Exhaust process for the dyeing of synthetic fibre materials

Abstract

Exhaust process for the dyeing of synthetic fibre materials from organic water-immiscible solvents wherein are used as dyestuffs sulphonamide group containing disperse dyestuffs. There are obtained without originating waste waters dyeings with excellent fastness to washing, rubbing, light and sublimation.

Description

The invention relates to an exhaust process for the dyeing of synthetic fibre materials from organic water-immiscible solvents; more particularly it concerns an exhaust process for the dyeing of synthetic fibre materials from organic water-immiscible solvents wherein are used as dyestuffs disperse dyestuffs containing sulphonamide groups.

Organic water-immiscible solvents suitable for the process according to the invention are those the boiling point of which lies between 40.degree. and 170.degree. C, e.g. aromatic hydrocarbons such as toluene, xylene; and halogenated hydrocarbons, especially aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,1,1-trichloropropane, 1-chlorobutane, 2-chlorobutane, 1,4-dichlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropane or dichlorohexane; as well as aliphatic fluorinated and fluoro-chlorinated hydrocarbons, such as perfluoro-n-hexane, 1,2,2-trifluoro-trichloroethane and trifluoro-pentachloropropane; aromatic chlorinated and fluorinated hydrocarbons, such as chlorobenzene, fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane and 1,1,1-trichloropropane have proved particularly satisfactory. Mixtures of the said solvents can also be used.

The sulphonamide group-containing disperse dyestuffs to be used according to the invention may be based on any type of dyestuffs, provided these contain at least one sulphonamide group. The dyestuffs to be used according to the invention may belong, for example, to the series of metal-containing or metal-free mono- or polyazo dyestuffs or (azo)methine dyestuffs; to the series of anthraquinone dyestuffs and of condensation products thereof containing more than three fused rings; other suitable dyestuffs are oxazine, nitrodiphenylamine, naphthalic acid, di- and triphenyl-methane dyestuffs; naphtholactum condensation dyestuffs, quinophthalone dyestuffs, and dyestuffs based on naphthoquinone and naphthoquinonimine; as well as other condensation dyestuffs. In addition to the sulphonamide groups required by definition, the dyestuffs may contain other conventional substituents, such as halogen, alkyl, cycloalkyl, aralkyl, aryl, alkoxy, aryloxy, nitro, sulphone, optionally substituted carboxamide groups, optionally substituted or acylated amino groups, alkylthio and arylthio, hydroxy, hydroxyalkyloxy, aminoalkyloxy, cyano, cyanoalkyl, and differently substituted alkyl, aryl, aralkyl radicals, and the like.

The dyestuffs contain one or more sulphonamide groups which are linked to the aromatic nuclei of the basic ring system of the dyestuff itself or to aryl, aralkyl, or aliphatic groupings in external positions. The number of sulphonamide groups preferably amounts to 1 to 3.

The sulphonamide groups are characterized by the formula ##STR1## in which the radicals B and B.sub.1, independently of one another, denote hydrogen or optionally substituted lower alkyl or alkenyl groups, aryl radicals or heteroaryl radicals. Furthermore, the radicals B and B.sub.1 together may form a ring which may be interrupted by hetero atoms.

Examples of radicals B and B.sub.1 are the methyl, ethyl or trifluoromethyl radicals; the .beta.-hydroxy, .beta.-chloro, .beta.-bromo, .beta.-methoxy, .beta.-methylthio, .beta.-methylsulphonyl or .beta.-cyanoethyl groups; or an ethylene or .beta.-chloro- or .beta.-bromoethylene radical. If B or B.sub.1 stands for an aryl radical, this is preferably a phenyl radical which may be substituted by one or more halogen atoms such as fluorine, chlorine or bromine; nitro groups; trifluoromethyl, hydroxy or lower alkoxy radicals; carboxyl or carboxamide groups; acylamino groups; sulphonamide or lower alkylsulphonyl radicals. Suitable heteroaryl radicals are, for example, the pyridyl, pyrrolyl, pyrimidinyl, furanyl, thienyl or sulpholanyl radicals. Examples of rings which may be formed by B and B.sub.1 and may be interrupted by hetero atoms are the pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl or thiomorpholinyl dioxide rings.

Dyestuffs containing sulphonamide groups are known in large numbers and are prepared by conventional methods in that suitable dyestuff intermediates containing one or more sulphonamide groups linked to the nucleus or in an external position are converted into the desired final products while retaining the sulphonamide groups and, if desired, further conversion reactions are carried out in the latter. Obviously, it is also possible to start from dyestuffs containing one or more sulphonic acid groups and to convert the sulphonic acid groups into the corresponding amides in the usual way via reactive intermediate stages, such as e.g. the ester and acid chloride. In the case of azo dyestuffs, the usual conversion reactions are diazotisation and coupling; for most other dyestuffs classes they are condensation reactions.

Examples of suitable azo dyestuffs containing sulphonamide groups are the following compounds in which the radical ##STR2## may have the following meaning: ##STR3##

Suitable anthraquinone dyestuffs are, for example, those in which one or more sulphonamide groups stand in the anthraquinone molecule itself or in aryl or alkyl radicals which are linked to the anthraquinone molecule via bridge members such as amino, ether, thioether, sulphonamide or sulphonylamino groups.

The anthraquinone compounds may have the following constitutions, for example, the group ##STR4## having the same meaning as above: ##STR5## furthermore, acylation products of amino-anthraquinones, e.g. of the formulae: ##STR6## with sulpho-carboxylic acids of the general formula ##STR7##

X = alkylene, arylene, a bivalent heterocyclic radical; or with a compound of the formula ##STR8## and furthermore, the anthraquinone dyestuffs assembled in the following Table:

##STR9## ##STR10## ##STR11## ##STR12## ##STR13## ##STR14## ##STR15## ##STR16## ##STR17## ##STR18## XX ##STR19## XXXX ##STR20## XXXXXXX ##STR21## XXXX ##STR22## XX XXX ##STR23## XXXXXXX (NH.sub.2) (NH.sub.2) ##STR24## XXXXXXX ##STR25## XXXXXX ##STR26## XXXXXX

The anthraquinone dyestuffs of the formula ##STR27## in which

R.sub.1 means an amino group

R.sub.2 means a hydroxy or amino group

X means --O-- or --S--

Y means a phenylene group and

D means ##STR28## have proved to be of special interest and among them the dyestuffs ##STR29## have proved to be especially valuable.

Among anthraquinone condensation products which contain sulphonamide groups and contain more than three fused rings, the following may be mentioned by way of example: Isothiazoloanthrones, such as ##STR30## Pyrazoloanthrones, such as ##STR31## furthermore, dyestuffs of the type ##STR32##

Anthraquinone dyestuffs of the formulae given above are prepared according to the synthesis principles known in anthraquinone chemistry. Condensation reactions with appropriate starting compounds are suitable in the first instance for this purpose. For example, amino group-containing anthraquinone compounds in which the amino groups stand either in an external position or, preferably, in a position linked to the nucleus, can be condensed with suitable sulphoaryl-acid halides or anhydrides, e.g. sulphophenyl- or naphthyl-carboxylic acid or -sulphonic acid chlorides or bromides to form the corresponding acid amides; or, for example, anthraquinone compounds with mobile halogen atoms can be reacted with sulphoaryl-amines such as sulphophenyl- or sulphonaphthyl-amines to form the corresponding sulphoarylamino-anthraquinone derivatives, and the free sulpho groups still present in the resultant dyestuffs can be converted into sulphonamide groups in known manner. Alternatively, for example, anthraquinone compounds containing amino groups can be condensed with sulphonamido-aryl-acid halides or anhydrides, or e.g. anthraquinone compounds containing mobile halogen atoms can be condensed with sulphonamido-arylamines.

Anthraquinone ether and thioether derivatives in which sulphonamide groups are contained in alkyl, aralkyl or aryl radicals of the ether or thioether component, can be prepared according to similar synthesis principles. Another possibility of synthetising sulphonamide group-containing anthraquinone dyestuffs to be used according to the invention consists in that anthraquinone-acid halides, such as carboxylic acid and sulphonic acid chlorides or bromides, are converted into the corresponding amides or esters with the aid of suitable amino or hydroxy compounds which contain at least one additional sulphonamide group. Obviously, it is also possible to use for the present process also those anthraquinone compounds in which one or more sulphonamide groups stand in a position linked to the nucleus or in which sulphonamide groups linked to the nucleus as well as externally linked sulphonamide groups are present.

As representatives of nitro dyestuffs containing sulphonamide groups, there may be mentioned for example dyestuffs of the formula ##STR33## or dyestuffs of the formula ##STR34## in which

R.sub.1 means hydrogen, a halogen atom, a trifluoro, cyano, hydroxy, C.sub.1 -C.sub.4 -alkyl or -alkoxy, a hydroxymethyl or -ethyl, a hydroxy-ethylene-oxy, acylamino, alkylsulphonyl-amino, alkylsulphone, carboxamido, aminosulphonyl-alkyleneamino or sulphonamide group;

R.sub.2 means hydrogen or a C.sub.1 -C.sub.4 -alkoxy group;

R.sub.3 means hydrogen, a halogen atom, a hydroxy, hydroxy-ethyleneoxy, carboxamido, aminosulphonyl-alkyleneoxy or sulphonamide group;

X stands for the group --SO.sub.2 -- or --CO; and

Y stands for --NH-- or --O--;

with the proviso that one of the radicals R.sub.1, R.sub.3 or ##STR35## is a sulphonamide group or a radical containing a sulphonamide group.

The nitro dyestuff of the formula ##STR36## has proved to be especially valuable.

In many cases it has proved advantageous for the dyebaths to contain small amounts of water, i.e. up to 1 per cent by weight, preferably 0.5 per cent by weight, referred to the weight of the organic solvent.

Furthermore, it has proved expedient in some cases to add non-ionic auxiliaries to the dyebaths. Suitable non-ionic auxiliaries are primarily the known interface-active ethoxylation and propoxylation products of fatty alcohols, alkylphenols, fatty acid amides and fatty acids as well as mixtures thereof; the auxiliaries are used in an amount of 0.05 - 2 per cent by weight, referred to the weight of the organic solvents. Instead of being immediately added to the dyebaths, the auxiliaries can also be used to advantage for pasting the sulphonamide group-containing dyestuffs and in this way be added to the dyebaths in the form of a dyestuff/auxiliary paste.

The synthetic fibre materials to be dyed according to the invention are primarily fibre materials of polyesters, such as polyethylene terephthalate, poly-cyclohexane-dimethylene terephthalate, heterogeneous polyesters from terephthalic acid, sulphoisophthalic acid and ethylene glycol, or copolyether ester fibres from p-hydroxybenzoic acid, terephthalic acid and ethylene glycol; cellulose triacetate, cellulose 21/2-acetate; polyacrylonitrile, synthetic polyamides such as hexamethylene-diamine adipate, poly-.epsilon.-caprolactam or 4-aminoundecanic acid; and polyurethanes. The fibre materials may be present in the most varied stages of processing, for example, as threads, loose material, combed material, yarn, as piece goods such as fabrics or knitted fabrics, or as ready-made goods.

Dyeing according to the invention is preferably carried out in closed apparatus, for example, by introducing the fibre materials at room temperature into the dyebath, heating the dyebath to 60.degree. - 170.degree. C and keeping it at this temperature until the bath is exhausted; this is usually the case after 10 - 60 minutes. After cooling to room temperature, the liquor is separated and the fibre materials are freed from any adhering solvent, optionally after a short rinsing with fresh organic solvent, by filtering with suction or by centrifuging and subsequent drying in a warm current of air. With the aid of the process according to the invention it is possible to dye synthetic fibre materials from organic solvents in a simple way, high dyestuff yields and excellent fastness properties being achieved.

The sulphonamide group-containing dyestuffs to be used according to the invention are largely insoluble in the organic water-immiscible solvents. They are distinguished from the dyestuffs hitherto used for dyeing synthetic fibre materials from organic solvents by their substantially better affinity and an increased fastness to sublimation.

It may be mentioned that mixtures of the dyestuffs to be used according to the invention sometimes give a better dyestuff yield than the individual dyestuffs.

The parts given in the following Examples are parts by weight.

EXAMPLE 1

100 Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperature, without previous cleaning, into a dyebath prepared from

1 part of the monoazo dyestuff 4-aminobenzene-sulphonic acid amide .fwdarw. 3-methyl-pyrazolone-(5) and

1000 parts tetrachloroethylene.

The bath is heated to 115.degree. C within 10 minutes and kept at the same temperature for 30 minutes, while the liquor is vividly circulating. The liquor is then separated and the dyed material is rinsed with fresh solvent at about 40.degree. C for 5 minutes. After separating of the rinsing liquor, the dyed material is centrifuged and dried in an air current. A strong yellow dyeing of excellent fastness to sublimation and very good fastness to washing and light is obtained.

An equally satisfactory yellow dyeing was obtained in the same way on a fabric of polycyclohexane-dimethylene terephthalate fibres.

Yellow dyeings of equally satisfactory fastness properties were also obtained when the dyestuff mentioned above was replaced with the same amount of one of the following monoazo dyestuffs:

__________________________________________________________________________Example Dyestuff Shade__________________________________________________________________________ 2 3-nitro-4-amino-benzene-sulphonic acid yellow ##STR37## 3 2-amino-benzene-sulphonic acid amide yellow ##STR38## 4 ##STR39## yellow 5-pyrazolone-1-sulphonic acid amide 5 ##STR40## yellow 1-sulphonic acid methylamide 6 4-methoxy-3-amino-benzene-sulphonic acid yellow ##STR41## 6-pyrazolone 7 3-nitro-4-amino-benzene-sulphonic acid orange ##STR42## pyrazole 8 ##STR43## orange lino-sulphonyl-phenyl)-3-ethoxy-5-amino- pyrazole 9 4-amino-benzene-sulphonic acid amide yellow ##STR44## acid ethyl ester10 4-amino-benzene-sulphonic acid amide yellow ##STR45## pyrazolone11 4-amino-benzene-sulphonic acid ethylamide yellow ##STR46## acid12 4-amino-benzene-sulphonic acid dimethyl- yellow ##STR47## carboxylic acid amide13 3-nitro-4-amino-benzene-sulphonic acid yellow ##STR48## carboxylic acid ethyl ester14 ##STR49## yellow sulphonyl-phenyl)-3-methyl-5-pyrazolone15 4-amino-benzene-sulphonic acid-(di-2- yellow ##STR50## 3-methyl-5-pyrazolone16 4-amino-benzene-sulphonic acid ethylamide yellow ##STR51## pyrazolone17 ##STR52## yellow sulphonyl-phenyl)-3-methyl-5-pyrazolone18 ##STR53## yellow sulphonyl-phenyl)-3-methyl-5-pyrazolone19 4-amino-benzene-sulphonic acid-dimethyl- yellow ##STR54## methyl-5-pyrazolone20 3-nitro-4-amino-benzene-sulphonic acid yellow ##STR55## pyrazolone-3-carboxylic acid21 ##STR56## yellow sulphonyl-ethyl)-3-methyl-5-pyrazolone22 ##STR57## yellow benzene-2-sulphonic acid-(di-2-cyanoethyl)- amide23 ##STR58## yellow benzene-2-sulphonic acid-(4-chlorophenyl)- amide24 4-(4-pyrrolidinosulphonylbutoxy)-aniline yellow ##STR59## (2-pyridino)-amide25 ##STR60## yellow benzene-2-sulphonic acid-(3-sulpholanyl)- amide26 4-amino-benzene-sulphonic acid amide yellow ##STR61##27 2-amino-benzene-sulphonic acid amide yellow ##STR62##28 3-nitro-4-amino-benzene-sulphonic acid amide yellow ##STR63##29 3-nitro-5-chloro-4-amino-benzene- yellow ##STR64##30 4-amino-benzene-sulphonic acid-piperidide yellow ##STR65## carboxylic acid31 4-amino-benzene-sulphonic acid-(2-methyl- yellow ##STR66## methyl-benzene-2-sulphonic acid amide32 ##STR67## yellow hydroxy-4-n-propyl-benzene33 ##STR68## yellow hydroxy-4-methyl-benzene34 4-dimethylamino-sulphonylamino-aniline yellow ##STR69##35 4-methylsulphonylamino-aniline yellow ##STR70## carboxylic acid amide__________________________________________________________________________

EXAMPLE 36

100 Parts of a fabric of triacetate fibres are introduced at room temperature into a dyebath prepared from

1 part of the monoazo dyestuff 4-methyl-sulphonylamino-aniline .fwdarw. 1-hydroxy-4-methyl-benzene and

1000 parts tetrachloroethylene.

The bath is heated to 110.degree. C within 20 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. The liquor is then separated and the fabric is rinsed with fresh tetrachloroethylene at 40.degree. C. After separation of the rinsing liquor, the dyed materials is freed from the adhering solvent by centrifuging and drying in an air current. A full brilliant yellow dyeing of excellent fastness properties is obtained.

EXAMPLE 37

100 Parts of yarn of acetate threads are introduced at about 22.degree. C into a dyebath prepared from

1 part of the monoazo dyestuff 4-piperidyl-sulphonylamino-aniline .fwdarw. 1-hydroxy-4-methyl-benzene,

1000 parts tetrachloroethylene

1.5 parts oleic acid ethanolamide

1.5 parts oleyl alcohol eicosaethylene glycol ether and

6 parts of water.

The bath is heated to 78.degree. C within 20 minutes and kept at the same temperature for 45 minutes. After separation of the dye liquor and rinsing with fresh tetrachloroethylene, the dyed material is freed from the adhering solvent by filtering with suction and drying in an air current. A brilliant yellow dyeing is obtained.

EXAMPLE 38

100 Parts of yarn of polyacrylonitrile fibres are dyed in a dyebath prepared as described in Example 36. The bath is heated to 100.degree. C within 20 minutes and kept at the same temperature for 30 minutes. After the usual washing and drying, there is obtained a yellow dyeing of good fastness properties.

EXAMPLE 39

100 Parts of a fabric of polyethylene terephthalate fibres are heated in a dyebath containing

1 part of the monoazo dyestuff 3-nitro-4-aminobenzene-sulphonic acid amide .fwdarw. 1-methyl-2,4-dihydroxy-quinoline in

1000 parts tetrachloroethylene

to 115.degree. C within 10 minutes and dyed at the same temperature for 30 minutes. After separation of the liquor, rinsing and drying, there is obtained a brilliant greenish yellow dyeing of very good fastness to sublimation, washing and light.

When the above dyestuff was replaced with the same amount of one of the dyestuffs listed in the following Table, dyeings of equally satisfactory fastness properties were obtained in the shades stated in the Table:

__________________________________________________________________________Example Dyestuff Shade__________________________________________________________________________40 4-amino-benzene-sulphonic acid amide yellow ##STR71##41 4-trifluoromethyl-2-amino-benzene- yellow ##STR72## dihydroxy-quinoline42 4-chloro-3-amino-benzene-sulphonic acid yellow ##STR73## dihydroxy-quinoline43 4-amino-benzene-sulphonic acid-(di-2- yellow ##STR74## dihydroxy-quinoline44 3-amino-benzene-sulphonic acid-(2-methyl- yellow ##STR75## dihydroxy-quinoline45 4-amino-benzene-sulphonic acid-(1-naphthyl)- yellow ##STR76##46 3,5-dichloro-4-amino-benzene-sulphonic acid yellow ##STR77## ethyl-aniline47 3,6-dichloro-4-amino-benzene-sulphonic acid orange ##STR78## ethyl-aniline48 3-nitro-4-amino-benzene-sulphonic acid amide reddish ##STR79## yellow49 3-nitro-5-bromo-4-amino-benzene-sulphonic yellowish ##STR80## red aniline50 3-nitro-4-amino-benzene-sulphonic acid reddish ##STR81## yellow ethyl)-aniline51 3-cyano-5-nitro-4-amino-benzene-sulphonic yellowish ##STR82## red ethyl)-aniline52 3,5-dicyano-4-amino-benzene-sulphonic acid red ##STR83##53 3-chloro-5-nitro-2-amino-benzene-sulphonic red ##STR84## ethyl)-aniline54 3-chloro-5-nitro-2-amino-benzene-sulphonic red ##STR85## ethyl)-aniline55 3-cyano-5-nitro-2-amino-benzene-sulphonic bluish ##STR86## red methoxycarbonyloxy-ethyl)-aniline56 3,5-dichloro-4-amino-benzene-sulphonic acid orange ##STR87## ethyl)-aniline57 3-cyano-5-bromo-4-amino-benzene-sulphonic reddish ##STR88## orange phenylamino)-ethyl]-succinimide58 5-methoxy-2-amino-benzene-sulphonic acid yellowish ##STR89## red ethyl)-aniline59 3-bromo-5-nitro-4-amino-benzene-sulphonic violet ##STR90## aniline60 3-bromo-5-cyano-4-amino-benzene-sulphonic red- ##STR91## violet aniline61 3,5-dicyano-4-amino-benzene-sulphonic acid violet ##STR92##62 3-bromo-5-nitro-4-amino-benzene-sulphonic violet ##STR93## N,N-dimethyl-aniline63 3-chloro-5-nitro-2-amino-benzene-sulphonic violet ##STR94## N,N-dimethyl-aniline 64 ##STR95## violet sulphonylamino-N,N-dimethylaniline65 2-bromo-4-nitro-6-cyano-aniline blue- ##STR96## violet N-(2-cyanoethyl)-aniline 66 ##STR97## blue 3-methylsulphonylamino-N,N-dimethyl- aniline 67 ##STR98## violet sulphonylamino-N,N-dimethyl-aniline 68 ##STR99## violet 3-methylsylphonylamino-N-(2-hydroxy- ethyl)-N-(2-cyanoethyl)-aniline 69 ##STR100## blue 5-methylsulphonylamino-N,N-(di-2- acetoxymethyl)-aniline 70 ##STR101## reddish sulphonyl-amino-N,N-(di-2-acetoxy- yellow ethyl)-aniline71 3-bromo-5-nitro-4-amino-benzene- brown ##STR102## sulphonylmethylamino-N,N-dimethyl- aniline 72 ##STR103## brown 3-(3-ethylaminosulphonylpropylamino)- N,N-diethyl-aniline 73 ##STR104## yellow- N-ethyl-N-(2-dimethylaminosulphonyl- brown ethyl)-aniline 74 ##STR105## reddish 3-methyl-N,N-(di-2-acetoxyethyl)- yellow aniline75 3-nitro-5-amino-benzene-sulphonic acid orange ##STR106## ethyl)-N-(2-methoxycarbonylethyl)- anilino 76 ##STR107## yellow sulphonyl-aniline 77 ##STR108## reddish ethyl-N-(2-methylsulphonylamino- yellow ethyl)-aniline78 4-amino-benzene-sulphonic acid methyl- yellow ##STR109##79 4-amino-benzene-sulphonic acid-thio- yellow morpholid-8-dioxide80 4-(3-methylaminosulphonyl-benzoyl- yellow ##STR110##81 6-methylaminosulphonyl-2-amino-1,3- red ##STR111## (2-acetoxyethyl)-aniline82 6-aminosulphonyl-2-amino-1,3-benzo- red ##STR112## aniline83 3-chloro-4-amino-benzene-sulphonic acid orange ##STR113## aniline84 5-methylaminosulphonyl-2-amino- bluish ##STR114## red ethyl)-aniline85 5-aminosulphonyl-2-amino-1,3- red- ##STR115## violet aniline86 4-(4-aminosulphonylphenyl)-2-amino- yellowish ##STR116## red ethyl)-aniline87 4-(4-methylaminosulphonylphenyl)-2- red ##STR117## amino-N,N-dimethyl-aniline 88 ##STR118## orange 3-methyl-N,N-(di-2-acetoxyethyl)- aniline 89 ##STR119## reddish 3-acetylamino-aniline orange 90 ##STR120## red naphthalene-6-sulphonic acid methylamide 91 ##STR121## red naphthalene-6-sulphonic acid amide92 4-methylsulphonylamino-2-nitro-aniline red ##STR122## 93 ##STR123## red 2-aminonaphthalene-5-sulphonic acid methylamide 94 ##STR124## yellow 1,2-dimethyl-indole 95 ##STR125## red naphthalene-6-sulphonic acid-N-methyl- N-(2-hydroxyethyl)-amide 96 ##STR126## red naphthalene-6-sulphonic acid-N-methyl- N-(2-acetoxyethyl)-amide97 4-amino-azobenzene-4'-sulphonic acid amide red ##STR127##98 3-chloro-5-amino-benzene-sulphonic acid reddish ##STR128## yellow99 4-methyl-5-aminosulphonyl-2-amino-1,3- red ##STR129## aniline100 5-nitro-3-amino-benzoisothiazole-(2,1) navy ##STR130## aniline101 5-nitro-3-amino-benzoisothiazole-(2,1)- red ##STR131## N,N-dimethyl-aniline__________________________________________________________________________

EXAMPLE 102

100 Parts of a knitted fabric of polyethylene terephthalate fibres are dyed in a dyebath containing

1 part of the disazo dyestuff 4-aminobenzene-sulphonic acid amide .fwdarw. aniline .fwdarw. phenol in

1000 parts tetrachloroethylene

at 115.degree. C for 30 minutes. After the usual rinsing and drying, there is obtained a reddish yellow dyeing of very good fastness to sublimation, washing and light.

Dyeings of equally valuable fastness properties were also obtained when the above dyestuff was replaced with the same amount of one of the following disazo dyestuffs:

__________________________________________________________________________Example Dyestuff Shade__________________________________________________________________________103 4-amino-benzene-sulphonic acid methyl- reddish ##STR132## orange104 3-chloro-4-amino-benzene-sulphonic acid orange ##STR133## 105 ##STR134## orange 1-hydroxy-benzene-2-sulphonic acid-(2- hydroxyethyl)-amide106 4-chloro-3-amino-benzene-sulphonic acid reddish ##STR135## yellow107 3-nitro-4-amino-benzene-sulphonic acid reddish ##STR136## yellow 108 ##STR137## ##STR138## 109 ##STR139## yellow 110 ##STR140## orange- brown 111 ##STR141## reddish yellow112 ##STR142## reddish yellow113 ##STR143## reddish yellow114 ##STR144## orange115 ##STR145## orange 116 ##STR146## orange117 ##STR147## reddish yellow 118 ##STR148## reddish yellow119 ##STR149## reddish yellow 120 ##STR150## reddish yellow 121 ##STR151## orange__________________________________________________________________________

EXAMPLE 122

50 Parts of a fabric of polyester fibres are introduced at room temperature into a dyebath prepared from

1 part 1-amino-4-hydroxy-2-(4-aminosulphonyl-phenyl-thio-anthraquinone

1.5 parts oleic acid ethanolamide

1.5 parts oleyl alcohol eicosaethylene glycol ether

6 parts of water and

500 parts tetrachloroethylene.

The bath is heated to 120.degree. C within 10 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. After separation of the dye liquor, the dyed material is rinsed with fresh solvent at 40.degree. C and, after removal of the rinsing liquor, dried in an air current. A brilliant violet dyeing of excellent fastness to light and sublimation is obtained.

Equally satisfactory violet dyeings are obtained when the 500 parts tetrachloroethylene are replaced with the same amount of 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1,2-dichloropropane, 2-chlorobutane, 1,4-dichlorobutane, perfluoro-n-hexane, 1,2,2-trifluoro-trichloroethane, trifluoro-pentachloropropane, chlorobenzene, fluorobenzene, chlorotoluene or benzotrifluoride.

The dyestuff used in Example 122 had been prepared as follows: 15 parts 1-amino-4-hydroxy-2-phenylthioanthraquinone are dissolved in 76 parts chlorosulphonic acid, and 22.5 parts thionyl chloride are added at 20.degree.-25.degree. C within 1 hour. The melt is stirred at 20.degree.- 25.degree. C for 3 hours, turned out on to ice, the precipitate is filtered off with suction and washed with ice-water until neutral. The product is subsequently introduced into 250 parts of 25% ammonia and stirred at 20.degree.-25.degree. C for 5 hours. It is filtered off with suction, washed with water, and after drying there are obtained 18.5 parts 1-amino-4-hydroxy-2-(4-aminosulphonyl-phenylthio)-anthraquinone = 96% of theory.

EXAMPLE 123

100 Parts of fibre yarn of poly-.epsilon.-caprolactam are introduced at room temperature into a dyebath containing

1 part of the dyestuff mentioned in Example 122 in 1000 parts tetrachloroethylene.

The bath is heated to 100.degree. C within 20 minutes and kept at the same temperature for 40 minutes while the liquor is vividly circulating. After this period of time, the liquor is separated, the dyeing is briefly rinsed with fresh solvent and dried in an air current after centrifuging. A brilliant violet dyeing of good fastness properties is obtained.

An equally satisfactory dyeing was also obtained on yarns of polyhexamethylene-diamine adipate fibres.

The strength of colour of the dyeing can be increased by .about. 10% by the addition of

1 part oleic acid ethanolamide

1 part oleyl alcohol eicosaethylene glycol ether and

4 parts of water

to the dyebath.

EXAMPLE 124

100 Parts polyethylene terephthalate fabric are dyed at 115.degree. C for 30 minutes in a dyebath consisting of

1 part 1-amino-4-hydroxy-2-(4-methylamino-sulphonyl-phenoxy)-anthraquinone,

3 parts oleic acid ethanolamide

3 parts oleyl alcohol eicosaethylene glycol ether 12 parts of water and

1600 parts tetrachloroethylene.

After rinsing with fresh tetrachloroethylene and drying, there is obtained a strong and brilliant red dyeing of very good fastness to sublimation, washing and light.

When the above dyestuff was replaced with the same amount of one of the dyestuff listed in the following Table, then dyeings of equally satisfactory fastness properties were obtained in the shades stated in the Table:

______________________________________Exam-ple Dyestuff Shade______________________________________125 1-amino-4-hydroxy-2-[4-(2-methoxyethyl- red amino)-sulphonyl-phenoxy]-anthraquinone126 1-amino-4-hydroxy-2-[4-(2-hydroxyethyl- red amino)-sulphonyl-phenoxy]-anthraquinone127 1-amino-4-hydroxy-6-chloro-2-(4-amino- red sulphonyl-phenoxy)-anthraquinone128 1-amino-4-hydroxy-6,7-difluoro-2- red (4-thiomorpholino-sulphonyl-phenoxy)- anthraquinone129 1-amino-4-hydroxy-2-(4-methylsulphonyl- red aminophenoxy)-anthraquinone130 1-amino-4-hydroxy-2-[2-(4-aminosulphonyl- red phenoxy)-ethoxy]-anthraquinone131 1-amino-4-hydroxy-2-[2-(4-methylamino- red sulphonylphenyl)-ethoxy]-anthraquinone132 1-amino-4-hydroxy-2-[4-aminosulphonyl red phenylthio)-ethoxy-]anthraquinone133 1-amino-4-hydroxy-2-(4-diethylamino- red sulphonylamino-phenoxy)-anthraquinone134 1-amino-4-hydroxy-2-[4-(3-methoxy- violet propylamino)-sulphonyl-phenyl-thio]- anthraquinone135 1-amino-4-hydroxy-2-[4-(2-hydroxy- violet ethylamino)-sulphonyl-phenyl-thio]- anthraquinone136 1-amino-4-hydroxy-2-[4-chloro-2-(di-2- violet hydroxyethyl)-amino-sulphonyl-phenyl- thio]-anthraquinone137 1-amino-4-hydroxy-2-(4-methylthio-3- violet amino-sulphonyl-phenyl-thio)-anthra- quinone138 1-amino-4-hydroxy-7-chloro-2-[(2-methyl- violet sulphonylethyl)-amino-sulphonyl-phenyl- thio]-anthraquinone139 1-amino-4-hydroxy-2-(3-aminosulphonyl- bluish propylthio)-anthraquinone red140 1-amino-4-hydroxy-2-(4-methylamino- bluish sulphonyl-benzylthio)-anthraquinone red141 1-amino-4-hydroxy-2-[2-(4-hexamethylene- bluish imino-sulphonyl-phenyl)-ethylthio]- red anthraquinone142 1-amino-4-hydroxy-2-[2-(3-methyl-4- bluish aminosulphonyl-phenoxy)-ethyl-thio]- red anthraquinone143 1-amino-4-hydroxy-2-(2-dimethylamino- bluish sulphonylethylthio)-anthraquinone red144 1-amino-4-methoxy-2-(4-methylamino- yellow- sulphonyl-phenoxy)-anthraquinone red145 1-amino-4-methoxy-2-(4-N-methyl-N- red phenylamino-sulphonyl-phenyl-thio)- anthraquinone146 1-amino-2-(4-morpholinosulphonyl- orange phenoxy)-anthraquinone147 1-amino-2-(4-aminosulphonyl-phenyl-thio)- yellow- anthraquinone red148 1,4-dihydroxy-2-[4-(2-cyanoethylamino)- orange sulphonyl-phenoxy]-anthraquinone149 1,4-dihydroxy-2-(4-aminosulphonyl-phenoxy)- orange anthraquinone150 1,4-dihydroxy-2-(4-methylamino- scarlet sulphonyl-phenyl-thio)-anthraquinone151 1,4-diamino-2-[4-(3-cyano-phenyl-amino)- blue- sulphonyl-phenoxy]-anthraquinone violet152 1,4-diamino-2,3-bis-(4-amino-sulphonyl- red- phenoxy)-anthraquinone violet153 1,4-diamino-2-(4-amino-sulphonyl-phenyl- reddish thio)-anthraquinone blue154 1,4-diamino-2-[4-(3-methoxypropylamino)- reddish sulphonyl-phenyl-sulphonyl]-anthraquinone blue155 1,4-diamino-anthraquinone-2-sulphonic acid reddish (4-ethyl-amino-sulphonyl-phenyl) ester blue156 1-hydroxy-4-(3-methylamino-sulphonyl- blue- phenyl-amino)-anthraquinone violet157 1-hydroxy-4-(4-methyl-3-amino-sulphonyl- blue- phenyl-amino)-anthraquinone violet158 1-hydroxy-4-(4-methylsulphonyl-amino- reddish phenyl-amino)-anthraquinone blue159 1-amino-4-[4-(2-cyanoethyl-2-hydroxy- blue ethyl-amino-sulphonyl)-phenyl-amino]- anthraquinone160 1-amino-4-(2,6-diethyl-4-methyl-3- reddish amino-sulphonyl-phenyl-amine)-anthra- blue quinone161 1-amino-2-bromo-4-(4-methoxy-3-amino- reddish sulphonyl-phenylamino)-anthraquinone blue162 1-amino-2-phenyl-thio-4-(4-methyl-3- blue amino-sulphonyl-phenylamino)-anthra- quinone163 1-amino-2-phenyl-sulphonyl-4-(3-amino- greenish sulphonyl-phenylamino)-anthraquinone blue164 1-amino-4-(4-amino-sulphonyl-phenyl- red thio)-anthraquinone165 1-amino-2-(4-amino-sulphonyl-phenoxy)- pink 4-(4-methylphenyl)-sulphonyl-amino)- anthraquinone166 1-amino-2-(4-amino-sulphonyl-phenoxy)- pink 4-methyl-sulphonyl-amino-anthraquinone167 1-amino-anthraquinone-2-sulphonic acid red (4-methoxyphenyl-amide)168 1-amino-4-hydroxy-anthraquinone-2- red sulphonic acid-(3-trifluoromethyl-phenyl- amide)169 1,4-diamino-anthraquinone-2-sulphonic acid blue amide170 1,4-diamino-anthraquinone-2-sulphonic acid blue (2-methoxy-ethyl)-amide171 1,5-dihydroxy-4,8-diamino-anthraquinone- blue 2-sulphonic acid ethylamide172 1,5-dihydroxy-4,8-diamino-anthraquinone- blue 2,6-disulphonic acid-(3-methoxypropyl)- amide173 1,4-diamino-2-[5-methylaminosulphonyl- blue benzoxazolyl-(2)]-anthraquinone174 1-amino-4-(4-methylphenyl-amino)- blue anthraquinone-2-sulphonic acid-(2-hydroxy- ethyl)-amide175 1-amino-4-cyclohexyl-amino-anthraquinone- blue 2-sulphonic acid amide176 1-(3-aminosulphonyl-propyl-amino)- red anthraquinone177 1,4-bis-(3-amino-sulphonyl-propyl- blue amino)-anthraquinone178 1,5-dihydroxy-4,8-diamino-2-(4-hydroxy- blue 3-ethylamino-sulphonyl-phenyl)- anthraquinone179 1,5-dihydroxy-4,8-diamino-3-(4-hydroxy- blue 3-methylamino-sulphonyl-phenyl)-anthra- quinone180 1,5-dihydroxy-8-nitro-4-(3-ethylamino- blue sulphonyl-phenylamino)-anthraquinone181 1,8-dihydroxy-5-nitro-4-(3-amino- blue sulphonyl-phenylamino)-anthraquinone182 1,5-dihydroxy-8-amino-4-(3-methylamino- blue sulphonyl-phenylamino)-anthraquinone -183 1,8-dihydroxy-5-amino-4-(3-amino- blue sulphonyl-phenylamino)-anthraquinone184 1,5-dihydroxy-8-amino-x-chloro-4- blue (3-amino-sulphonyl-phenylamino)- anthraquinone185 1,5-dihydroxy-8-nitro-x-bromo-4- blue (3-amino-sulphonyl-phenylamino)- anthraquinone186 1,8-dihydroxy-5-amino-x-bromo-4- blue (3-amino-sulphonyl-phenylamino)- anthraquinone187 1,8-dihydroxy-5-amino-x-bromo-4- blue (3-amino-sulphonyl-phenylamino)- anthraquinone188 1,8-dihydroxy-5-methylamino-4- blue (4-methyl-3-amino-sulphonyl-phenyl- amino)-anthraquinone189 1,9-isothiazolanthrone-2-sulphonic acid yellow (4-bromo-phenyl)-amide190 5-(2-aminosulphonyl-ethylamino)-1,9- yellow isothiazoloanthrone191 1,9-pyrazoloanthrone-2-sulphonic acid-N- yellow (2-hydroxyethyl)-N-phenyl-amide192 5-(2-amino-sulphonyl-ethylamino)-1,9- yellow pyrazoloanthrone193 4-(3-amino-sulphonylphenylamino)- red N-methyl-1,9-anthrapyridone194 7-(2-hydroxyethyl)-amino-sulphonyl- red 3,4-phthaloyl-acridone195 7-(3-methoxypropyl)-amino-sulphonyl- 2-amino-3,4-phthaloyl-acridone196 1,8-naphthoylene-benzimidazole-Bz-3- yellow sulphonic acid methylamide197 1,8-naphthoylene-benzimidazole-4- yellow sulphonic acid amide198 1,8-naphthoylene-benzimidazole-4,5- yellow dicarboxylic acid-(2-methoxy-ethylimide)- Bz-3-sulphonic acid ethylamide199 phthaloylene-(1,8-naphthopyrimidine)- yellow 3- or 6-sulphonic acid amide200 4-(3-amino-sulphonyl-phenyl-amino)- yellow 1,9-isothiazolo-anthrone201 5-(3-amino-sulphonyl-phenyl-amino)- yellow 1,9-isothiazolo-anthrone202 4-(3-methylamino-sulphonyl-phenyl- yellow amino)-1,9-pyrazolo-anthrone203 5-[3-(2-methoxyethyl-amino-sulphonyl)- yellow phenyl-amino]-1,9-pyrazolo-anthrone______________________________________

EXAMPLE 204

100 Parts polyethylene terephthalate filaments are dyed in a dyebath consisting of

1 part 4-phenylamino-3-nitrobenzene-sulphonic acid amide

3 parts oleic acid ethanolamide

3 parts oleyl alcohol eicosaethylene glycol ether

12 parts of water and

1600 parts tetrachloroethylene

at 115.degree. C for 30 minutes while the liquor is vividly circulating, they are centrifuged and rinsed with tetrachloroethylene at 40.degree. C for 5 minutes. A strong greenish yellow dyeing of very good fastness to sublimation, washing and light is obtained.

An equally satisfactory dyeing is obtained when the tetrachloroethylene is replaced with the same amount of 1,1,2-trichloroethane.

When 1 part 4-phenylamino-3-nitrobenzene-sulphonamide is replaced with a mixture of 0.5 parts 4-phenylamino-3-nitrobenzene-sulphonic acid amide and 0.5 parts 4-(4-methoxy-phenylamino)-3-nitrobenzene-sulphonamide, then a somewhat more reddish strong dyeing is obtained.

Similar dyeings are also obtained when the polyethylene terephthalate filaments are replaced with fibres of anion-modified polyethylene terephthalate (Dacron 64) or anion-modified polyhexamethylene-diamine adipate (Nylon T 844).

The dyestuff used in Example 204 had been prepared as follows: 900 parts of n-butanol saturated with ammonia are mixed with 550 parts of 79% 4-chloro-3-nitrobenzene sulphochloride and the mixture is stirred at 55.degree.-60.degree. C for 1 hour. 200 Parts aniline were added and the mixture was heated to boiling temperature while slowly introducing ammonia, until the dyestuff formation was completed. After cooling, the crystallised product was filtered off with suction, washed with methanol and water and after drying there were obtained 460 parts 4-phenylamino-3-nitrobenzene-sulphonic acid amide = 92% of theory; m.p. 155.degree. C.

EXAMPLE 205

100 Parts of polycarbonate filaments are dyed in a dyebath consisting of

1 part 4-(4-methoxy-phenylamino)-3-nitrobenzene-sulphonic acid amide

2.5 parts oleic acid ethanolamide

2.5 parts oleyl alcohol eicosaethylene glycol ether

10 parts of water and

1000 parts tetrachloroethylene

as described in Example 204. A yellow dyeing of very good fastness to sublimation, washing and light is obtained.

When the dyestuffs given in Examples 204 and 205 were replaced with the same amount of one of the dyestuffs listed in the following Table, then dyeings of equally satisfactory fastness properties were obtained in the shades stated in the Table:

__________________________________________________________________________Example Dyestuff Shade__________________________________________________________________________206 4-(4-ethoxy-phenylamino)-3-nitro- reddish benzene-sulphonic acid methylamide yellow207 4-(2-methoxy-phenylamino)-3-nitro- reddish benzene-sulphonic acid dimethylamide yellow208 4-phenylamino-3-nitro-benzene-sulphonic yellow acid-(di-2-hydroxyethyl)-amide209 4-(4-phenyl-phenylamino)-3-nitro- yellow benzene-sulphonic acid amide210 4-(4-phenoxy-phenylamino)-3-nitro- reddish benzene-sulphonic acid yellow211 4-(4-azobenzeneamino)-3-nitro-benzene- reddish sulphonic acid-(di-2-hydroxyethyl-amide yellow212 4-[4-(2-hydroxyethoxy)-phenylamino]- reddish 3-nitro-benzene-sulphonic acid phenyl- yellow amide213 4-(4-benzyloxy-phenylamino)-3-nitro- reddish benzene-sulphonic acid morpholide yellow214 4-(3-methoxy-phenylamino)-3-nitro- reddish benzene-sulphonic acid-(4-aminosulphonyl- yellow phenyl)-amide215 4-(4-methoxycarbonyl-phenylamino)-3- greenish nitro-benzene-sulphonic acid-(2-hydroxy- yellow ethyl)-amide216 4-(2,4-dimethoxy-phenylamino)-3-nitro- reddish benzene-sulphonic acid amide yellow217 4-(4-carboxy-phenylamino)-3-nitro- greenish benzene-sulphonic acid ethylamide yellow218 4-[4-(2-hydroxyethyl-aminosulphonyl)- greenish phenylamino]-benzene-sulphonic acid- yellow (2-hydroxyethyl)-amide219 4-(3-fluoro-phenylamino)-3-nitro- greenish benzene-sulphonic acid-(2-methoxyethyl)- yellow amide220 4-(3-trifluoromethyl-phenylamino)-3- greenish nitro-benzene-sulphonic acid-(2-cyano- yellow ethyl)-amide221 4-(3,4-dichloro-phenylamino)-3-nitro- greenish benzene-sulphonic acid-(3-methoxypropyl)- yellow amide222 4-(3-cyano-phenylamino)-3-nitro- yellow benzene-sulphonic acid-(4-methylamino- carbonyl-phenyl)-amide223 4-(2-nitro-phenylamino)-3-nitro- greenish benzene-sulphonic acid piperidide yellow224 4-(4-methyl-phenylamino)-3-nitro- yellow benzene-sulphonic acid amide225 4-(4-ethyl-phenylamino)-3-nitro- yellow benzene-sulphonic acid[4-(2-hydroxy- ethoxy)-phenyl]-amide226 4-(4-aminosulphonyl-phenylamino)-3- greenish nitro-benzene-sulphonic acid-(di-2-hydroxy- yellow ethyl)-amide227 4-(4-aminosulphonyl-phenylamino)-3- greenish nitro-benzene-sulphonic acid-(3-diethyl- yellow amino-sulphonyl-phenyl)-amide228 4-(4-acetylamino-phenylamino)-3- yellow nitro-benzene-sulphonic acid ethylamide229 4-(4-methylsulphonylamino-phenylamino)- yellow 3-nitro-benzene-sulphonic acid phenylamide230 4-(4-methylsulphonylamino-phenylamino)- yellow 3-nitro-benzene-sulphonic acid-(2-hydroxy- ethyl)-amide231 4-phenylamino-3-nitro-benzene-sulphonic greenish acid-(4-aminosulphonyl-phenyl)-amide yellow232 4-(4-methoxy-phenylamino)-3-nitro- reddish benzene-sulphonic acid-(3-methylamino- yellow sulphonyl-phenyl)-amide233 4-(4-ethoxy-phenylamino)-3-nitro- reddish benzene-sulphonic acid-[3-(2-cyanoethyl- yellow aminosulphonyl)-phenyl]-amide234 4-(4-methyl-phenylamino)-3-nitro- yellow benzene-sulphonic acid-(4-aminosulphonyl- phenyl)-amide235 4-(3-trifluoromethyl-phenylamino)-3- greenish nitro-benzene-sulphonic acid-[ 3-(2-cyano- yellow ethyl-2-hydroxyethyl-aminosulphonyl)- phenyl]-amide236 4-phenylamino-3-nitro-benzene-sulphonic greenish acid-[4-(2-aminosulphonylethoxy)-phenyl]- yellow amide237 4-[4-(3-aminosulphonyl-propoxy)- reddish phenyl-amino]-3-nitro-benzene-sulphonic yellow acid-(3-chloro-phenyl)-amide238 4-phenylamino-3-nitro-benzene-sulphonic yellow acid-(4-aminosulphonyl-phenyl) ester239 4-(4-methoxy-phenylamino)-3-nitrobenzene- reddish sulphonic acid-(3-methylamino-sulphonyl- yellow phenyl) ester240 4-(3-ethoxy-phenylamino)-3-nitrobenzene- reddish sulphonic acid-[4-(di-2-hydroxy-ethyl- yellow sulphonylamino)-phenyl] ester241 4-(4-aminocarbonyl-phenylamino)-3- greenish nitrobenzene-sulphonic acid-(4-ethylamino- yellow sulphonyl-phenyl) ester242 4-(3-acetylamino-phenylamino)-3-nitro- yellow benzene-sulphonic acid-(4-aminosulphonyl- phenyl) ester243 4-phenylamino-3-nitro-benzoic acid yellow (4-aminosulphonyl-phenyl) amide244 4-(4-ethoxyphenylamino)-3-nitro- reddish benzoic acid-[3-(2-hydroxyethylamino- yellow sulphonyl)-phenyl]-amide245 4-(2,4-dimethoxy-phenylamino)-3-nitro- reddish benzoic acid-(4-methylaminosulphonyl- yellow phenyl)-amide246 4-(4-methyl-phenylamino)-3-nitro- yellow benzoic acid-(3-methylaminosulphonyl- phenyl)-amide247 4-(4-nitro-phenylamino)-3-nitro- yellow benzoic acid-(3-pyrrolidinosulphonyl- phenyl)-amide248 4-(3-bromo-phenylamino)-3-nitro- yellow benzoic acid-(4-hydroxy-3-n-propyl- amino-sulphonyl-phenyl)-amide249 4-(4-acetylamino-phenylamino)-3-nitro- yellow benzoic acid-(4-thiomorpholinosulphonyl- phenyl)-amide250 4-(4-methylsulphonylamino-phenylamino)- yellow 3-nitro-benzoic acid-(3-dimethylamino- sulphonyl-phenyl)-amide251 4-phenylamino-3-nitro-benzoic acid-(4- yellow aminosulphonyl-phenyl) ester252 4-(4-methoxy-phenylamino)-3-nitro- yellow benzoic acid-(3-methylaminosulphonyl- phenyl) ester253 4-(3-methylsulphonylamino-phenylamino)- yellow 3-nitro-benzoic acid-[4-(3-hydroxypropyl- aminosulphonyl)-phenyl] ester254 4-(4-methylsulphonyl-phenylamino)-3- greenish nitro-benzene sulphonic acid-4-(amino- yellow sulphonyl-phenyl)-amide255 4-(4-methylsulphonyl-phenylamino)-3-nitro- greenish benzene sulphonic acid-(2-hydroxyethyl)- yellow amide256 4-(3-hydroxymethyl-phenylamino)-3- yellow nitro-benzene-sulphonic acid-(4-methyl- amino-sulphonyl-phenyl)-amide257 4-(3-hydroxymethylphenylamino)-3- yellow nitro-benzene-sulphonic acid-morpholide258 4-(4-hydroxyethyl-phenylamino)-3-nitro- yellow benzene-sulphonic acid-(3-aminosulphonyl- phenyl)-amide259 4-(4-hydroxyethyl-phenylamino)-3-nitro- yellow benzene-sulphonic acid amide__________________________________________________________________________

EXAMPLE 260

100 Parts of yarn of polyethylene terephthalate fibres are dyed in a dyebath consisting of

1 part of the quinophthalone dyestuff of the formula ##STR152##

2.5 parts oleic acid ethanolamide

2.5 parts oleyl alcohol

10 parts of water and

1600 parts tetrachloroethylene

as described in Example 204. A clear yellow dyeing is obtained, which is characterised by good fastness to sublimation, washing and light.

An equally satisfactory dyeing is obtained when the above quinophthalone-sulphonamide dyestuff is replaced with a bromination product which contains about 1 bromine atom per molecule and can be obtained in known manner by bromination in nitrobenzene or glacial acetic acid.

Clear yellow dyeings are also obtained when the dyestuff mentioned in Example 260 is replaced with equal amounts of the quinophthalone-sulphonic acid amides listed in the following Table:

__________________________________________________________________________ ##STR153## Example R.sub.1 R.sub.2 R.sub.3 ##STR154##__________________________________________________________________________261 H H H NHCH.sub.3262 H H H N(CH.sub.3).sub.2263 H H H NHC.sub.2 H.sub.5264 H H H NHCH.sub.2CH.sub.2OH265 H H H N(CH.sub.2CH.sub.2OH).sub.2266 H H H NHCH.sub.2CH.sub.2CN267 Cl H H ##STR155##268 Br H H NH.sub.2269 Cl Cl H NHCH.sub.3270 NO.sub.2 H H NH.sub.2271 CH.sub.3 O H H NHCH.sub.2CH.sub.2OH272 CH.sub.3 . CO . NH H H N(CH.sub.3).sub.2273 H H CH.sub.3 NH.sub.2274 H H CH.sub.3 O NH.sub.2__________________________________________________________________________

Greenish yellow dyeings are obtained when the quinophthalone-sulphonamide dyestuff mentioned in Example 260 is replaced with equal parts of one of the methine dyestuffs of the formulae ##STR156## or with a styryl dyestuff of the formula ##STR157##

EXAMPLE 275

100 Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperature, without previous cleaning, into a dyebath prepared from

1 part 1 -amino-4-hydroxy-2-[4-(4'-hydroxyanilinosulphonyl)-phenoxy]-anthraquinone and

1000 parts tetrachloroethylene.

The bath is heated to 115.degree. C within 10 minutes and kept at the same temperature for 30 minutes, while the liquor is vividly circulating. The liquor is then separated and the dyed material is rinsed with fresh solvent at about 40.degree. C for 5 minutes. After separating of the rinsing liquor, the dyed material is centrifuged and dried in an air current.

There is obtained a strong red dyeing of excellent fastness to washing, light, rubbing and sublimation.

An equivalent red dyeing was obtained in the same way on a knitted fabric of poly-.epsilon.-caprolactame.

EXAMPLE 276

50 Parts of a fabric of polyester fibres are introduced at room temperature into a dyebath prepared from

1 part 1-amino-4-hydroxy-2-[4-(4'-hydroxyanilinosulphonyl)-phenoxy]-anthraquinone and

1,5 parts oleic acid ethanolamide

1,5 parts oleyl alcohol eicosaethylene glycol ether

6 parts of water and

500 parts tetrachloroethylene.

The bath is heated to 120.degree. C within 10 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. After separation of the dye liquor, the dyed material is rinsed with fresh solvent at 40.degree. C and, after removal of the rinsing liquor, dried in an air current. A brilliant red dyeing of excellent fastness to washing, rubbing, light and sublimation is obtained.

EXAMPLE 277

100 parts of fibre yarn of poly-.epsilon.-caprolactame are introduced at room temperature into a dyebath containing

1 part 1,4-diamino-2-[4-(4-hydroxyanilinosulphonyl)-phenylthio]-anthraquinone in

1000 parts tetrachloroethylene.

The bath is heated to 100.degree. C within 20 minutes and kept at the same temperature for 40 minutes while the liquor is vividly circulating. After this period of time, the liquor is separated, the dyeing is briefly rinsed with fresh solvent and dried in an air current after centrifuging. A brilliant reddish blue dyeing of excellent fastness to washing, light, rubbing and sublimation is obtained.

An equivalent dyeing was obtained in the same manner on a yarn of poly-hexamethylene diamine adipate fibres.

EXAMPLE 278

100 Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperature, without previous cleaning, into a dyebath prepared from

1 part 4-(4-hydroxyphenylamino)-3-nitro-benzenesulphonic acid-4-(hydroxyphenyl)-amide and

1000 parts tetrachloroethylene.

The bath is heated to 115.degree. C within 10 minutes and kept at the same temperature for 30 minutes, while the liquor is vividly circulating. The liquor is then separated and the dyed material is rinsed with fresh solvent at about 40.degree. C for 5 minutes. After separating of the rinsing liquor, the dyed material is centrifuged and dried in an air current. A strong yellow dyeing of excellent fastness to washing, rubbing, light and sublimation is obtained.

An equivalent yellow dyeing was obtained in the same manner on a fabric of poly-.epsilon.-caprolactame fibres.

EXAMPLE 279

50 Parts of a fabric of polyester fibres are introduced at room temperature into a dyebath prepared from

1 part 4-(4-hydroxyphenylamino)-3-nitro-benzenesulphonic acid-(4-hydroxyphenyl)-amide

1,5 parts oleic acid ethanolamide

1,5 parts oleyl alcohol eicosaethylene glycol ether

6 parts of water and

500 parts tetrachloroethylene.

The bath is heated at 120.degree. C within 10 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. After separation of the dye liquor, the dyed material is rinsed with fresh solvent at 40.degree. C and, after removal of the rinsing liquor, dried in an air current. A brilliant yellow dyeing of excellent fastness to washing, rubbing, light and sublimation is obtained.

Claims

1. A process for dyeing synthetic fiber material by exhaustion comprising introducing synthetic fiber material into a dyebath which is a dispersion consisting essentially of

A. organic solvent;

B. nitro dyestuff containing 1 to 3 sulfonamide groups and largely insoluble in said dyebath; and

C. up to 1% by weight of said organic solvent of water; said organic solvent consisting of water immiscible aliphatic halogenated hydrocarbon; and dyeing at a temperature of 60.degree. to 170.degree. C for 10-60 minutes until the dyebath is exhausted;

said nitro dyestuff free of reactive groups, acid groups and carboxamide groups having the formula ##STR158## in which R.sub.1 means hydrogen, a halogen atom, a trifluoro, cyano, hydroxy, C.sub.1 -C.sub.4 -alkyl or -alkoxy, a hydromethyl or -ethyl, a hydroxy-ethylene-oxy, acylamino, alkylsulphonylamino, alkylsulphone, carboxamido, aminosulphonylalkylene-amino or sulphonamide group;

R.sub.2 means hydrogen or a C.sub.1 -C.sub.4 -alkoxy group;

R.sub.3 means hydrogen, a halogen atom, a hydroxy, hydroxyethylene-oxy, carboxamido, aminosulphonyl-alkylene-oxy or sulphonamide group;

X stands for the group --SO.sub.2 -- or --CO; and

Y stands for --NH-- or --O--,

with the proviso that one of the radicals R.sub.1, R.sub.3 or ##STR159## is a sulphonamide group or a radical containing a sulphonamide group.

2. Process of claim 1 in which said nitro dyestuff has the formula ##STR160##

3. Process for dyeing synthetic fiber material by exhaustion comprising introducing synthetic fiber material into a dyebath which is a dispersion consisting essentially of

A. organic solvent;

B. nitro dyestuff containing 1 to 3 sulfonamide groups and largely insoluble in said dyebath; and

C. up to 1% by weight of said organic solvent of water; said organic solvent consisting of water immiscible aliphatic halogenated hydrocarbon; and dyeing at a temperature of 60.degree. C to 170.degree. C for 10-60 minutes until the dyebath is exhausted;

said nitro dyestuff free of reactive groups, acid groups and carboxamide groups having the formula ##STR161## in which R.sub.1 means hydrogen, a C.sub.1 -C.sub.4 -alkyl or -alkoxy group, halogen, a trifluoromethyl, nitro, hydroxymethyl, hydroxyethyl, phenyl, phenoxy, phenylazo, benzyloxy, carboxy, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -acylamino, C.sub.1 -C.sub.4 -alkylsulphonyl or sulphonamide group;

R.sub.2 means hydrogen, halogen or a C.sub.1 -C.sub.4 -alkoxy group; and D means a sulphonamide group.

4. The process of claim 1 in which said synthetic fiber material is polyester, polyamide, cellulose, triacetate, cellulose 21/2 acetate, polyacrylonitrile, or polyurethane.

5. The process of claim 1 in which said synthetic fiber material is polyester.

6. The process of claim 1 in which said synthetic fiber material is polyamide.

7. The process of claim 1 in which said dyebath contains 0.05 to 2% by weight of non-ionic dyeing auxiliary based on the weight of said aliphatic halogenated hydrocarbon.