GB1581469A

GB1581469A - Production of water-miscible stock solutions of 1:2 chromium complex dyes containing sulphonic acid groups

Info

Publication number: GB1581469A
Application number: GB3348977A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1976-08-25
Filing date: 1977-08-10
Publication date: 1980-12-17
Also published as: DE2638222A1; DE2638222C3; DE2638222B2; IT1115775B; FR2362900A2; JPS5326825A; CH626113A5

Abstract

Concentrated water-soluble stock solutions of sulpho-containing 1:2 chromium complexes are prepared by addition of azo dyes to 1:1 chromium complexes. The addition takes place in a solvent mixture of 55 to 90% of water and 45% to 10% of an organic solvent of the formula 6. The stock solutions contain 14 to 40% by weight, based on the weight of the solution, of 1:2 chromium complexes. The starting compounds for the 1:2 chromium complexes are specified in Claim 1. <IMAGE>

Description

(54) PRODUCTION OF WATER-MISCIBLE STOCK SOLUTIONS OF 1:2 CHROMIUM COMPLEX DYES CONTAINING SULPHONIC ACID GROUPS (71) We, BASF AKTIENGESELL5CHAFT, a German Joint Stock Company, of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The invention relates to a process for the production of a water-miscible stock solution of a 1:2 chromium complex dye containing one or more sulphonic acid groups.

Our G.B. Patent Specification No. 1,350,297 describes and claims a process for the manufacture of a water-miscible stock solution of a chromium-complex o,o'dihydroxyazo dye which in the metal-free form has the formula I:

where R1 denotes hydrogen or nitro and R2 stands for a radical of the formula

the said stocking solution having the following composition: from 14 to 40% by weight, based on the stock solution, of the chromium containing dye as defined above, and from 86 to 60% by weight, based on the stock solution, of a solvent mixture consisting of from 55 to 90% by weight, based on the solvent mixture, of water, from 45 to 10% by weight, based on the solvent mixture, of an organic solvent of the formula II::

where R5 denotes hydrogen, alkyl of 1 to 8 carbon atoms, acetyl or propionyl, Rs denotes hydrogen or methyl, and n is 0 or one of the integers 1 to 6, and from 0 to 12% by weight, based on the solvent mixture, of a formamide of the formula III:

where R5 denotes methyl or hydrogen, in which process the appropriate quantity of the o,o'-dihydroxyazo dye of the formula I, or the components which couple in situ to form the dye, is treated in an appropriate quantity of the solvent mixture specified above with an appropriate quantity of chromium(III) salt or precursor therefor, at elevated temperature, to form the chormium complex dye.

We have found, surprisingly, that a water-miscible stock solution of a 1:2 chromium complex dye having an anion IV or V of the formula

where B' denotes hydrogen or nitro, B2 - denotes hydrogen or hydroxysulphonyl, Ba denotes hydrogen, chloro or nitro, and B4 denotes hydrogen, chloro or methyl, can be produced by contacting an azo dye of the formula VI:

where B1 has the above meaning, with a 1:1 chromium complex having a cation of the formula VII and VIII:

the contacting being effected in a solvent mixture as defined in G.B. Patent Specification No. 1,350,297, or in a solvent mixture modified as explained below.

The quantities of azo dye, chromium complex and solvent mixture will generally be such as to provide a stock solution containing from 14% to 40%, preferably 16 to 29%, by weight of compound IV or compound V, but if desired more or less solvent mixture may be present in the product and the concentration adjusted subsequently to provide the above-mentioned concentration of compound IV or compound V.

In a particularly advantageous variant of the process according to the present invention, the azo dyes of the formula VI are produced by reacting the appropriate naphthoquinone diazide compounds with,P-naphthol in the solvent mixture according to G.B. Patent Specification No. 1,350,297. This may then be contacted with the 1:1 chromium complex without isolation of the dye VI.

The solvent mixture may contain, instead of, or in addition to, the formamides of the formula

specified in G.B. Patent Specification No. 1,350,297, and in corresponding amount, N-methylpyrrolidone, dimethylacetamide and/or a compound of the formula

where Rf denotes hydrogen or methyl and X denotes a direct bond, -CH2- or oxygen. Such alternative solvents can be used in the same manner and in the same quantities as the formamides.

The addition of the compounds of formula VI to the said 1:1 chromium complexes is preferably carried out at pH values of from 8 to 10 because particularly good results are obtained in this case.

Further details of the composition, the method of manufacture and use of the stock solutions according to the present invention, for example their use in the dyeing or printing of natural or synthetic polyamide material, are given in the Examples which follow and in G.B. Patent Specification No. 1.350,297.

The addition of dicarboxylic or oxycarboxylic acids, such as oxalic acid, malonic acid, tartaric acid, glycolic acid and r-hydroxybutyric acid, in the production of the solutions according to the present invention may be advantageous in many cases.

In the Examples parts are by weight unless otherwise indicated.

EXAMPLE 1.

210 parts of a water-wet paste containing 148 parts of 6-nitro-2-naphthoquinone1-diazide-4-sulphonic acid, 76 parts of water and 6 parts of H2SO" are added to a mixture of 250 parts of butyl diglycol and 420 parts of ice. 40 parts of 50% strength aqueous caustic solution, 76 parts of -naphthol and 41 parts of 25% strength aqueous ammonia are then introduced in the course of 40 minutes. After stirring for 15 hours coupling is over. 520 parts of a water-wet paste containing 234 parts of the 1:1 chromium complex of the azo dye prepared from diazotized 1-amino-2-oxy-5-nitrobenzene-3-sulphonic acid and 1-phenyl-3-methylpyrazolone; 80 parts of 50% strength aqueous caustic solution; and 8 parts of oxalic acid (crystals) are introduced into the resulting dye mixture. The batch is then boiled under reflux for 2 hours.After cooling, small quantities of impurities are removed from the batch by filtration. The filtrate constitutes the concentrated stock solution. It dyes wool in brown shades.

EXAMPLES t4.

Solutions of other 1:2 chromium complex dyes are prepared in an analogous manner to Example 1 when the 1:1 chromium complexes of the following o,o'dihydroxyazo dyes are used: Example No. Azo Dye Shade

NO2 -N = N - C - C - CH If II 3 2 OH ,c N brown c N brown .

CH3 CH3 NO2 = N - C - C - CH 3 Hd11 II If 3 brown S 3H OH HO N 1 C1 =N-C-r-CH3 4 CN = N - dark brown 803H H HOCN/N ( EXAMPLE 5.

195 parts of a water-wet paste containing 125 parts of 2-naphthoquinone-1diazide-4-sulphonic acid and 70 parts of water are added to a mixture of 300 parts of butyl diglycol and 600 parts of ice. 44 parts of 50% strength aqueous caustic solution, 78 parts of ss-naphthol and 30 parts of 25% strength aqueous ammonia are then introduced in the course of 40 minutes. After stirring for 15 hours coupling is over. 194 parts of the 1:1 chromium complex of the azomethine dye prepared from l-amino-2-oxy-5-nntrobenzene-3-sulphonic acid and salicylaldehyde; and 60 parts of 50% strength aqueous caustic solution are introduced into the resulting dye mixture. The batch is then boiled under reflux for 2 hours. After cooling, small quantities of impurities are removed from the batch by filtration. The filtrate constitutes the concentrate(+ stock solution. It dyes wool in olive shades.

EXAMPLES bs.

Solutions of other 1:2 chromium complex dyes are prepared in an analogous manner to Example 5 when the 1:1 chromium complexes of the following azomethines are used:- Example No. Azo Dye Shade

NO2 6 hut N = CH--- olive OH HK N02 7 ss N = CH43 No2 yellowish SO3H OH HO olive C1 8 ss N = CH p blush olive SO H OH WHAT WE CLAIM IS: 1. A process for the production of a water-miscible stock solution of a 1:2 chromium complex dye containing one or more sulphonic acid groups, which comprises contacting an azo dye of the general formula VI:

where Bl is hvdrozen or nitro with a 1:1 chromium complex having a cation of the general formula VII or VIII:

where B' is hydrogn or nitro. B2 is hvdrogen or hydroxysulphonyl, BS is hydrogen, chloro or nitro and B4 is hydrogen, chloro or methyl, to form a compound having an anion of the general formula IV or V:

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

Example No. Azo Dye Shade

NO2 6 hut N = CH--- olive OH HK N02 7 ss N = CH43 No2 yellowish SO3H OH HO olive C1 8 ss N = CH p blush olive SO H OH WHAT WE CLAIM IS: 1.A process for the production of a water-miscible stock solution of a 1:2 chromium complex dye containing one or more sulphonic acid groups, which comprises contacting an azo dye of the general formula VI:

where Bl is hvdrozen or nitro with a 1:1 chromium complex having a cation of the general formula VII or VIII:

where B' is hydrogn or nitro. B2 is hvdrogen or hydroxysulphonyl, BS is hydrogen, chloro or nitro and B4 is hydrogen, chloro or methyl, to form a compound having an anion of the general formula IV or V:

where B1, B2, B3 and B4 are each as defined above, the contact being effected in a solvent mixture comprising from 55 to 90% by weight (based on the solvent mixture) of water, from 45 to 10% by weight (based on the solvent mixture) of an organic solvent of the general formula II:

where R3 is hydrogen, alkyl of from 1 to 8 carbon atoms, acetyl or propionyl, R4 is hydrogen or methyl, and n is 0 or one of the integers 1 to 6, and from 0 to 12% by weight (based on the solvent mixture) of one or more of N-methylpyrrolidone, dimethylacetamide, a compound of the formula:

where R6 is hydrogen or methyl, a compound of the formula:

where R6 is hydrogen or methyl and X is a direct bond or is -0- or -CH2-, and a formamide of the general formula::

where R5 is methyl or hydrogen, using such amounts of azo dye, chromium complex and solvent mixture as to provide, if desired after subsequent adjustment of the solvent mixture content, a stock solution containing from 14% to 40% by weight of compound IV or V on the basis of the stock solution.
2. A process as claimed in claim I wherein components which couple to form said azo dye of formula VI are reacted to form said azo dye in a solvent mixture as defined in claim 1 and wherein the chromium complex of formula VII or formula VIII is contacted with said azo dye without isolation of the dye VI from the solvent mixture.
3. A process as claimed in claim 1 or 2 wherein the solvent mixture, azo dye and chromium complex are used in such amounts as to provide a stock solution containing from 16% to 29% by weight of compound IV or V on the basis of the stock solution.
4. A process as claimed in any of claims 1 to 3 wherein the contacting is carried out at a pH of from 8 to 10.
5. A process as claimed in any of claims 1 to 4 wherein a dicarboxylic acid or oxycarboxylic acid is also present.
6. A process as claimed in claim 1 carried out substantially as described in any one of the foregoing specific Examples.
7. A stock solution whenever obtained by a process as claimed in any preceding claim.
8. Natural or synthetic polyamide material when dyed or printed with the aid of a stock solution as claimed in claim 7.