylsulfones having 1 to 4 C atoms in the alkyl group, 4-marifl 5- N
-Methylsulfonyl-N-methylamino-2-aminophenol, 2-aminoenol-4- or -5-sulfanilide, 4- or 5-N-methyl-N-benzenesulfonylamino-2-aminephenol, 2-amino Phenol-4- or -5-phenylsulfone and 4- or 5-methyl-2-amino-1-hydroxybenzene.

Suitable amines (9) are chosen, for example, among the following: 2-aminophenol-4-sulfonic acid, 2-aminophenol-5- or -6-nitro-4-sulfonic acid, 2-aminophenol-4-sulfonic acid, 2-aminophenol-5- or -6-nitro-4-sulfonic acid, 6-chloro-4-sulfonic acid, 2-aminophenol 6-from-4-sulfonic acid,
2-Aminephenol-6-methyl-4-sulfonic acid and 2-aminophenol-6-ethyl-4-sulfonic acid.

Possible coupling components (10) are selected, for example, from among the following: 1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-3-aminocarbonyl-5-pyrazolone 1-phenyl-3-cyano-5 -pyrazolone,
1-(2-13- or 4-chlorophenyl)-3-methyl-5-pyrazolone, 1-(2-13- or 4-bromphenyl)-3-methyl-5-pyrazolone, 1-(
2-3-or 4-methylphenyl)-3-methyl5-
Pyrazolone, 1-(2-13- or 4-methoxyphenyl)-3-nonal-5-pyrazoone, 1-(2-13
- or 4-nitrophenyl)3-methyl-5-pyrazolone, 1-(2-ethylphenyl)-3-methyl-5-
Pyrazolone, 1(3,4-dichlorophenyl) -3-
,,' Chiru-5 hilasolone, 1-(2,5-dichlorophenyl)3-methyl-5-vilanurone, ■-(2,4-
6-dolychlorphenyl)-3-methyl-5-pyrazolone, 1-(2,4-dichloro-5-methylphenyl)-
3-Methyl-5-pyrazolone, 1(2-chloro-6-methylphenyl)-3-methyl-5-pyrazolone, ■-(
3-chloro-4-methylphenyl)-3-methyl-5-
Vira/”lon, 1-(2-methyl-4- or -5-chlorophenyl)-3-methyl-5-pyrazolone, ■-(
2-methoxy-5-methylphenyl)-3-methyl-5
-Pyrazolone, 1-(2,5-dimethoxyphenyl)-
3-Methyl-5-pyrazolone, (3-cyanophenyl)-3-methyl-5-pyrazolone, 1-(3-aminocarbonylphenyl)3-methyl-5-pyrazolone, 1-
(2- or -3-sulfamoylphenyl)-3-methyl-5-pyrazolone, ■-(2,6-dimethyl-3-sulfamoylphenyl)-3-methyl-5-pyrazolone, 1
-(3-sulfodimethylamido-phenyl)-3-methyl-5-bilanurone, ■(4-#lsulfonylphenyl)-3-methyl5-pyrazolone, 1,3-diphenyl-
5-pyrazolone and 1-phenyl-3-methoxycarbonyl-5-pyrazolone.

Suitable O-hydroxyaldehydes (8) are selected, for example, from among the following: 3- or 5-methyl-2-hydroxybenzaldehyde, 3,5- or 3,6-dimethyl-2-hydroxybenzaldehyde, 5-chloro-
or 5-bromo-2hydroxybenzaldehyde, 3
- or 4-chloro-2-hydroxybenzaldehyde,
3,5-dichloro-2-hydroxybenzaldehyde,
3-Chlor-5-methyl-L2-hydroxybenzaldehyde, 3-methyl-5-chloro-2-hydroxybenzaldehyde, 2,4- or 2,5 dihydroxybenzaldehyde, 3- or 4-methoxy-2-hydroxybenzaldehyde, l- Carbaldehyde-2-hydroxynaphthalene, 1-carbaldehyde-2,4-dihydroxynaphthalene, 2-carbaldehyde-1-hydroxynaphthalene and 2-carbaldehyde-4-chloro-1-hydroxynaphthalene.

The conversion of the azo dye of formula (5) or the azomethine dye of formula (6) into the corresponding 1:1 chromium complex can be carried out, for example, by converting the dye in an acid medium at the boiling point of the reaction medium in an open apparatus or in a closed apparatus. The reaction can be carried out in a reactor, optionally at high temperature, with at least 1 molar equivalent of a chromium donor.

Trivalent chromium salts such as chromium formate, chromium acetate, chromium fluoride, chromium chloride or chromium sulfate can be utilized as chromium donors.

The dyes can be chromated in aqueous medium, optionally in the presence of organic solvents such as alcohols, butanol or formamide.

To generate a hybrid chromium complex in which two different dyes of general condition 5) or (6) are bonded together via a chromium atom by addition reaction of a metal-free dye with a 1:1 chromium complex, This can be done by heating the two reactants in an aqueous solution or suspension in the presence of an acid binder.

The temperature is preferably maintained at 40-100°C.

Examples of acid binders that can be used are alkali metal hydroxides or alkali metal carbonates or alkali metal acetates, such as sodium hydroxide solution, sodium carbonate or sodium acetate, or the corresponding lithium, potassium or ammonium salts.

If appropriate, the reaction can be accelerated by the addition of organic solvents, such as alcohols or formamide, or surfactants.

The molar ratio of 1:1 chromium complex to metal-free dye is usually 0.
．． It can range from 85:1 to 1:0.85.

An excess of 1:1 complex is generally less harmful than an excess of metal-free dye.

Best results can be obtained with a molar ratio l:'1.

According to the above process, highly glossy orange-colored 1:2 hybrid ROM complexes are obtained which can be used with nitrogen-containing fiber materials such as wool, silk, leather and polyamide or polyurethane fibers as well as with fiber hybrids such as wool and polyamide. It is suitable for dyeing and printing blended textiles.

The dyeing process is preferably carried out in a neutral to weakly acidic bath, for example a bath acidified with acetic acid.

Substances which decompose during the dyeing process into volatile bases and acid components remaining in the dyebath, such as ammonium acetate or ammonium sulfate, can be added to lower the pH value.

Furthermore, customary dyeing auxiliaries such as sodium sulfate or condensation products of ethylene oxide and amines or alcohols can be added to the dyebath.

Example 1 Diazotized 2-aminophenol-6-nitro-4-
■:l Chromium complex dye Q, 1 mol, obtained by reacting sulfonic acid with 1-phenyl-3-methyl-5-pyrazole and then chromating the reaction product, 4-nitro-2
-aminophenol 0.1 mol and 3,5-dichloro-
0.1 mol of 2-hydroxybenzaldehyde and 1 liter of water
The mixture was stirred in l.

The resulting suspension was heated to 70-80°C and the p
The H value was maintained at a pH value of 8-9 by dropwise addition of dilute sodium hydroxide solution.

After a short time, a clear orange solution resulted, which was stirred for a further 1 hour at a pH value of 8-9 and 70-80°C.

Sodium chloride was added to the reaction solution and the precipitated dye in the free acid form corresponding to the formula was separated and dried.

The aX (nm) was 472. When wool or polyamide was dyed from a weak acid bath, a bright orange dyeing with good fastness to light and wet processing was obtained.

Example 2 Diazotized 2-aminophenol-6-nitro-4-
Sulfonic acid and 1-(4-methyl-3chlorophenyl)
-3-Methyl-5-hif 7"07 and 1
Dyes containing one complex-bonded chromium atom per molecule 0.1
0 moles of 4-nitro-2-aminophenol in 1 liter of water
．． Suspended with 1 mol.

The mixture was warmed to 70-80° C. and the pH value was kept in the range 8-9 by addition of dilute sodium hydroxide solution.

During heating, 0.1 mol of 2-hydroxybenzaldehyde was added dropwise over 20 minutes.

After some time, the resulting orange clear solution has a pH value of ~8.
The mixture was further stirred at 9 and 70-80°C for 1 hour.

Sodium chloride was added, and the precipitated mixed ROM complex was separated by P.

When dried, the dye in the free acid form corresponding to the formula was a red powder with a λmaX (nm) of 448.

This dyed wool and polyamide in a mildly acidic bath in a bright orange color.

The dyeing showed good fastness to light and wet processing.

Examples 3 to 42 When using the azo dyes ■ and the azomethine dyes ■ shown in the following table, hybrid rom complex dyes with similar properties were obtained, which dyed wool and polyamide in a bright orange color. .

In addition, λmax (nm) of the main dyes among these dyes
was as follows.

Example 43 (Dyeing Example) The hybrid ROM complex dye 12 described in Example 1 was dissolved in water 21.

To this solution was added 40 ml of 30% acetic acid and a dispersant containing a long chain ethoxylated amine.

This dyebath was heated to 30-40°C, pre-moistened wool 1002 was introduced and the entire dye bath was heated to 30-40°C for 30 minutes.
Heat to 0° C., hold at boiling temperature for 45 minutes and rinse the wool with warm water.

The resulting glossy orange dyeing showed good fastness to light and wet processing.

Example 44 (Dyeing Example) The dye obtained in Example 1 was used to dye a polyamide wind. i was dissolved in 200 ml of water.

Add 31 rL of 10% ammonium phosphate aqueous solution and 4 ml of 3% acetic acid to 10 ml of wet skeins to be dyed. introduced.

The dyebath was heated to boiling temperature at a uniform rate over a period of 30 minutes and held at boiling point for 45 minutes.

It was then cooled and rinsed with warm water, giving a bright orange polyamide dyeing with good fastness properties.

Example 45 (Printing example) Hybrid ROM complex dye 10' described in Example 1? was dissolved in 10or/Ll of water with as little solvent as possible.

Add 41% ammonium sulfate and mix this solution with 180% paste former. It was processed into a dyed paste.

Wool was printed with this dyeing paste and treated with steam at 100-105°C to fix the dye.

After washing with water, a bright orange print was obtained which had good fastness to light and wet processing.

Claims (1)

[Claims] In the general formula 1, one of R1 and R2 is hydrogen, the other is hydrogen, chlorine, bromine, nitro or methyl, R3 is methyl, phenyl or -CONH2, and R4 is hydrogen, chlorine or nitro, R5 is hydrogen or nitro, R6 is hydrogen, chlorine, nitro, methyl, -8O2NH2, -8O2NH-C6H5, -8O2C
H3 or -N(CH3)SO2CH3, R7 and R8 are hydrogen, chlorine, nitro, cyano, methyl, methoxy, -C0NH2, -NHCOCH3, SO2NH2, -
8O2CH3 or -5O2NHC6H6, R9 and Rlo are hydrogen, chlorine, nitro or methyl, and M is a cation.