USRE45686E1

USRE45686E1 - Disperse dyes, their preparation and their use

Info

Publication number: USRE45686E1
Application number: US13/667,106
Authority: US
Inventors: Hartwig Jordan; Stefan Neubauer
Original assignee: Dystar Colours Distribution GmbH
Current assignee: Dystar Colours Distribution GmbH
Priority date: 2006-10-27
Filing date: 2007-10-16
Publication date: 2015-09-29
Also published as: JP5635774B2; ES2670396T3; PT2113011T; WO2008049758A2; CA2667542C; TW200844183A; EP2113011B1; CN101522816A; US20100092670A1; CA2667542A1; BRPI0718192A2; JP2010507700A; WO2008049758A3; US7824450B2; KR101431853B1; MX2009004435A; CN101522816B; EP2113011A2; TWI510558B; KR20090069284A

Abstract

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

where D, R¹to R⁷and n are each as defined in claim 1, processes for their preparation and their use.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371) of PCT/EP2007/061002, filed Oct. 16, 2007, which claims benefit of German application 10 2006 050642.1, filed Oct. 27, 2006.

BACKGROUND OF THE INVENTION

The present invention relates to disperse azo dyes in which a 2-oxoalkyl ester is linked to the chromophore. Dyes having this structural element are already known and described for example in GB 909843, WO95/20014 and WO05/056690. It has now been found that disperse azo dyes in which the structural element in question is linked to further selected structural elements in a certain manner have excellent properties and provide dyeings having excellent wash fastnesses and very good sublimation fastnesses.

BRIEF SUMMARY OF THE INVENTION

The invention relates to a dye of the formula (I)

where

D is the radical of a diazo component;
R¹is hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, halogen, —NHCHO, —NHCO(C₁-C₆)-alkyl, —NHCOaryl, —NHSO₂(C₁-C₆)-alkyl or —NHSO₂aryl;
R²is hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, phenoxy or halogen;
R³is hydrogen, (C₁-C₆)-alkyl, substituted (C₁-C₆)-alkyl, (C₃-C₄)-alkenyl or substituted (C₃-C₄)-alkenyl;
or R²and R³combine to form the radical —C*H(CH₃)CH₂C(CH₃)₂—, where the carbon atom marked by * is attached to the phenyl nucleus;
R⁴is hydrogen, (C₁-C₅)-alkyl or phenyl;
R⁵is (C₁-C₆)-alkyl or substituted (C₁-C₆)-alkyl;
R⁶is hydrogen or (C₁-C₆)-alkyl;
R⁷is hydrogen, (C₁-C₆)-alkyl or phenyl; and
n 0, 1, 2 or 3;
although the compounds of the formulae

shall be excluded. The invention also relates to the process to make the dye and the process of using the dye.

DETAILED DESCRIPTION OF THE INVENTION

D radicals of a diazo component are in particular those customary in the field of disperse dyes and known to one skilled in the art.

Preferably, D represents a group of the formula (IIa)

where

T¹and T²independently are hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, —SO₂(C₁-C₆)-alkyl, —SO₂aryl, cyano, halogen or nitro; and
T⁴and T³independently are hydrogen, halogen, trifluoromethyl, cyano, —SCN, —SO₂CH₃or nitro;
although at least one of T¹, T², T³and T⁴is not hydrogen;
or represents a group of the formula (IIb)

where

T⁵and T^5′independently are hydrogen or halogen; and
T⁶is hydrogen, —SO₂CH₃, —SCN, (C₁-C₄)-alkoxy, halogen or nitro;
although at least one of T⁵, T^5′and T⁶is not hydrogen;
or represents a group of the formula (IIc)

where

T¹²is hydrogen or halogen;
or represents a group of the formula (IId)

where

T⁷is nitro, —CHO, cyano, —COCH₃or a group of the formula

- where T¹⁰is hydrogen, halogen, nitro or cyano;
- T⁸is hydrogen, (C₁-C₆)-alkyl or halogen; and
- T⁹is nitro, cyano, —COCH₃or —COOT¹¹; where T¹¹is (C₁-C₄)-alkyl;
  or represents a group of the formula (IIe)

where T⁷and T⁸are each as defined above;
or represents a group of the formula (IIf)

where T¹³is phenyl or S—(C₁-C₄)-alkyl.

(C₁-C₆)-Alkyl groups may be straight chain or branched and are, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or n-hexyl. A similar logic applies to alkoxy groups, which are methoxy or ethoxy for example. (C₃-C₄)-Alkenyl groups are in particular allyl.

Substituted (C₁-C₆)-alkyl and (C₃-C₄)-alkenyl groups are in particular substituted by 1 to 3 substituents from the group consisting of halogen, cyano, hydroxyl, (C₁-C₆)-alkoxy, —COO(C₁-C₆)-alkyl, —COOaryl, —OCOO(C₁-C₆)-alkyl, —OCOOaryl, —OCO(C₁-C₆)-alkyl, phenyl, —OCOphenyl and phenoxy.

Aryl is in particular phenyl or naphthyl, —NHSO₂aryl is in particular phenylsulfonylamino. Halogen preferably represents chlorine or bromine.

R¹is preferably hydrogen, chlorine, methyl, ethyl, hydroxyl, methoxy, ethoxy, acetylamino, propionylamino, benzoylamino, methylsulfonylamino, ethylsulfonylamino or phenylsulfonylamino.

R²is preferably hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy or phenoxy.

R³is preferably hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl, cyanoethyl, —C₂H₄OCOCH₃, —C₂H₄OCOC₂H₅, —C₂H₄COOCH₃, —C₂H₄COOC₂H₅or allyl.

R⁴and R⁷are each preferably hydrogen, methyl or phenyl, more preferably hydrogen. R⁶is preferably hydrogen or methyl.

R⁵is preferably methyl or ethyl.

n is preferably 0 or 1, more preferably 0.

Preferred dyes according to the present invention conform to the general formula (Ia)

where T¹to T⁴, R¹to R⁷and n are each as defined above, but the compouds of the formula

shall be excluded.

In preferred dyes of the general formula (Ia), R³is not ethyl when R¹is hydrogen and n=0. In further preferred dyes of the general formula (Ia), R³is not n-propyl or n-butyl when R¹is —NHCOCH₃and n=0.

In particularly preferred dyes of the general formula (Ia),

R¹is acetylamino, propionylamino, benzoylamino or methylsulfonylamino;
R²is hydrogen, chlorine, methoxy or ethoxy;
R³is hydrogen, methyl, ethyl, allyl or benzyl;
R⁴is hydrogen or methyl;
R⁵methyl or ethyl;
R⁶is hydrogen or methyl and
R⁷is hydrogen, methyl or phenyl.

Particularly preferred dyes of the general formula (Ia) according to the present invention conform to the general formula (Iaa)

where

T¹is hydrogen, nitro or methyl;
T²is hydrogen, nitro or chlorine;
T³is hydrogen, cyano, chlorine or bromine;
T⁴is hydrogen, cyano, nitro, chlorine, bromine or trifluoromethyl;
R¹is hydrogen, hydroxyl, chlorine, methyl, acetylamino, propionylamino, benzoylamino or methylsulfonylamino;
R²is hydrogen, chlorine, methyl, phenoxy, methoxy or ethoxy;
R³is hydrogen, methyl, ethyl, butyl, benzyl, phenylethyl, phenoxyethyl or allyl;
R⁵is methyl or ethyl; and
R⁴and R⁷are hydrogen, methyl or phenyl;
although the compounds of the formulae

shall be excluded.

In preferred dyes of the general formula (Iaa), R³is not ethyl when R¹is hydrogen. In further preferred dyes of the general formula (Ia), R³is not n-propyl or n-butyl when R¹is —NHCOCH₃.

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

where T¹², R¹to R⁷and n are each as defined above.

Particularly preferred dyes of this type according to the present invention conform to the general formula (Iba)

where

T¹²is hydrogen, chlorine or bromine;
R¹is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
R²is hydrogen, methyl, chlorine or methoxy;
R³is hydrogen, ethyl, butyl, benzyl or allyl; and
R⁵is methyl or ethyl.

Further preferred dyes according to the present invention conform to the general formula (Ic)

where T⁵, T^5′, T⁶, R¹to R⁷and n are each as defined above. 40

Particularly preferred dyes of this type according to the present invention conform to the general formula (Ica)

where

T⁵and T^5′independently are hydrogen or halogen;
T⁶is halogen or nitro;
R¹is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
R²is hydrogen, methyl, chlorine or methoxy;
R³is hydrogen, ethyl, butyl, benzyl or allyl; and
R⁵is methyl or ethyl.

Further preferred dyes according to the present invention conform to the general formula (Id)

where T⁷to T⁹, R¹to R⁷and n are each as defined above.

Particularly preferred dyes of this type according to the present invention conform to the general formula (Ida)

where

T⁷is nitro, —CHO or cyano;
T⁸is hydrogen, methyl or chlorine;
T⁹is nitro, cyano or —COCH₃;
R¹is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
R²is hydrogen, methyl, chlorine or methoxy;
R³is hydrogen, methyl, ethyl, butyl, benzyl, phenoxyethyl or allyl; and
R⁵is methyl or ethyl.

Further particularly preferred dyes of this type according to the present invention conform to the general formula (Idb)

where

T¹⁰is nitro;
T⁹is cyano or —COCH₃;
¹is hydrogen, methyl or acetylamino;
³is methyl, ethyl, butyl or allyl; and
R⁵methyl or ethyl.

Further preferred dyes according to the present invention conform to the general formula (Ie)

where T⁷, T⁸, R¹to R⁷and n are each as defined above and T⁷is in particular nitro, —CHO, COCH₃or cyano.

Particularly preferred dyes of this type according to the present invention conform to the general formula (Iea)

where

T⁷is nitro, —CHO or cyano;
T⁸is hydrogen or chlorine;
R¹is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
R²is hydrogen, methyl, chlorine or methoxy;
R³is hydrogen, methyl, ethyl, butyl, benzyl, phenoxyethyl or allyl; and
R⁵is methyl or ethyl.

Further preferred dyes according to the present invention conform to the general formula (If)

where

T¹³, R¹to R⁷and n are each as defined above.

Particularly preferred dyes of this type according to the present invention conform to the general formula (Ifa)

where

R¹is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
R²is hydrogen, methyl, chlorine or methoxy;
R³is hydrogen, methyl, ethyl, butyl, benzyl, phenoxyethyl or allyl; and
R⁵is methyl or ethyl.

The dyes of the general formula (I) according to the present invention are obtainable using methods known to one skilled in the art.

For instance, a compound of the general formula (III)
D-NH_{2 tm (III)}
where D is as defined above, is diazotized and coupled onto a compound of the general formula (IV)

where R¹to R⁷and n are each as defined above.

The diazotizing of the compounds of the general formula (III) is generally effected in a known manner, for example using sodium nitrite in an aqueous medium rendered acidic, for example with hydrochloric or sulfuric acid, or using nitrosylsulfuric acid in dilute sulfuric acid, phosphoric acid or in a mixture of acetic acid and propionic acid. The preferred temperature range is between 0° C. and 15° C.

The coupling of the diazotized compounds onto the compounds of the general formula (IV) is generally likewise effected in a known manner, for example in an acidic, aqueous, aqueous-organic or organic medium, particularly advantageously at temperatures below 10° C. Acids used are in particular sulfuric acid, acetic acid or propionic acid.

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

The present invention's dyes of the general formula (I) are very useful for dyeing and printing hydrophobic materials, the dyeings and prints obtained being notable for level hues and high service fastnesses. Deserving of particular mention are excellent wash fastnesses and very good sublimation fastnesses.

The present invention thus also provides for the use of the dyes of the general formula I for dyeing and printing hydrophobic materials, i.e., processes for dyeing or printing such materials in a conventional manner wherein one or more dyes of the general formula (I) according to the present invention are used as a colorant.

The hydrophobic materials mentioned may be of synthetic or semisynthetic origin. Useful hydrophobic materials include for example secondary cellulose acetate, cellulose triacetate, polyamides and, in particular, high molecular weight polyesters. Materials of high molecular weight polyester are in particular those based on polyethylene glycol terephthalates.

The hydrophobic synthetic materials can be present in the form of sheet- or threadlike constructions and can have been processed, for example, into yarns or into woven or knit textile materials. Preference is given to fibrous textile materials, which may also be present in the form of microfibers for example.

The dyeing in accordance with the use provided by the present invention can be carried out in a conventional manner, preferably from an aqueous dispersion, if appropriate in the presence of carriers, at between 80 to about 110° C. by the exhaust process or by the HT process in a dyeing autoclave at 110 to 140° C., and also by the so-called thermofix process, in which the fabric is padded with the dyeing liquor and subsequently fixed/set at about 180 to 230° C.

Printing of the materials mentioned can be carried out in a manner known per se by incorporating the dye of the general formula (I) of the present invention in a print paste and treating the fabric printed therewith at temperatures between 180 to 230° C. with HT steam, high-pressure steam or dry heat, if appropriate in the presence of a carrier, to fix the dye.

The dyes of the general formula (I) of the present invention shall be in a very fine state of subdivision when they are used in dyeing liquors, padding liquors or print pastes.

The dyes are converted into the fine state of subdivision in a conventional manner by slurrying the as-fabricated dye together with dispersants in a liquid medium, preferably in water, and subjecting the mixture to the action of shearing forces to mechanically communinute the original dye particles to such an extent that an optimal specific surface area is achieved and sedimentation of the dye is minimized. This is accomplished in suitable mills, such as ball or sand mills. The particle size of the dyes is generally between 0.5 and 5 μm and preferably equal to about 1 μm.

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

The dye preparations thus obtained should be pourable for most applications. Accordingly, the dye and dispersant content is limited in these cases. In general, the dispersions are adjusted to a dye content up to 50 percent by weight and a dispersant content up to about 25 percent by weight. For economic reasons, dye contents are in most cases not allowed to be below 15 percent by weight. The dispersions may also contain still further auxiliaries, for example those which act as an oxidizing agent, for example sodium m-nitrobenzenesulfonate, or fungicidal agents, for example sodium o-phenylphenoxide and sodium pentachlorophenoxide, and particularly so-called “acid donors”, examples being butyrolactone, monochloroacetamide, sodium chloroacetate, sodium dichloroacetate, the sodium salt of 3 -chloropropionic acid, monosulfate esters such as lauryl sulfate for example, and also sulfuric esters of ethoxylated and propoxylated alcohols, for example butylglycol sulfate.

The dye dispersions thus obtained are very advantageous for making up dyeing liquors and print pastes.

There are certain fields of use where powder formulations are preferred. These powders comprise the dye, dispersants and other auxiliaries, for example wetting, oxidizing, preserving and dustproofing agents and the abovementioned “acid donors”.

A preferred method of making pulverulent preparations of dye consists in stripping the above-described liquid dye dispersions of their liquid, for example by vacuum drying, freeze drying, by drying on drum dryers, but preferably by spray drying.

The dyeing liquors are made by diluting the requisite amounts of the above-described dye formulations with the dyeing medium, preferably water, such that a liquor ratio of 5:1 to 50:1 is obtained for dyeing. In addition, it is generally customary to include further dyeing auxiliaries, such as dispersing, wetting and fixing auxiliaries, in the liquors. Organic and inorganic acids such as acetic acid, succinic acid, boric acid or phosphoric acid are included to set a pH in the range from 4 to 5, preferably 4.5. It is advantageous to buffer the pH setting and to add a sufficient amount of a buffering system. The acetic acid/sodium acetate system is an example of an advantageous buffering system.

To use the dye or dye mixture in textile printing, the requisite amounts of the abovementioned dye formulations are kneaded in a conventional manner together with thickeners, for example alkali metal alginates or the like, and if appropriate further additives, for example fixation accelerants, wetting agents and oxidizing agents, to give print pastes.

The present invention also provides inks for digital textile printing by the ink jet process, comprising a present invention dye of the general formula (I).

The inks of the present invention are preferably aqueous and comprise one or more of the present invention's dyes of the general formula (I), for example in amounts of 0.1% to 50% by weight, preferably in amounts of 1% to 30% by weight and more preferably in amounts of 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 one skilled in the art, are commercially available and include for example sulfonated or sulfomethylated lignins, condensation products of aromatic sulfonic acids and formaldehyde, condensation products of substituted or unsubstituted phenol and 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 inks of the present invention may further comprise customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in the temperature range of 20 to 50° C. Preferred inks have a viscosity in the range from 1.5 to 20 mPas and particularly preferred inks have a viscosity in the range from 1.5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example polyvinyl-caprolactam, polyvinylpyrrolidone and also their copolymers, polyetherpolyol, associative thickeners, polyureas, sodium alginates, modified galactomannans, polyetherurea, polyurethane and nonionic cellulose ethers.

By way of further additives, the inks of the present invention may include surface-active substances to set surface tensions in the range from 20 to 65 mN/m, which are if appropriate adapted depending on the process used (thermal or piezo technology). Useful surface-active substances include for example surfactants of any kind, preferably nonionic surfactants, butyldiglycol and 1,2 hexanediol.

The inks may further include customary additives, for example chemical species to inhibit fungal and bacterial growth in amounts from 0.01% to 1% by weight based on the total weight of the ink.

The inks of the present invention can be prepared in conventional manner by mixing the components in water.

EXAMPLE 1

4.6 g of 6-chloro-2,4-dinitroaniline are introduced into a mixture of 9.8 ml of sulfuric acid (96%), 0.5 ml of water and 3.5 ml of nitrosylsulfuric acid (40%) at 30 to 35° C. After 3 hours of stirring at 30-35° C., excess nitrite is destroyed with amidosulfonic acid. The diazonium salt solution thus obtained is expediently added dropwise to a mixture of 7.0 g of 2-oxopropyl 3-[(5-acetylamino-2-methoxyphenyl)ethylamino]-propionate, 50 ml of methanol and 200 g of ice. After stirring for one hour the solids are filtered off with suction, washed with water and dried to leave 7.3 g of the dye of the formula (Iab)

(λ_max[DMF]=606 nm), which dyes polyester in blue hues having good wash and sublimation fastnesses.

EXAMPLE 2

7.5 g of 2-oxopropyl 3-{[3-acetylamino-4-(2,6-dibromo-4-nitrophenylazo)phenyl]-ethylamino}propionate and 2.15 g of copper(I) cyanide are stirred in 30 ml of N-methylpyrrolidone at 80° C. for 4 hours. After cooling, 200 ml of methanol and 30 ml of water are added dropwise. The precipitate is filtered off with suction, washed with 5% hydrochloric acid and water and dried under reduced pressure to leave 4.9 g of the dye of the formula (Iac)

(λ_max[DMF]=612 nm), which dyes polyester in brilliant, blue shades and has excellent wash and sublimation fastnesses.

EXAMPLE 3

Example 2 is repeated except it proceeds from 2-oxopropyl 3-{[3-acetylamino-4-(6-bromo-2,4-dinitrophenylazo)phenyl]ethylamino}propionate and utilizes only one equivalent of copper(I) cyanide. The dye thus obtained has the formula (Iad)

(λ_max[DMF]=602 nm) and dyes polyester in brilliant, blue shades and gives excellent wash and sublimation fastnesses.

Examples 4 to 145 of Table 1 were prepared in a similar manner.

TABLE 1

λ_max

Exam-

(nm)

ple

T¹

T²

T³

T⁴

R¹

R²

R³

R⁵

R⁴

R⁶

R⁷

n

DMF

4

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

CH₂CH₃

CH₃

H

0

604

5

NO₂

H

NO₂

NHCOCH₃

OCH₃

CH₂CH₃

CH₃

H

0

582

6

NO₂

H

Br

CN

NHCOCH₃

OCH₃

CH₂CH₃

CH₃

H

0

632

7

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

CH₂CH₃

C₂H₅

H

0

604

8

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

CH₂CH₃

C₂H₅

H

0

604

9

NO₂

H

NO₂

NHCOCH₃

OCH₃

CH₂CH₃

C₂H₅

H

0

582

10

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

CH₃

H

0

600

11

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

CH₃

H

0

598

12

NO₂

H

NO₂

NHCOCH₃

OCH₃

CH₃

H

0

572

13

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

CH₂CH═CH₂

CH₃

H

0

598

14

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

CH₂CH═CH₂

CH₃

H

0

598

15

NO₂

H

NO₂

NHCOCH₃

OCH₃

CH₂CH═CH₂

CH₃

H

0

574

16

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

CH₂C₆H₅

CH₃

H

0

590

17

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

CH₂C₆H₅

CH₃

H

0

590

18

NO₂

H

NO₂

NHCOCH₃

OCH₃

CH₂C₆H₅

CH₃

H

0

570

19

NO₂

H

CN

NO₂

NHCOCH₃

OCH₃

CH₂C₆H₅

CH₃

H

0

634

20

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

0

592

21

NO₂

H

Cl

NO₂

NHCOCH₃

OC₂H₅

H

CH₃

H

0

594

22

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

0

594

23

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

H

C₂H₅

H

0

594

24

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

H

C₂H₅

H

0

600

25

NO₂

H

NO₂

NHCOCH₃

OCH₃

H

C₂H₅

H

0

574

26

NO₂

H

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

0

574

27

NO₂

H

CF₃

NHCOCH₃

OCH₃

H

CH₃

H

0

542

28

NO₂

H

Br

CN

NHCOCH₃

OCH₃

H

CH₃

H

0

624

29

NO₂

H

Br

CF₃

NHCOCH₃

OCH₃

H

CH₃

H

0

562

30

NO₂

H

Br

NO₂

NHCOC₂H₅

OCH₃

H

CH₃

H

0

596

31

NO₂

H

Cl

NO₂

NHCOC₂H₅

OCH₃

H

CH₃

H

0

596

32

NO₂

H

NO₂

NHCOC₂H₅

OCH₃

H

CH₃

H

0

576

33

NO₂

H

Br

NO₂

NHCOC₆H₅

OCH₃

H

CH₃

H

0

586

34

NO₂

H

Cl

NO₂

NHCOC₆H₅

OCH₃

H

CH₃

H

0

586

35

NO₂

H

NO₂

NHCOC₆H₅

OCH₃

H

CH₃

H

0

572

36

NO₂

Cl

H

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

0

576

37

NO₂

H

Br

NO₂

NHCOC₆H₅

OCH₃

CH₂CH₃

CH₃

H

0

596

38

NO₂

H

Br

NO₂

NHCOC₂H₅

OCH₃

CH₂CH₃

CH₃

H

0

606

39

NO₂

H

Cl

NO₂

NNCOC₂H₅

OCH₃

CH₂CH₃

CH₃

H

0

608

40

NO₂

H

CN

NO₂

NHCOCH₃

OCH₃

CH₂CH₃

CH₃

H

0

648

41

NO₂

H

Br

NO₂

NHCOC₆H₅

H

CH₂CH₃

CH₃

H

0

560

42

NO₂

H

Br

NO₂

NHCOC₂H₅

H

CH₂CH₃

CH₃

H

0

558

43

NO₂

Cl

H

NO₂

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

548

44

NO₂

H

Cl

NO₂

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

560

45

NO₂

H

Cl

NO₂

NHCOCH₃

H

CH₂CH₃

C₂H₅

H

0

560

46

NO₂

H

Br

NO₂

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

558

47

NO₂

H

Cl

NO₂

NHCOCH₃

H

n-C₄H₉

CH₃

H

0

562

48

NO₂

H

Cl

H

NHCOCH₃

H

n-C₄H₉

CH₃

H

0

534

49

NO₂

H

NHCOCH₃

H

n-C₄H₉

CH₃

H

0

516

50

NO₂

H

Br

CN

NHCOCH₃

H

n-C₄H₉

CH₃

H

0

584

51

NO₂

H

CN

NO₂

NHCOCH₃

H

n-C₄H₉

CH₃

H

0

604

52

NO₂

H

NO₂

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

548

53

NO₂

H

CN

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

552

54

NO₂

H

Br

CN

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

582

55

NO₂

H

Cl

CN

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

582

56

NO₂

H

Cl

H

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

534

57

NO₂

H

Br

H

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

530

58

NO₂

H

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

514

59

NO₂

H

Cl

NO₂

NHCOCH₃

H

CH₂C₆H₅

CH₃

H

0

554

60

NO₂

H

CN

NHCOCH₃

H

CH₂C₆H₅

CH₃

H

0

546

61

NO₂

H

Br

NO₂

NHCOCH₃

H

CH₂C₆H₅

CH₃

H

0

552

62

NO₂

H

Cl

H

NHCOCH₃

H

CH₂C₆H₅

CH₃

H

0

524

63

NO₂

H

NO₂

NHCOCH₃

H

CH₂C₆H₅

CH₃

H

0

540

64

NO₂

H

NHCOCH₃

H

CH₂C₆H₅

CH₃

H

0

506

65

H

Cl

H

Cl

NHCOCH₃

H

CH₂C₆H₅

CH₃

H

0

476

66

NO₂

H

Br

CN

NHCOCH₃

H

CH₂C₆H₅

CH₃

H

0

574

67

NO₂

H

CN

NHCOCH₃

H

n-C₄H₉

CH₃

H

0

554

68

NO₂

H

Cl

NO₂

NHCOCH₃

H

CH₂CH═CH₂

CH₃

H

0

556

69

NO₂

H

CN

NHCOCH₃

H

CH₂CH═CH₂

CH₃

H

0

548

70

NO₂

H

Cl

NHSO2CH₃

H

CH₂C₆H₅

CH₃

H

0

534

71

NO₂

H

NHSO2CH₃

H

CH₂C₆H₅

CH₃

H

0

494

72

NO₂

H

CN

CH₃

H

CH₂CH₃

CH₃

H

0

548

73

NO₂

H

CN

CH₃

H

n-C₄H₉

CH₃

H

0

550

74

NO₂

H

Cl

CH₃

H

n-C₄H₉

CH₃

H

0

526

75

NO₂

H

CN

CH₃

H

n-C₄H₉

CH₃

H

0

600

76

NO₂

H

CN

NO₂

CH₃

H

n-C₄H₉

CH₃

H

0

590

77

NO₂

H

Br

CN

CH₃

H

n-C₄H₉

CH₃

H

0

562

78

NO₂

H

Cl

H

CH₃

H

CH₂CH₃

CH₃

H

0

524

79

NO₂

H

Cl

H

CH₂CH₃

CH₃

H

0

512

80

NO₂

H

Cl

H

CH₂CH₃

CH₃

H

0

440

81

NO₂

H

Br

Cl

H

CH₂CH₃

CH₃

H

0

442

82

NO₂

H

Br

H

CH₂CH₃

CH₃

H

0

440

83

NO₂

H

Br

H

CH₂CH₃

CH₃

H

0

508

84

NO₂

Cl

H

Cl

H

CH₂CH₃

CH₃

H

0

512

85

NO₂

H

Br

Cl

H

n-C₄H₉

CH₃

H

0

444

86

NO₂

H

Cl

H

CH₂C₆H₅

CH₃

H

0

432

87

NO₂

H

Br

Cl

H

CH₂C₆H₅

CH₃

H

0

434

88

NO₂

H

Cl

H

CH₂C₆H₅

CH₃

H

0

500

89

NO₂

H

CN

H

CH₂C₆H₅

CH₃

H

0

526

90

NO₂

H

CF₃

H

CH₂C₆H₅

CH₃

H

0

506

91

NO₂

H

Br

H

CH₂C₆H₅

CH₃

H

0

432

92

NO₂

H

Br

H

CH₂C₆H₅

CH₃

H

0

498

93

NO₂

H

Cl

H

CH₂CH₂C₆H₅

CH₃

H

0

440

94

NO₂

H

Br

Cl

H

CH₂CH₂C₆H₅

CH₃

H

0

442

95

NO₂

H

Cl

H

CH₂CH₂OC₆H₅

CH₃

H

0

436

96

NO₂

H

Br

Cl

H

CH₂CH₂OC₆H₅

CH₃

H

0

432

97

NO₂

H

Cl

H

CH₂CH₂OC₆H₅

CH₃

H

0

502

98

NO₂

H

CN

H

CH₂CH₂OC₆H₅

CH₃

H

0

526

99

NO₂

H

Cl

H

CH₂CH₂CN

CH₃

H

0

424

100

NO₂

H

Br

H

CH₂CH₂CN

CH₃

H

0

422

101

NO₂

H

Cl

CH₃

H

CH₂CH₃

CH₃

H

0

462

102

NO₂

H

Br

Cl

CH₃

H

CH₂CH₃

CH₃

H

0

460

103

NO₂

H

Cl

CN

CH₃

H

CH₂CH₃

CH₃

H

0

562

104

NO₂

H

Br

CN

CH₃

H

CH₂CH₃

CH₃

H

0

560

105

NO₂

H

CN

CH₃

H

CH₂CH₃

CH₃

H

0

596

106

NO₂

H

CH₃

H

CH₂CH₃

CH₃

H

0

500

107

NO₂

H

Br

CH₃

H

CH₂CH₃

CH₃

H

0

522

108

NO₂

Cl

H

Cl

CH₃

H

CH₂CH₃

CH₃

H

0

524

109

H

NO₂

H

CH₃

H

CH₂CH₃

CH₃

H

0

452

110

NO₂

Cl

H

CH₂C₆H₅

CH₃

H

0

500

111

NO₂

H

OH

H

CH₂CH₃

CH₃

H

0

494

112

NO₂

H

Cl

OH

H

CH₂CH₃

CH₃

H

0

530

113

NO₂

H

CN

OH

H

CH₂CH₃

CH₃

H

0

544

114

NO₂

H

Cl

OH

H

CH₂CH₃

CH₃

H

0

486

115

NO₂

H

Cl

OC₆H₃

H

CH₃

H

0

478

116

NO₂

H

CN

Cl

OC₆H₃

H

CH₃

H

0

524

117

NO₂

H

Cl

OC₆H₅

H

CH₃

H

0

498

118

NO₂

H

Cl

OC₆H₅

H

CH₃

H

0

444

119

NO₂

H

Cl

H

CH₃

H

0

450

120

NO₂

H

Cl

H

Cl

H

CH₃

H

0

472

121

NO₂

H

Cl

H

C₂H₅

H

0

450

122

NO₂

H

NO₂

NHCOCH₃

Cl

H

CH₃

H

0

520

123

NO₂

H

NHCOCH₃

Cl

H

CH₃

H

0

486

124

NO₂

H

Cl

NO₂

NHCOCH₃

Cl

H

CH₃

H

0

536

125

NO₂

11

Cl

H

NHCOCH₃

Cl

H

CH₃

H

0

508

126

NO₂

H

CN

NHCOCH₃

Cl

H

CH₃

H

0

530

127

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

0

596

128

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

0

596

129

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

CH₃

H

0

592

130

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

1

601

131

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

1

600

132

NO₂

H

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

1

582

133

NO₂

H

Br

CN

NHCOCH₃

OCH₃

H

CH₃

H

1

630

134

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

CH₃

0

594

135

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

CH₃

0

594

136

NO₂

H

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

CH₃

0

576

137

NO₂

H

Cl

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

C₆H₅

0

594

138

NO₂

H

Br

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

C₆H₅

0

594

139

NO₂

H

NO₂

NHCOCH₃

OCH₃

H

CH₃

H

C₆H₅

0

576

140

NO₂

H

Br

NO₂

NHCOCH₃

CH₃

H

CH₃

H

0

558

141

NO₂

H

Cl

NO₂

NHCOCH₃

CH₃

H

CH₃

H

0

558

142

NO₂

H

Cl

H

NHCOCH₃

CH₃

H

CH₃

H

0

532

143

NO₂

H

Br

CN

NHCOCH₃

CH₃

H

CH₃

H

0

584

144

NO₂

H

NO₂

NHCOCH₃

CH₃

H

CH₃

H

0

538

145

CH₃

H

CN

NHCOCH₃

H

CH₂CH₃

CH₃

H

0

532

EXAMPLE 146

4.3 g of 3-amino-5-nitrobenzisothiazole are introduced into a mixture of 11 ml of sulfuric acid (96%) and 4 ml of phosphoric acid (85%). Then, 4.6 ml of nitrosylsulfuric acid (40%) are added dropwise at 10 to 15° C. The mixture is subsequently stirred at 10 to 15° C. for 4 hours. The diazonium salt solution thus obtained is speedily added dropwise to a mixture of 6.6 g of 2-oxopropyl 3-[(5-acetylaminophenyl)ethylamino]-propionate, 100 ml of methanol, 1.1 g of urea and 100 g of ice. The mixture is stirred at room temperature overnight and the precipitate is filtered off with suction, washed with 1:1 methanol/water and dried to leave 7.9 g of the dye of the formula (Ibb)

(λ_max[DMF]=622 nm), which dyes polyester in greenish blue shades and has very good wash and sublimation fastnesses.

Examples 147 to 173 of Table 2 were prepared in a similar manner.

TABLE 2

Exam-						λ_MAX
ple	D	R¹	R²	R³	R⁵	[DMF]

147		NHCOCH₃	OCH₃	H	CH₃	648

148		H	H	CH₂CH₃	CH₃	606

149		H	H	CH₂C₆H₅	CH₃	594

150		CH₃	H	CH₂CH₃	CH₃	618

151		H	H	CH₂CH₃	CH₃	622

152		CH₃	H	CH₂CH₃	CH₃	636

153		CH₃	H	CH₂CH₃	CH₃	562

154		H	H	CH₂CH₃	CH₃	550

155		H	H	CH₂C₆H₅	CH₃	540

156		NHCOCH₃	H	CH₂CH₃	CH₃	564

157		CH₃	H	CH₂CH₃	CH₃	540

158		H	H	CH₂CH₃	CH₃	530

159		NHCOCH₃	H	CH₂CH₃	CH₃	542

160		NHCOCH₃	H	CH₂CH₃	CH₃	596

161		NHCOCH₃	OCH₃	H	CH₃	608

162		NHCOCH₃	H	CH₂CH₃	CH₃	556

163		NHCOCH₃	H	CH₂CH₃	CH₃	526

164		NHCOCH₃	H	CH₂C₆H₅	CH₃	520

165		CH₃	H	CH₂CH₃	CH₃	520

166		NHCOCH₃	H	CH₂CH₃	CH₃	644

167		CH₃	H	CH₂CH₃	CH₃	668

168		H	H	CH₂CH₃	CH₃	650

169		NHCOCH₃	H	CH₂CH₃	CO₃	604

170		CH₃	H	CH₂CH₃	CH₃	607

171		H	H	CH₂CH₃	CH₃	592

172		NHCOCH₃	OCH₃	CH₂CH₃	CH₃	650

173		H	H	CH₂CH₃	CH₃	664

EXAMPLE 174

A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of 8% sodium alginate solution, 100 g/l of 8-12% carob flour ether solution and 5 g/l of monosodium phosphate in water and then dried. The wet pickup is 70%.

The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing

3.5% of the dye of Example 1,
2.5% of Disperbyk 190 dispersant,
30% of 1,5-pentanediol,
5% of diethylene glycol monomethyl ether,
0.01% of Mergal K9N biocide, and
58.99% of water
using a drop-on-demand (piezo) ink jet print head. The print is fully dried. Fixing is effected by means of superheated steam at 175° C. for 7 minutes. The print is subsequently subjected to an alkaline reduction clear, rinsed warm and then dried.

Claims

We claim:

1. A dye of the formula (I)

where

D is the radical of a diazo component represents a group of the formula (IIa)

where

T¹and T²independently are hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, —SO₂(C₁-C₆)-alkyl, —SO₂aryl, cyano, halogen or nitro; and

T⁴and T³independently are hydrogen, halogen, trifluoromethyl, cyano, —SCN, —SO₂CH₃or nitro;

although at least one of T¹, T², T³and T⁴is not hydrogen;

or represents a group of the formula (IIb)

where

T⁵and T^5′independently are hydrogen or halogen; and

T⁶is hydrogen, —SO₂CH₃, —SCN, (C₁-C₄)-alkoxy, halogen or nitro;

although at least one of T⁵, T^5′and T⁶is not hydrogen;

or represents a group of the formula (IIc)

where

T¹²is hydrogen or halogen;

or represents a group of the formula (IId)

where

T⁷is nitro, —CHO, cyano, —COCH₃or a group of the formula

where T¹⁰is hydrogen, halogen, nitro or cyano;

T⁸is hydrogen, (C₁-C₆)-alkyl or halogen; and

T⁹is nitro, cyano, —COCH₃or —COOT¹¹; where T¹¹is (C₁-C₄)-alkyl;

or represents a group of the formula (IIe)

where T⁷and T⁸are each as defined above;

or represents a group of the formula (IIf)

where T¹³is phenyl or S-(C₁-C₄)-alkyl;

R¹is hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, halogen, —NHCHO, —NHCO(C₁-C₆)-alkyl, —NHCOaryl, —NHSO₂(C₁-C₆)-alkyl or —NHSO₂aryl;

R²is hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, phenoxy or halogen;

R³is hydrogen, (C₁-C₆)-alkyl, substituted (C₁-C₆)-alkyl, (C₃-C₄)-alkenyl or substituted (C₃-C₄)-alkenyl;

or R²and R³combine to form the radical —C*H(CH₃)CH₂C(CH₃)₂—, where the carbon atom marked by * is attached to the phenyl nucleus;

R⁴is hydrogen, (C₁-C₆)-alkyl or phenyl;

R⁵is (C₁-C₆)-alkyl or substituted (C₁-C₆)-alkyl;

R⁶is hydrogen or (C₁-C₆)-alkyl;

R⁷is hydrogen, (C₁-C₆)-alkyl or phenyl; and

n 0, 1, 2 or 3;

although the compounds of the formulae

shall be excluded.

2. The dye as claimed in claim 1, wherein D represents a group of the formula (IIa)

where

although at least one of T¹, T², T³and T⁴is not hydrogen;

or represents a group of the formula (IIb)

where

T⁵and T^5′independently are hydrogen or halogen; and

T⁶is hydrogen, —SO₂CH₃, —SCN, (C₁-C₄)-alkoxy, halogen or nitro;

although at least one of T⁵, T^5′and T⁶is not hydrogen;

or represents a group of the formula (IIc)

where

T¹²is hydrogen or halogen;

or represents a group of the formula (IId)

where

T⁷is nitro, —CHO, cyano, —COCH₃or a group of the formula

where T¹⁰is hydrogen, halogen, nitro or cyano;

T⁸is hydrogen, (C₁-C₆)-alkyl or halogen; and

T⁹is nitro, cyano, —COCH₃or —COOT¹¹; where T¹¹is (C₁-C₄)-alkyl;

or represents a group of the formula (IIe)

where T⁷and T⁸are each as defined above;

or represents a group of the formula (IIf)

where T¹³is phenyl or S—(C₁-C₄)-alkyl.

3. The dye as claimed in claim 1, wherein

R¹is hydrogen, chlorine, methyl, ethyl, methoxy, hydroxyl, ethoxy, acetylamino, propionylamino, benzoylamino, methylsulfonylamino, ethylsulfonylamino or phenylsulfonylamino;

R²is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy or phenoxy;

R³is hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl, cyanoethyl, —C₂H₄OCOCH₃, —C₂H₄OCOC₂H₅, —C₂H₄COOCH₃, —C₂H₄COOC₂H₅or allyl;

R⁴and R⁷are hydrogen, methyl or phenyl;

R⁵is methyl or ethyl;

R⁶is hydrogen or methyl; and

n is 0 or 1;

although the compounds of the formulae

shall be excluded.

4. The dye as claimed in claim 2, wherein

R²is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy or phenoxy;

R⁴and R⁷are hydrogen, methyl or phenyl;

R⁵is methyl or ethyl;

R⁶is hydrogen or methyl; and

n is 0 or 1;

although the compounds of the formulae

shall be excluded.

5. The dye according to claim 1, conforming to the wherein in the dye of formula (I) is a dye of formula (Ia)

where T¹to T⁴, R¹to R⁷and n are each as defined in claim 1, although the compounds of the formulae

shall be excluded.

6. The dye as claimed in claim 5, wherein

R¹is acetylamino, propionylamino, benzoylamino or methylsulfonylamino;

R²is hydrogen, chlorine, methoxy or ethoxy;

R³is hydrogen, methyl, ethyl, allyl or benzyl;

R⁴is hydrogen or methyl;

R⁵methyl or ethyl;

R⁶is hydrogen or methyl and

R⁷is hydrogen, methyl or phenyl.

7. The dye as claimed in claim 5, conforming to the formula (Iaa)

where

T¹is hydrogen, nitro or methyl;

T²is hydrogen, nitro or chlorine;

T³is hydrogen, cyano, chlorine or bromine;

T⁴is hydrogen, cyano, nitro, chlorine, bromine or trifluoromethyl;

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

R²is hydrogen, chlorine, methyl, phenoxy, methoxy or ethoxy;

R³is hydrogen, methyl, ethyl, butyl, benzyl, phenylethyl, phenoxyethyl or allyl;

R⁵is methyl or ethyl; and

R⁴and R⁷are hydrogen, methyl or phenyl;

although the compounds of the formulae

shall be excluded.

8. The dye as claimed in claim 7, wherein T³is chlorine or bromine and R¹is hydrogen or methyl.

9. A process for preparing a dye of the formula (I) as claimed in claim 1, which comprises diazoting a compound of the formula (III)

D-NH₂ (III)

where D is as defined in claim 1, and coupling onto a compound of the formula (IV)

where R¹to R⁷and n are each as defined in claim 1.

10. A process for dyeing and printing a hydrophobic material which comprises contacting the material with the dye as claimed in claim 1.

11. An ink for digital textile printing by the ink jet process, comprising the dye of the formula (I) as claimed in claim 1.

12. An ink for digital textile printing by the ink jet process, comprising the dye of the formula (I) as claimed in claim 8.