HK1142620A - Disperse dyes, their preparation and use - Google Patents

Description

Disperse dyes, their preparation and use

The present invention relates to disperse azo dyes in which a acetophenone ester is attached to a chromophore. Dyes comprising such structural elements are known and are described, for example, in WO 05/056690.

Disperse azo dyes in which the acetophenone ester is substituted by another phenyl or phenoxy group have been found to have outstanding properties, and the dyeings prepared from them are notable for good wash fastness and outstanding sublimation fastness. More specifically, such dyeings meet the special requirements of industrial laundering, wherein the fabric is exposed to high temperatures after the wash cycle.

Surprisingly, we have found that the dyes of the present invention, despite their relatively high molecular weight, are readily dyeable on polyester and polyester blend fabrics.

The present invention provides dyes of the general formula (I):

wherein

D is the residue of a diazo component;

R¹is hydrogen, C₁-C₆Alkyl radical, C₁-C₄Alkoxy, hydroxy, halo, -NHCHO, -NHCO-C₁-C₆Alkyl or-NHSO₂-C₁-C₆An alkyl group;

R²is hydrogen, C₁-C₆Alkyl radical, C₁-C₄Alkoxy or halogen;

R³is hydrogen, C₁-C₆Alkyl, substituted C₁-C₆Alkyl radical, C₃-C₄Alkenyl orOr substituted C₃-C₄An alkenyl group; or

R²And R³Combined to form a group-C H (CH)₃)CH₂C(CH₃)₂-, wherein the carbon atom marked is attached to the benzene nucleus;

R⁴is hydrogen or C₁-C₆An alkyl group;

R⁵is hydrogen or C₁-C₆An alkyl group;

R⁶is hydrogen or C₁-C₆An alkyl group;

x is phenyl, thiophenyl, phenylsulfonyl or phenoxy;

n is 0, 1 or 2; and

m is 0 or 1.

The residue D of the diazo component is in particular the residue customary in the art of disperse dyes and is known to the person skilled in the art.

Preferably, D

A group of formula (IIa)

Wherein

T¹And T²Independently of one another hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Alkoxy, cyano, -SO₂-C₁-C₄Alkyl or nitro; and

T⁴and T³Independently hydrogen, halogen, trifluoromethyl, cyano, -SO₂CH₃-SCN or nitro;

provided that T is¹、T²、T³And T⁴At least one of which is not hydrogen;

or a group of the formula (IIb)

Wherein

T⁵And T⁵' is independently hydrogen or halogen; and

T⁶is hydrogen, -SO₂CH₃、-SCN、C₁-C₄Alkoxy, halogen, cyano or nitro;

provided that T is⁵、T⁵' and T⁶At least one of which is not hydrogen;

or a group of the formula (IIc)

Wherein

T¹²Is hydrogen or halogen;

or a group of the formula (IId)

Wherein

T⁷Is nitro, -CHO, -COCH₃Cyano or a group of the formula

Wherein T is¹⁰Is hydrogen, halogen, nitro or cyano;

T⁸is hydrogen, (C)₁-C₆) Alkyl or halogen; and

T⁹is nitro, cyano or-COCH₃or-COOT¹¹(ii) a Wherein T is¹¹Is C₁-C₄An alkyl group;

or a group of the formula (IIe)

Wherein T is⁷And T⁸Each as defined above;

or a group of the formula (IIf)

Wherein T is¹³Is phenyl or C₁-C₄An alkylthio group;

or a group of the formula (IIg)

Wherein T is¹⁴Is cyano or-COCH₃or-COOT¹¹Wherein T is¹¹Is C₁-C₄An alkyl group; and T¹⁵Is phenyl or C₁-C₄An alkyl group;

or a group of the formula (IIh)

Wherein T is¹⁴As defined above and T¹⁶Is C₁-C₄An alkyl group;

or a group of the formula (IIi)

Wherein T is¹⁷Is cyanomethyl, benzyl or allyl;

or a group of the formula (IIj)

C₁-C₆Alkyl radical R¹～R⁷May be linear or branched and is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl.

Similar considerations apply to C₁-C₆An alkoxy group.

Substituted C₁-C₆Alkyl radical R³Specifically selected from halogen, cyano, hydroxy, C₁-C₆Alkoxy, -COO-C₁-C₆Alkyl, -OCOO-C₁-C₆Alkyl and-OCO-C₁-C₆1 to 3 substituents of the alkyl group.

C₃-C₄Alkenyl radical R³Specifically, allyl is mentioned.

Halogen is preferably chlorine or bromine.

R¹Preferably hydrogen, chloro, methyl, ethyl, hydroxy, methoxy, ethoxy, acetylamino, propionylamino, methylsulfonylamino or ethylsulfonylamino.

R²Preferably hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy.

R³Preferably hydrogen, methyl, ethyl, propyl, butyl, methoxyethyl, cyanoethyl, C₂H₄OCOCH₃、C₂H₄OCOC₂H₅、C₂H₄COOCH₃、C₂H₄COOC₂H₅Or an allyl group.

R⁴、R⁵And R⁶Each is preferably methyl or hydrogen, more preferably hydrogen.

X is preferably phenyl or phenoxy, and more preferably phenyl.

n is preferably 0 or 1, more preferably 0.

m is preferably 1.

m + n is preferably 1.

Preferred dyes according to the invention correspond to the general formula (Ia)

Wherein T is¹～T⁴、R¹～R⁶M and n are each as defined above.

Dyes of the type which are particularly preferred according to the invention correspond to the general formula (Iaa)

Wherein

T¹Is nitro;

T³is hydrogen, cyano, chlorine or bromine;

T⁴hydrogen, cyano, nitro, chlorine, bromine or trifluoromethyl;

R¹is hydrogen, hydroxy, methyl, acetylamino or propionylamino;

R²is hydrogen, chlorine, methyl or methoxy;

R³hydrogen, methyl, ethyl, butyl or allyl.

Further preferred dyes according to the invention correspond to the general formula (Ib)

Wherein T is¹～T⁴、R¹～R⁶M and n are each as defined above.

Dyes of the type which are particularly preferred according to the invention correspond to the general formula (Iba)

Wherein

T¹Is nitro;

T³is hydrogen, cyano, chlorine or bromine;

T⁴is hydrogen,Cyano, nitro, chloro, bromo, or trifluoromethyl;

R¹is hydrogen, hydroxy, methyl, acetylamino or propionylamino;

R²is hydrogen, chlorine, methyl or methoxy;

R³hydrogen, methyl, ethyl, butyl or allyl.

The dyes of the general formula (I) according to the invention can be prepared by methods known to the person skilled in the art.

For example, diazotizing and coupling the compound of the formula (III) on to the compound of the formula (IV),

D-NH₂ (III)

wherein D is as defined above, and wherein,

wherein R is¹～R⁶X, m and n are each as defined above.

The compounds of the formula (III) are generally diazotized in a known manner, for example in an acidic aqueous medium, for example in an aqueous medium made acidic with hydrochloric acid or sulfuric acid, with sodium nitrite, or in dilute sulfuric acid, phosphoric acid or a mixture of acetic acid and propionic acid with nitrosylsulfuric acid. The preferable temperature range is 0-15 ℃.

These diazotized compounds are likewise coupled in a known manner to the compounds of the formula (IV), for example in an acidic, aqueous-organic or organic medium, particularly advantageously at temperatures below 10 ℃. The acid used is in particular sulfuric acid, acetic acid or propionic acid.

These compounds of the general formulae (III) and (IV) are known and can be prepared by known methods.

The dyes of the general formula (I) according to the invention are outstandingly suitable for dyeing and printing hydrophobic materials, since the dyeings and prints obtained are notable for a level shade and high durability.

Of note are good wash fastness, especially in combination with very good sublimation fastness.

It has further been determined that the disperse dyes of the present invention are outstandingly suitable for the continuous dyeing of polyester-cotton blends, for example for use in work clothes. In particular, the moisture resistance achieved according to the "Hoechst binding test" is outstanding, the "Hoechst binding test" being particularly relevant for this application and in which the dyed material is exposed to a temperature of 190 ℃ for 5 minutes before the ISO 105-C05 test.

The present invention therefore also provides for the use of the dyes of the formula I for dyeing and printing hydrophobic materials, and also for dyeing and printing such materials in conventional steps, using one or more dyes of the formula (I) according to the invention as colorant.

The hydrophobic materials mentioned may be of synthetic or cellulosic origin. Hydrophobic materials contemplated include, for example, diacetate cellulose, triacetate cellulose, polyamides, and in particular macromolecular polyesters. The material consisting of macromolecular polyester is in particular a material based on polyethylene terephthalate.

These hydrophobic synthetic materials can be in sheet-like or thread-like structures and can be processed, for example, into yarns or woven or knitted fabrics. Preference is given to fibrous textile materials, which can also be present, for example, in the form of microfibers.

The dyeing in accordance with the use according to the invention can be carried out in a conventional manner, preferably in aqueous dispersion, if appropriate in the presence of a carrier, by the exhaust process at from 80 to about 110 ℃ or by the HT process at from 110 to 140 ℃ in a dyeing autoclave, and also by the so-called thermosetting process (thermofix method) in which the fabric is padded with a dyeing liquor and subsequently fixed/fixed at from about 180 to 230 ℃.

The printing of the materials mentioned can be carried out in a manner known per se by incorporating the dyes of the general formula (I) according to the invention in a printing paste and fixing the dyes by treating the textiles printed therewith with HT steam, high-pressure steam or dry heat, if appropriate in the presence of a carrier, at temperatures of from 180 to 230 ℃.

When the dyes of the general formula (I) according to the invention are used in dyeing liquors, padding liquors or printing pastes, they should be in a very finely divided state.

The dye is converted in the customary manner into a finely divided state by slurrying the ready-made dye together with a dispersant in a liquid medium, preferably in water, and subjecting the mixture to shear forces to mechanically break up the original dye particles to an optimum specific surface area and to minimize precipitation of the dye. This is done in a suitable mill, such as a ball mill or a sand mill. The particle size of the dye is generally between 0.5 and 5 μm and preferably equal to about 1 μm.

The dispersant used in the milling operation may be nonionic or anionic. Nonionic dispersants include, for example, the reaction products of alkylene oxides, such as ethylene oxide or propylene oxide, with alkylatable compounds, such as fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxamides. Anionic dispersants are, for example, lignosulfonates, alkyl-or alkylaryl sulfonates or alkylaryl polyglycol ether sulfates.

The dye preparations thus obtained should be pourable for most applications. Thus, the dye and dispersant content is limited in these cases. Overall, these dispersions are adjusted to a dye content of up to 50% by weight and a dispersant content of up to about 25% by weight. For reasons of economy, the dye content is in most cases not less than 15% by weight.

The dispersion may also contain further auxiliaries, for example auxiliaries which act as oxidizing agents, such as sodium m-nitrobenzenesulfonate, or fungicidal agents, such as sodium o-phenylphenol and sodium pentachlorophenolate, and in particular the so-called "acid donors", examples being butyrolactone, monochloroacetamide, sodium chloroacetate, sodium dichloroacetate, the sodium salt of 3-chloropropionic acid, monosulfates, such as lauryl sulfate, and also sulfates of ethoxylated and propoxylated alcohols, such as butyl glycol sulfate.

The dye dispersions thus obtained are very advantageous for the construction of dyeing liquors and printing pastes.

There are certain fields of application in which powder formulations are preferred. These powders contain the stated dyes, dispersants and other auxiliaries, such as wetting agents, oxidizing agents, preservatives and dust-proofing agents, and the "acid donors" mentioned above.

The preferred method for preparing pulverulent preparations of the dyes consists in removing the liquid from the abovementioned liquid dye dispersions, for example by vacuum drying, freeze drying, drying on a drum dryer, but preferably by spray drying.

These dyeing liquors are prepared by diluting the necessary amount of the above-mentioned dye preparations with a dye medium, preferably water, so that a bath ratio of 1: 5 to 1: 50 for dyeing is obtained. Furthermore, it is generally customary to include further dyeing auxiliaries, such as dispersants, wetting agents and fixing auxiliaries, in these liquids. Organic and inorganic acids such as acetic acid, succinic acid, boric acid or phosphoric acid are included to set a pH value in the range of 4 to 5, preferably 4.5. It is advantageous to buffer the pH setting and add a sufficient amount of buffer system. The acetic acid/sodium acetate system is an example of an advantageous buffer system.

In order to use the dyes or dye mixtures in textile printing, the necessary amounts of the above-mentioned dye formulations are mixed together with thickeners, for example alkali metal alginates and the like, and, where appropriate, further additives, such as fixing accelerators, wetting agents and oxidizing agents, in a conventional manner to give printing pastes.

The invention also provides inks for digital textile printing by the inkjet process, which comprise the dyes of the general formula (I) according to the invention.

The inks of the invention are preferably aqueous and comprise one or more dyes of the general formula (I) of the invention, for example in an amount of from 0.1 to 50% by weight, preferably in an amount of from 1 to 30% by weight and more preferably in an amount of from 1 to 15% by weight, based on the total weight of the ink. They further comprise in particular from 0.1% to 20% by weight of a dispersant. Suitable dispersants are known to those skilled in the art, are commercially available and include, for example, sulfonated or sulfomethylated lignins, condensation products of aromatic sulfonic acids with formaldehyde, condensation products of substituted or unsubstituted phenols with formaldehyde, polyacrylates and corresponding copolymers, modified polyurethanes and reaction products of alkylene oxides with alkylatable compounds, for example fatty alcohols, fatty amines, fatty acids, carboxamides and substituted or unsubstituted phenols.

The ink of the present invention may further comprise conventional additives such as a viscosity moderating agent to set the viscosity to a range of 1.5 to 40.0mPas in a temperature range of 20 to 50 ℃. Preferred inks have a viscosity in the range of 1.5 to 20mPas and particularly preferred inks have a viscosity in the range of 1.5 to 15 mPas.

Useful viscosity moderators include rheology additives such as polyvinyl caprolactam, polyvinyl pyrrolidone and also copolymers thereof, polyether polyols, associative thickeners, polyureas, sodium alginate, modified galactomannans, polyether ureas, polyurethanes, and nonionic cellulose ethers.

By means of further additives, the inks of the invention can comprise surface-active substances to set the surface tension in the range from 20 to 65mN/m, which are adjusted as appropriate according to the method used (thermal or piezoelectric technique). Useful surface-active substances include, for example, any type of surfactant, preferably nonionic surfactants, butyl diglycol and 1, 2-hexanediol.

These inks may further comprise conventional additives, such as materials inhibiting the growth of fungi and bacteria, in an amount of from 0.01% to 1% by weight, based on the total weight of the ink.

The inks of the present invention may be prepared in conventional manner by mixing the ingredients in water.

Example 1

66.2g of 6-bromo-2, 4-dinitroaniline are suspended in 185ml of acetic acid at room temperature. 7.5ml sulfuric acid (96%) was added with gentle cooling. 45ml of nitroso sulfuric acid (40%) was added dropwise at 15-20 ℃. The mixture is then stirred for one hour at 15-20 ℃. The diazonium salt solution thus obtained was added dropwise to a mixture of 111.6g of 2-biphenyl-4-yl-2-oxoethyl 3- (5-acetamido-2-methoxyphenylamino) propionate, 11 g of acetone and 10g of urea at 5 to 10 ℃ over one hour. Followed by stirring for 1 hour, dilution with 500ml of water, suction filtration, washing with water and drying, to give 86g of the dye of the formula (Iab)

(λ_max[DMF]594nm) produced a blue hue on polyester with good wash and sublimation fastness.

Example 2

51.6g of 2-chloro-4-nitroaniline are stirred with 100ml of water and 85ml of hydrochloric acid (30%) for 18 hours at room temperature. After 160g of ice was added, 40ml of nitrous acid solution (53g/l) was added within 1 to 2 minutes. The mixture was then stirred at no more than 5 ℃ for 2 hours and excess nitrite was subsequently destroyed by sulfamic acid. The diazonium salt solution thus obtained was added dropwise to a solution of 116.3g of 2-biphenyl-4-yl-2-oxoethyl 3- (ethylphenylamino) propionate in 1.41 g of acetone at 0 to 5 ℃ over 1 hour. The mixture is then stirred at 5-10 ℃ for 18 hours and poured onto 6.51 water. The precipitate is filtered off with suction, washed with water and dried, to give 167g of the dye of the formula (Iac)

(λ_max[DMF]514nm) gives a red shade on polyester with good wash fastness and excellent sublimation fastness.

Example 3

14.3g of 2-biphenyl-4-yl-2-oxoethyl 3- { [ 3-acetylamino-4- (2-bromo-4, 6-dinitrophenylazo) phenyl ] ethylamino } propanoate and 1.9g of copper (I) cyanide are stirred in 80ml of N-methylpyrrolidone at 100 ℃ for 2 hours. After cooling, 250ml of methanol was added dropwise to the batch. The precipitate is filtered off with suction and washed with a little methanol and water. The water-wet solid is stirred for one hour in 150ml of hydrochloric acid (10%), filtered with suction and washed with water. Drying under reduced pressure gives 8.8g of the dye of the formula (Iad)

(λ_max[DMF]602nm) dyes polyester to a brilliant blue shade and has good wash fastness and excellent sublimation fastness.

The compounds of examples 4-45 in Table 1 were prepared in analogy to the methods described in examples 1-3.

TABLE 1

Examples	T1	T2	T3	T4	R1	R2	R3	R4	R5	n	m	X	λmax(nm)DMF
														4	NO2	H	Br	NO2	NHCOCH3	OCH3	CH2CH3	H	H	0	1	C6H5	604
5	NO2	H	Cl	NO2	NHCOCH3	OCH3	CH2CH3	H	H	0	1	C6H5	604
														6	NO2	H	H	NO2	NHCOCH3	OCH3	CH2CH3	H	H	0	1	C6H5	582
7	NO2	H	Br	NO2	NHCOCH3	OCH3	CH2CH3	H	H	0	0	C6H5	590

Examples	T1	T2	T3	T4	R1	R2	R3	R4	R5	n	m	X	λmax(nm)DMF
														8	NO2	H	Cl	NO2	NHCOCH3	OCH3	H	H	H	2	0	C6H5	600
9	NO2	H	Cl	NO2	NHCOCH3	OCH3	CH2CH＝CH2	H	H	0	1	C6H5	598
														10	NO2	H	Cl	NO2	NHCOCH3	OCH3	CH3	H	H	0	1	C6H5	600
11	NO2	H	Cl	NO2	NHCOCH3	OCH3	H	H	H	0	1	C6H5	594
														12	NO2	H	Br	NO2	NHCOCH3	OCH3	H	H	H	0	1	OC6H5	594
13	NO2	H	Cl	NO2	NHCOC2H5	OCH3	H	H	H	0	1	C6H5	594
														14	NO2	H	Br	CN	NHCOCH3	OCH3	H	H	H	0	1	C6H5	624
15	NO2	H	Cl	NO2	NHCOCH3	OCH3	H	CH3	H	0	1	C6H5	596
														16	NO2	H	Cl	NO2	NHCOCH3	OCH3	H	H	CH3	0	1	C6H5	592
17	NO2	H	H	NO2	NHCOCH3	H	CH2CH3	H	H	0	1	C6H5	548
														18	NO2	H	Cl	NO2	NHCOCH3	H	CH2CH3	H	H	0	1	C6H5	560
19	NO2	H	CN	NO2	NHCOCH3	H	CH2CH3	H	H	0	0	C6H5	584
														20	NO2	H	Br	NO2	NHCOCH3	H	CH2CH3	H	H	0	1	C6H5	558
21	NO2	H	H	CN	NHCOCH3	H	CH2CH3	H	H	0	1	C6H5	552
														22	NO2	H	Br	CN	NHCOCH3	H	CH2CH3	H	H	0	1	C6H5	584
23	NO2	H	H	Cl	NHCOCH3	H	CH2CH3	H	H	0	1	C6H5	534
														24	NO2	H	H	Cl	NHCOCH3	H	N-butyl	H	H	0	1	C6H5	534
25	NO2	H	H	H	NHCOCH3	H	CH2CH3	H	H	0	1	C6H5	514
														26	NO2	H	H	H	NHCOCH3	Cl	H	H	H	0	1	C6H5	450
27	NO2	H	H	CN	CH3	H	CH2CH3	H	H	0	1	C6H5	548
														28	NO2	H	H	Cl	CH3	H	CH2CH3	H	H	0	1	C6H5	524

Examples	T1	T2	T3	T4	R1	R2	R3	R4	R5	n	m	X	λmax(nm)DMF
														29	NO2	H	Cl	Cl	CH3	H	CH2CH3	H	H	0	1	C6H5	462
30	NO2	H	Br	Cl	CH3	H	CH2CH3	H	H	0	1	C6H5	460
														31	NO2	H	CN	CN	CH3	H	CH2CH3	H	H	0	1	C6H5	598
32	NO2	H	CN	CN	CH3	H	N-butyl	H	H	0	1	C6H5	600
														33	NO2	H	Br	CN	CH3	H	CH2CH3	H	H	0	1	C6H5	560
34	NO2	H	H	CN	H	H	CH2CH3	H	H	0	1	C6H5	536
														35	NO2	H	H	CN	H	H	N-propyl radical	H	H	0	1	C6H5	538
36	NO2	H	Cl	Cl	H	H	CH2CH3	H	H	0	1	C6H5	442
														37	NO2	H	Br	Cl	H	Hl	CH2CH3	H	H	0	1	C6H5	440
38	NO2	H	H	H	H	H	CH2CH3	H	H	0	1	C6H5	488
														39	NO2	H	H	H	H	H	CH2CH3	H	H	0	0	C6H5	476
40	NO2	H	H	CN	H	H	CH2CH3	H	H	0	0	C6H5	522
														41	NO2	H	H	Cl	H	H	CH2CH3	H	H	0	1	OC6H5	514
42	NO2	H	H	H	H	Cl	H	H	H	0	1	C6H5	452
														43	NO2	Cl	H	Cl	H	H	CH2CH3	H	H	0	1	C6H5	510
44	H	NO2	H	H	CH3	H	CH2CH3	H	H	0	1	C6H5	452
														45	CH3	H	CN	CN	NHCOCH3	H	CH2CH3	H	H	0	1	C6H5	532

Example 46

6.5g of 3-amino-5-nitrobenzoisothiazole were introduced into a mixture of 16.6ml of sulfuric acid (96%) and 6ml of phosphoric acid (85%). Then, 6.9ml of nitrososulfuric acid (40%) was added dropwise at 10 to 15 ℃. Subsequently, the mixture was stirred at 10 to 15 ℃ for 4 hours. The diazonium salt solution thus obtained is rapidly added dropwise to a mixture of 12.9g of 2-biphenyl-4-yl-2 oxoethyl 3- (ethylphenylamino) propionate, 250ml of acetone and 1.7g of urea at 0 to 5 ℃. After this time, stirring overnight at room temperature, suction filtration and washing with methanol, then with water and drying, 13.7g of the dye of the formula (Ibb) are obtained

(λ_max[DMF]604nm) dyes the polyester in blue shades and has very good wash and sublimation fastness.

The compounds of examples 47-55 in Table 2 were prepared in analogy to the procedure described in example 46.

TABLE 2

Example 56

A fabric composed of polyester was pad-dyed with a liquid composed of 50g/l of an 8% sodium alginate solution, 100g/l of an 8-12% carob bean flour ether (carob flur ether) solution and 5g/l sodium dihydrogen phosphate in water, and then dried. The moisture absorption was 70%.

The fabric thus pretreated was subsequently printed with an aqueous ink prepared according to the process described above and containing the following components using a drop-on-demand (piezo) ink jet print head:

3.5% of the dye of example 1,

2.5% of Disperbyk 190 dispersant,

30% of 1, 5-pentanediol,

5 percent of diethylene glycol monomethyl ether,

0.01% of Mergal K9N fungicide, and

58.99% water.

The print was fully dried. Fixation was effected with superheated steam at 175 ℃ for 7 minutes. The print is then subjected to alkaline reduction cleaning, rinsed warm and then dried.

Claims (8)

1. A dye of the general formula (I):

wherein

D is the residue of a diazo component;

R¹is hydrogen, C₁-C₆Alkyl radical, C₁-C₄Alkoxy, hydroxy, halo, -NHCHO, -NHCO-C₁-C₆Alkyl or-NHSO₂-C₁-C₆An alkyl group;

R²is hydrogen, C₁-C₆Alkyl radical, C₁-C₄Alkoxy or halogen;

R³is hydrogen, C₁-C₆Alkyl, substituted C₁-C₆Alkyl radical, C₃-C₄Alkenyl or substituted C₃-C₄An alkenyl group;

or R²And R³Combined to form a group-C^*H(CH₃)CH₂C(CH₃)₂-, wherein the carbon atom marked is attached to the benzene nucleus;

R⁴is hydrogen or C₁-C₆An alkyl group;

R⁵is hydrogen or C₁-C₆An alkyl group;

R⁶is hydrogen or C₁-C₆An alkyl group;

x is phenyl, thiophenyl, phenylsulfonyl or phenoxy;

n is 0, 1 or 2; and

m is 0 or 1.

2. The dye according to claim 1, wherein D represents

A radical of the formula (IIa)

Wherein

T¹And T²Independently of one another hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Alkoxy, cyano, -SO₂-C₁-C₄Alkyl or nitro; and

T⁴and T³Independently hydrogen, halogen, trifluoromethyl, cyano, -SO₂CH₃-SCN or nitro;

provided that T is¹、T²、T³And T⁴In (1)At least one is not hydrogen;

or a group of the formula (IIb)

Wherein

T⁵And T⁵' is independently hydrogen or halogen; and

T⁶is hydrogen, -SO₂CH₃、-SCN、C₁-C₄Alkoxy, halogen, cyano or nitro;

provided that T is⁵、T⁵' and T⁶At least one of which is not hydrogen;

or a group of the formula (IIc)

Wherein

T¹²Is hydrogen or halogen;

or a group of the formula (IId)

Wherein

T⁷Is nitro, -CHO, -COCH₃Cyano or a group of the formula

Wherein T is¹⁰Is hydrogen, halogen, nitro or cyano;

T⁸is hydrogen, C₁-C₆Alkyl, phenyl or halogen;

T⁹is nitro, cyano or-COCH₃or-COOT¹¹(ii) a Wherein T is¹¹Is C₁-C₄An alkyl group;

or a group of the formula (IIe)

Wherein T is⁷And T⁸Each as defined above;

or a group of the formula (IIf)

Wherein T is¹³Is phenyl or C₁-C₄An alkylthio group;

or a group of the formula (IIg)

Wherein T is¹⁴Is cyano or-COCH₃or-COOT¹¹Wherein T is¹¹Is C₁-C₄An alkyl group; and T¹⁵Is phenyl or C₁-C₄An alkyl group;

or a group of the formula (IIh)

Wherein T is¹⁴As defined above and T¹⁶Is C₁-C₄An alkyl group;

or a group of the formula (IIi)

Wherein T is¹⁷Is cyanomethyl, benzyl or alkenePropyl;

or a group of the formula (IIj)

3. The dye according to claim 1 and/or 2, wherein

R¹Is hydrogen, chlorine, methyl, ethyl, hydroxyl, methoxy, ethoxy, acetylamino, propionylamino, methylsulfonylamino or ethylsulfonylamino;

R²hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy;

R³is hydrogen, methyl, ethyl, propyl, butyl, methoxyethyl, cyanoethyl, C₂H₄OCOCH₃、C₂H₄OCOC₂H₅、C₂H₄COOCH₃、C₂H₄COOC₂H₅Or an allyl group;

R⁴、R⁵and R⁶Each is methyl or hydrogen;

x is phenyl or phenoxy; and is

m and n are each 0 or 1.

4. The dye according to claim 1 and/or 2, which corresponds to the general formula (Ia):

wherein T is¹～T⁴、R¹～R⁶M and n are each as defined in claim 1.

5. The dye according to claim 4, which corresponds to the general formula (Iaa):

wherein

T¹Is nitro;

T³is hydrogen, cyano, chlorine or bromine;

T⁴hydrogen, cyano, nitro, chlorine, bromine or trifluoromethyl;

R¹is hydrogen, chlorine, hydroxyl, methyl, acetylamino or propionylamino;

R²is hydrogen, chlorine, methyl or methoxy;

R³is hydrogen, methyl, ethyl, butyl or allyl; and is

X is phenyl or phenoxy.

6. A process for the preparation of the dyes of the general formula (I), which comprises diazotizing and coupling a compound of the general formula (III) to a compound of the general formula (IV),

D-NH₂ (III)

wherein D is as defined in claim 1,

wherein R is¹～R⁶X, m and n are each as defined in claim 1.

7. Use of a dye of the general formula I as claimed in claim 1 for dyeing and printing hydrophobic materials.

8. Ink for digital textile printing by the inkjet process, comprising a dye of the general formula (I) as claimed in claim 1.