DE1644283A1 - Process for the preparation of water-insoluble monoazo dyes - Google Patents

Description

Folder 21310 ~ Dr. P / hr
Case D.19468

NOTIFICATION to the patent application of

Imperial Chemical Industries Limited, London SW 1 » Great Britain,

concerning

"Process for the production of water-insoluble monoazo dyes" ο

You priority registration in Great Britain rome 15 * 7.1966 and 2.6.1967 is used.

The invention relates to water-insoluble azo dyes, in particular water-insoluble monoazo dyes, which are suitable for dyeing synthetic textiles, especially Textiles made from polyethylene terephthalate are suitable.

According to the invention, the water-insoluble monoazo dyes the formula

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16U283

.-. N = H - Jf \\ - jraAOOOH

created, whereby

A is an alkylene radical with 1 to 6 carbon atoms, X is a hydrogen atom »or a lower alkyl or

Represents Niederalkozyradikal, T is a hydrogen atom or a Hiederalkyl-, Nieder-

represents alkoxy or aoylamino radical, ü a chlorine or broa atom or a nitro, cyano,

Lower alkyl sulfonic or carbo-lower alkoxy radical

represents and 1 represents a hydrogen, chlorine or broa atom or a nitro * radical.

For the purposes of the invention, the expressions ^R lower alkyl ⁿ and ^{N lower alkoxy n should} each be alkyl- bsw. Alkozyradikaleait 1 to 4 carbon atoms .

As examples of the alkyl ene radicals represented by A, one can mention methylene, trimethylene, propylene, tetramethylene and, above all, ethylene radicals .

As examples of the lower alkyl represented by X and Y and lower alkoxy radicals can be methyl, ethyl, methoxy, Mention ethoxy, propoxy and butoxy radicals.

As examples of the lower alkyl represented by ü

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16U283

sulfonyl radicals can be methylsulfonyl, ethylsulfonyl and mention n-propylsulfonyl radicals. As examples of the carbo-lower alkoxy radicals represented by U may mention carbomethoxy and carboethoxy groups.

The acylamino groups represented by Y are preferred

2 2 acylamino groups of the formula -HHCOR, where R is water etoffatom or an optionally substituted hydrocarbon radical, in particular an optionally substituted lower alkyl, phenyl or cyclohexyl radical. The best examples for the acylamino groups one can Foimylamiao-, Acetylamino-, I-Äethylacetyltmino-, Mention propionylaaino- and bensoylamino grapes.

Gremäse a further feature of the invention, a manufacturing retracts, sor avr what "erunlöBllch" n Itenoasofarbst off rorgesohlagen β according to the invention, the d "rln b""t" ht _v that an amine of formula

iormel I

is diazotized and the resulting diazo compound bit a coupling component of the formula

f \

SHACOOE Formula II

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~ 4

is coupled, where A, U, V ₁ Z and Y have the meanings given o

The method according to the invention can be expediently thereby Realize that sodium nitrate becomes a solution or suspension of the amine in an aqueous hydrochloric acid solution added or the amine to a solution of nitrosylsulfuric acid is added, and that the resulting solution or suspension of the diazo compound to a solution of the Coupling component in an aqueous hydrochloric acid solution or in a water-soluble organic liquid such as ZoB ° Acetone is added. The resulting mixture is then stirred, preferably at a pH of 0 to 2, until until the azo dye is formed, which is then isolated in the usual way »

Examples of the amines of the formula I can be 4-nitro-2-cyanoaniline, 2,4-dinitroaniline, 2,4,6-trinitroaniline, 2,4-dinitro-6- (chloro- or -bromo) aniline, 2,6-di (chloro- or -bromo) -4-nitroaniline, 2-carbometho: Ey-4-nitroaniline, 2-methylsulfonyl-4-nitroaniline and mention 2 ~ cyano-4,6-dinitroaniline.

The coupling components of the formula II can be produced by using a primary amine of the formula

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with an acid of the formula Hal.AeCOOH or with the corresponding oc, i3-unsaturated acid reacted where Hai represents a chlorine or bromine atom.

As examples of the coupling components of the formula III you can use N- (ß ~ carboxyethyl) aniline, H- (ß-carboxyethyl) -mtoluidine, 3-acetylamino-N- (ß-carboxyethyl) aniline, 2-methoxy-5-methyl-N- (ß-carboxyethyl) aniline and 2,5-dimethoxy-H- (ß-carboxyethyl) mention aniline,

The water-insoluble monoazo dyes after the invention are suitable for dyeing synthetic textiles. The following can be mentioned as examples of such fabrics: fabrics made from cellulose acetate and cellulose triacetate, polyamide fabrics such as fabrics made from polyhexamethylene adipamide, polyacrylonitrile fabrics and preferably aromatic polyether fabrics such as fabrics made from polyethylene terephthalate. Such textiles can be in the form of threads, yarn, or knitted or woven fabric. The synthetic textile material may be ₀ for example blends of polyester textile materials with cellulose or woolen textile materials, whether in the form of blends with other textile materials, such as Z "

Such textiles can be conveniently with the o.a " Color monoazo dyes by turning the fabric into a dyebath consisting of an aqueous dispersion of one or more of the dyes is immersed and preferably a nonionic, cationic and / or contains anionic surfactant, after which the dye bath for a period of time at an appropriate

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16U283

Temperature is heated. In the case of secondary cellulose acetate textiles, the dyeing process is preferably "carried out at a ^{temperature between 60 and 65 °} C.". In the case of cellulose triacetate or polyamide textiles, the dyeing process is preferably carried out ^{at 95 to 100 ° C.} dyeing, either at 90 to 100 ⁰ C, preferably in the presence of a carrier such as diphenyl or o-hydroxydiphenyl, or performed Verden effected at a 100 ⁰ C _1, preferably lying between 120 and 140 C temperature under overpressure.

However, one can also proceed in such a way that the aqueous dispersion of the dye mentioned is applied to the textile fabric by a clot or printing process, after which the textile fabric, depending on the type, up to au. 230 ⁰ C heated or treated with steam. In such processes, the aqueous dispersion of the monoazo dye mentioned preferably contains a thickening agent such as tragacanth, gum arabic or sodium alginate,

k At the end of the dyeing process, the dyed textile is preferably rinsed with water or briefly treated with soapy water before it is finally dried. For aromatic polyester fabrics, the dyed fabric is preferably subjected to a treatment with an alkaline aqueous solution of sodium hydrosulfite before being treated with soapy water to remove loosely adhering dye from the surface of the fabric.

The monoazo dyes have an excellent affinity and an excellent build-up capacity with regard to synthetic

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shear fabrics, especially aromatic polyether fabrics, so that dark hues can be reached bind. The corresponding colorations are excellent Fastness to light, wet treatments and especially dry heat treatments, how they are carried out at high temperatures when pleating.

The monoazo dyes of the invention can be used as desired in conjunction with other disperse dyes, such as those in the British patents 806 271, 835 819, 840 903, 847 175, 852 396, 852 493, 859 899, 865 328, 872 204, 894 012, 908 656, 909 843, 910 306, 913 856, 919 424, 944 523, 944 722, 953 887, 959 816, 960 235, 961 412, 976 218, 993 162 and 998 858 described Bind.

The invention is explained in more detail below with the aid of exemplary embodiments, purely by way of example, with the Quantities are based on weight.

example 1

There are 0.7 parts of sodium nitrate added to 8 parts Scnwefelsäuremonohydrat below 35 C, and the mixture avjf 70 ⁰ C. and is then brought to 0 ° 0th Then 2.08 parts of 2-cyano-4,6-dinitroaniline and then 15 parts of phosphoric acid are added while the temperature is kept at 0 to 5 ° C. by external cooling. The mixture is then stirred for a further hour at this temperature.

The resulting solution of the dlazo compound gradually becomes to a solution of 2.09 parts of 2-methoxy-5-methyl-H- (ß-carboxyethyl) aniline and 1 part of urea in 200 parts

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Acetone was added with stirring, ice being added gradually to keep the temperature at 0 to 5 ° C. Then 500 parts of water are added and the deposited dye is filtered off, washed with water and then dried. After recrystallization from xylene, the dye has a melting point of 185 to 186 ^° C.

An aqueous dispersion of the dye results in dyeing of textile fabrics made of aromatic polyester blue shades, which are extremely lightfast.

The table below shows further examples of the monoazo dyes according to the invention can be generated by the fact that the labels in the 2 »column of the labeile indicated amines are diazotized and the resulting diazo compounds with those indicated in the 3rd column Coupling components are coupled, as in Example 1. The 4 "column are those used in the dyeing of aromatic Color shades of the polyester textile fabrics To find dyes.

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Example «

Amine coupling component

Color tint

2 3 4 5 6 7

10

12th

13 14 15

16

2-ChlΟΓ-4-nitroaniline 2-0yano-4 ~ nitroaniline 2-methyl-K- (ß-carboxyethyl) aniline

3-methyl-] J- (β-arboxyethyl) aniline

2-chloro-4-nitroanilixi 2 ~ cyano-4-nitroaniline 2-bromo-4,6-dinitroaniline

dto _o

2-Gyano-4 »6-Dinitroaniline

2-bromo-4t 6-dinitroaniline

2-cyano-4-nitroaniline

dto.

2-cyano-4-ilitro-6-bromoaniline

2-Ethyleulfonyl-4-nitro aniline

2-Ca! * Bometlioacy-4-ni troaniline Red

blue red

Ruby red

Red

Ruby red

blue red

blue red

navy blue

violet

Ruby red

Ruby red

violet 2,5-dimethyl "N- (β-arboxyethyl) aniline" violet

2-Methy 1-N- (ß-carboxy-ß-methylityl) * red aniline

2-methoxy-5-methy l-X - (Ύ-oarboxypropyl) * ruby red aniline

2,5-dimethyl-N- (ß-carboxyethyl) aniline

2-M © thoxy «5-methyl-K * (ß-carboxyethyl) * aniline

2,5-dimethoxy-N- (ß-carboxyethyl) aniline

2,5-dimethyl-N- (β-carboxyethyl) aniline 3-acetylamino-N- (ß-carboxyethyl) aniline

2-methoxy-5-methyl-N ~ (ß-earboxyethyl) aniline

Claims (1)

16U283 ■■ - ίο - Claim: Process for the preparation of water-insoluble monoazo carbates the formula where A represents an alkylene radical with 1 to 6 carbon atoms, X is a hydrogen atom or, a l-lower alkyl or Represents lower alkylene radical, Y is a water atom or an Äiederalkyl-, Hiederalkoxy- or represents acylamino radical, U is a chlorine or bromine atom or a Hltro-, Cyano-, Lower alkylsulfonyl or carbo-lower alkoxy radical represents and V represents a hydrogen, chlorine or bromine atom or a nitro radical, characterized in that an amine of the formula is diazotized and the resulting diazo compound with a Coupling component of the Pormel 109820/1972 HHACOOH is coupled, where A, U, V, X and Y have the ο.a · meanings 109820/1972