AU2003205777B2 - Process for the treatment of textile fibre materials - Google Patents

Description

WO 03/070869 PCT/EP03/01618 Process for the treatment of textile fibre materials The present invention is directed to detergent formulations containing certain fluorescent whitening agents or mixtures of fluorescent whitening agents, as well as to mixtures of fluorescent whitening agents.

It is commonly known to use fluorescent whitening agents in detergent formulations. They exhaust during the treatment on to the material to be washed and, by virtue of their special light absorption/emission property, result in elimination of the yellowish shades.

However there is still a need to find improved fluorescent whitening agents for this application. It has now been found that mixtures of the following compounds of formulae (1) and or compounds of formula possess superior properties with regard to, for example, solubility, build-up properties, light-fastness degree of whiteness, and also possess excellent white aspects in the solid state. The whiteness properties, like whiteness maintenance, can even be enhanced by the use of mixtures of compounds of formulae (1) and or those of formula (1 a) in detergents containing cellulase, protease, amylase or lipase enzymes. Favourable results are even obtained at low washing temperatures.

Accordingly, the present invention provides, as a first aspect, a detergent composition comprising at least one compound of formula

N

SOM N >N

N

X4 wherein

R

1 and R 2 are, independently of each other, hydrogen or unsubstituted or substituted

C

1

-C

8 alkyl, X1, X 2

X

3 and X 4 are, independently of each other, -N(R 3

)R

4 or -ORs, wherein R 3 and R 4 are hydrogen, cyano, unsubstituted or substituted Ci-Caalkyl or Cs-C 7 cycloalkyl, or R 3 and R 4 WO 03/070869 PCT/EP03/01618 -2together with the nitrogen atom linking them, form a heterocyclic ring, and R 5 is unsubstituted or substituted C 1 -Cealkyl, and M is hydrogen or a cation, together with at least one compound of formula S03M SO3M R R R6 R, wherein Rs and Ry, independently of each other, are hydrogen, C 1 -Csalkyl, C 1 -Cealkoxy or halogen, and M is as defined above under formula Within the scope of the above definitions, C 1 -Csalkyl may be methyl, ethyl, n- or isopropyl, n-, sec.- or t-butyl, or linear or branched pentyl, hexyl, heptyl or octyl. Preferred are C 1

-C

4 alkyl groups. In case the alkyl groups are substituted examples of possible substituents are hydroxyl, halogen, like fluorine, chlorine or bromine, sulfo, sulfato, carboxy and C 1

-C

4 alkoxy, like methoxy and ethoxy. Other substituents of such alkyl groups are, for example, cyano,

-CONH

2 and phenyl. Preferred substituents are hydroxy, carboxy, cyano, -CONH 2 and phenyl, especially hydroxy and carboxy. Furthermore, highly preferred substituents are hydroxy and C 1

-C

4 alkoxy, especially hydroxy. The alkyl groups can also be uninterrupted or interrupted by (in case of alkyl groups containing two or more carbon atoms).

Examples for Cs-C 7 cycloalkyl groups are cyclopentyl and especially cyclohexyl. These groups can be unsubstituted or substituted by, for example, C 1

-C

4 -alkyl, like methyl.

Preferred are the corresponding unsubstituted cycloalkyl groups.

Within the scope of the above definitions, Ci-Cealkoxy may be methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.-butoxy, tert.-butoxy, or linear or branched higher alkoxy groups. Preferred are C 1

-C

4 alkoxy groups, especially methoxy or ethoxy. Highly preferred is methoxy.

Halogen may be fluorine, chlorine, bromine or iodine, preferably chlorine.

WO 03/070869 PCT/EP03/01618 -3- If R, and R 4 together with the nitrogen atom form a heterocyclic ring such a ring system can be, for example, morpholino, piperidine or pyrrolidine. The heterocyclic ring can be unsubstituted or substituted. An example for such substituents is C 1

-C

4 alkyl, especially methyl.

The cation M is preferably an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine. Preferred are Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C 1

-C

4 alkylammonium, mono-, di- or tri-C 2

-C

4 -hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of C 1

-C

4 -alkyl and C 2

-C

4 -hydroxyalkyl groups. Highly preferred is sodium.

R

1 and R 2 are preferably hydrogen or C 1

-C

4 alkyl, especially hydrogen.

R

3 and R 4 are preferably hydrogen; cyano; C 1 -Cealkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl, especially by hydroxy or carboxy, and wherein the C 1 -Cealkyl group is uninterrupted or interrupted by unsubstituted or C 1

-C

4 alkylsubstituted C 5

-C

7 cycloalkyl, especially cyclohexyl; or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1

-C

4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.

More preferably, R 3 and R 4 are hydrogen, unsubstituted or hydroxy-substituted C 1 -Caalkyl, unsubstituted or C 1

-C

4 alkyl-substituted C-C 7 cycloalkyl, or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1

-C

4 alkyl-substituted morpholino, piperidine or pyrrolidine ring. Highly preferred meanings for R 3 and R 4 are hydrogen, unsubstituted or hydroxy-substituted C 1

-C

8 alkyl, or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1

-C

4 alkyl-substituted morpholino, piperidine or pyrrolidine ring. Most preferred are unsubstituted or C 1

-C

4 alkyl-substituted morpholino, piperidine or pyrrolidine rings, especially morpholino, formed by R 3 and R 4 together with the nitrogen atom linking them.

Examples of -N(R 3

)R

4 groups are -NH 2

-NHCH

3

-NHC

2

H

5 -NH(n-C 3

H

7 -NH(i-C 3

H

7 -NH(i-C 4

H

9

-N(CH

3 2

-N(C

2

H

52 -N(i-C 3

H

7 2

-NH(CH

2

CH

2 0H), -N(CH 2

CH

2 0H) 2

-N(CH

2

CH(OH)CH

3 2

-N(CH

3

)(CH

2

CH

2 0H), -N(C 2

H

5

)(CH

2

CH

2 0H), -N(i-C 3

H

7

)(CH

2

CH

2

CH

2

-NH(CH

2

CH(OH)CH

3

-N(C

2

H

5

)(CH

2

CH(OH)CH

3 WO 03/070869 PCT/EP03/01618 -4-

-NH(CH

2

CH

2

OCH

3

-NH(OH

2

CH

2 0CH 2

CH

2 OH), -NH(CH 2 CQOH), -NH(CH 2

CH

2

COOH),

-N(HA)CH

2 C00H), -NH(ON),

OH

3 OH 3 -NH-C-H-OH '-NH-C-HOH N 2Ull;' -NH -0 Njj1

OH

3 OH 3 COD 3O 0 H 3

CH

3 NN N N OH 3

N

I I I I I I

OH

3

H

3 0

OH

3

-NH-H-OOH

I NH- H-COOH

CHT-C-NH

2

NH

11 11 a. OH 2

OH

2

CHTNH-O-NH

2

R

5 is preferably 0 1 -Oaalkyl, especially 0 1

-O

4 alkyl, which is unsubstituted or substituted by Cj-

C

4 alkoxy or especially hydroxy. Highly preferred for R5 is methyl or ethyl, especially methyl.

X

1

X

2

X

3 and X 4 are preferably a radical of formula -N(R 3

)R

4 X, and X 3 have preferably the same meanings. In addition it is preferred that X 2 and X 4 have preferably the same meanings. Furthermore, it is preferred that the four radicals X 1

X

2

X

3 and X 4 do not have identical meanings.

Preferred are compounds of formula wherein R, and R 2 are hydrogen or Cl-C 4 alkyl,

R

3 and R 4 are hydrogen; cyano; 0 1 -Cealkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl and wherein the Cl-C 8 alkyl group is uninterrupted or interrupted by unsubstituted or C 1

-C

4 alkyl-substituted 0 6

-C

7 cycloalkyl; or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or O 1

-C

4 alkyl-substituted morpholino, piperidine or pyrrolidine ring; and WO 03/070869 PCT/EP03/01618

R

5 is C 1 -Csalkyl which is unsubstituted or substituted by hydroxy.

As to R 3

R

4 and Rs the above preferences apply.

Highly preferred are compounds of formula wherein

X

1 and X 3 are amino, and

X

2 and X 4 are a radical of formula -N(R 3

)R

4 wherein R3 and R 4 are hydrogen; cyano; C1- Csalkyl which is unsubstituted or substituted by hydroxy or carboxy, and wherein the C 1 Csalkyl group is uninterrupted or interrupted by unsubstituted or C 1

-C

4 alkyl-substituted cyclohexyl; or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1

-C

4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.

As to R 3 and R 4 the above preferences apply.

Of particular interest are compounds of formula wherein X, and X3 are amino,'and

X

2 and X 4 are a radical of formula -N(R 3

)R

4 wherein Rg and R 4 are hydrogen, unsubstituted or hydroxy-substituted C 1

-C

8 alkyl, unsubstituted or C 1

-C

4 alkyl-substituted cyclopentyl or cyclohexyl, or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring. Most interesting compounds of formula are those wherein R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1

-C

4 alkyl-substituted morpholino, piperidine or pyrrolidine ring. As to R 3 and R 4 the above preferences apply.

Further interesting compounds of formula are those of formula (la) given below.

R

6 and R 7 are preferably hydrogen. Each of the sulfo groups indicated in formula are preferably bonded in ortho position. Interesting compounds of formula are those wherein Re and R 7 are hydrogen and each of the sulfo groups indicated in formula are bonded in ortho position.

M is preferably hydrogen, an alkaline- or alkaline earth-metal, or ammonium, especially sodium.

In the mixtures of compounds of formulae and the molar ratio of compound to compound is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 00 0 99:1 and more preferably from 5:95 to 95:5. Highly preferred is a molar ratio of from 10:90 to 90:10, especially 20:80 to 80:20. Most important is a molar ratio of from 30:70 to 70:30,

IND

especially 40:60 to 60:40.

The compounds of formulae and are known or can be prepared in analogy to known processes.

r Compounds of formula may be produced by reacting, under known reaction conditions, 0 cyanuric chloride, successively, in any desired sequence, with each of C1 4,4'-diaminostilbene-2,2'- disulfonic acid, and amino compounds capable of introducing the groups Xi, X 2

X

3 and X 4 Preferably, 2 moles of cyanuric chloride are initially reacted with 1 mole of 4,4'-diaminostilbene-2,2'- disulfonic acid and then reacting the intermediate obtained in any order with amino compounds capable of introducing the groups X 1

X

2

X

3 and X 4 For the preparation of compounds wherein X, and X 3 having the same meaning, and also X 2 and

X

4 have the same meaning, it is preferred to react the intermediate obtained first with an amino compound capable of introducing X 1 and X 3 and, finally with an amino compound capable of introducing X 2 and X 4 It is also possible to carry out the reaction with the amino compounds in one step by reacting the intermediate with a mixture of amino compounds; in such a case usually correponding mixtures of compounds of formula are obtained.

Compounds of formula containing a radical of formula -ORs can for example be prepared by first reacting cyanuric chloride with the correponding alcohol HORs, reacting the product obtained with 4,4'-diaminostilbene-2,2'- disulfonic acid and then reacting the intermediate with further compounds capable of introducing the remaining groups of X 1

X

2

X

3 and X 4 The last reaction is preferably carried out with the corresponding amines.

6a- 00 In one embodiment of this invention, there is provided a detergent composition comprising at least one compound of formula X 2 X, N\ N (1) S0 3M S /-X3

N

C X4 wherein RI and R 2 are, independently of each other, hydrogen or unsubstituted or substituted

C

1 -Csalkyl,

X

1 and X 3 are amino, and to X 3 and X 4 are a radical of formula -N(R 3

)R

4 wherein R 3 and R 4 are hydrogen, cyano; CI-Cgalkyl which is unsubstituted or substituted by hydroxy or carboxy, and wherein the Ci-C 8 alkyl group is uninterrupted or interrupted by unsubstituted or C 1

C

4 alkyl-substituted cyclohexyl; or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or Ci-C 4 alkyl-substituted morpholino, piperidine or is pyrrolidine ring, M is hydrogen or a cation, together with at least one compound of formula

SO

3 M

SO

3

M

R 2 R6 R7 wherein

R

6 and R 7 independently of each other, are hydrogen, C1-Calkyl, Ci-Csalkoxy or halogen, and M is as defined above under formula In another embodiment of this invention, there is provided a detergent composition comprising at least one compound of formula A1121(1064931_1):JJP 6b 00 x 2 O X2 SN= MO 3

S

N R2 R N (1 a)

SO

3 M

N

N /X3

N

r X4 wherein O R 1 and R 2 are, independently of each other, hydrogen or unsubstituted or substituted gq CI-Csalkyl, Xi and X 3 are amino,

X

2 and X 4 are a radical of formula -N(R 3

)R

4 wherein R 3 and R 4 are hydrogen; cyano or Ci-Csalkyl which is unsubstituted or substituted by hydroxy or carboxy, and wherein the C -Csalkyl group is uninterrupted or interrupted by unsubstituted or Ci-C 4 alkylsubstituted cyclohexyl; or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or Cl-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, M is hydrogen, an alkaline- or alkaline earth-metal, or ammonium, preferably sodium, and wherein the detergent contains at least one enzyme selected from the group consisting of cellulose, protease, amylase and lipase.

Furthermore, the present invention is directed to mixtures of compounds of formulae and As to compounds of formulae and the preferences given above apply. Compounds of formula wherein R 6 and R 7 are hydrogen and each of the sulfo groups indicated in formula are bonded in ortho position are preferred. In such mixtures, the molar ratio of compound to compound is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 99:1 and more preferably from 5:95 to 95:5.

Highly preferred is a molar ratio of from 10:90 to 90:10, especially 20:80 to 80:20. Most important is a molar ratio of from 30:70 to 70:30, especially 40:60 to 60:40.

AH21(1064931_1)-JJP WO 03/070869 PCT/EP03/01618 -7- The detergent compositions used preferably comprise i) 1-70% of an anionic surfactant and/or a nonionic surfactant; ii) 0-75% of a builder; iii) 0-30% of a peroxide; iv) 0-10% of a peroxide activator; and v) 0.001-5% of a mixture of compounds of formulae and each by weight, based on the total weight of the detergent.

More preferably the detergent compositions used comprise i) 5-70% of an anionic surfactant and/or a nonionic surfactant; ii) 5-70% of a builder; iii) 0.5-30% of a peroxide; iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; and v) 0.01-5% of a mixture of compounds of formulae and each by weight, based on the total weight of the detergent.

In general, an amount of a mixture of compounds of formulae and of 0.001-5%, especially an amount of 0.01-5% is used. Highly preferred is an amount of 0.05-5%, especially 0.05 to In general, amounts given in percent are to be understood as being percent by weight, based on the total weight, unless otherwise stated.

The detergent may be formulated as a solid, as an aqueous liquid comprising, 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not more than preferably 0-1 wt.% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, in GB-A-2158454.

The anionic surfactant component may be, an alkylbenzenesulfonate, an alkylsulfate, an alkylethersulfate, an olefinsulfonate, an alkanesulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or an a-sulfofatty acid salt or an ester thereof. Preferred are alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl group, alkylsulfates having 8 to 18 carbon atoms, alkylethersulfates having 8 to 18 carbon atoms, and fatty acid salts being derived from palm oil or tallow and having 8 to 18 carbon atoms. The average molar number of ethylene oxide added in the alkylethersulfate is preferably 1 to 20, preferably 1 to WO 03/070869 PCT/EP03/01618 -8- The salts are preferably derived from an alkaline metal like sodium and potassium, especially sodium. Highly preferred carboxylates are alkali metal sarcosinates of formula

R-CO(R')CH

2 COOM' in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R 1 is C 1

-C

4 alkyl and M' is alkali metal, especially sodium.

The nonionic surfactant component may be, primary and secondary alcohol ethoxylates, especially the C 8

-C

2 0 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -Cis primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).

The total amount of anionic surfactant and nonionic surfactant is preferably 5-50% by weight, preferably 5-40% by weight and more preferably 5-30% by weight. As to these surfactants it is preferred that the lower limit is 10% by weight.

The builder component may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.

Preferred silicates are crystalline layered sodium silicates of the formula NaHSimO 2 or Na 2 SimO 2 m,,.pH20 in which m is a number from 1.9 to 4 and p is 0 to Preferred aluminosilicates are the commercially-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.

Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.

Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.

Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.

WO 03/070869 PCT/EP03/01618 -9- The amount of builders is preferably 5-70% by weight, preferably 5-60% by weight and more preferably 10-60% by weight. As to the builders it is preferred that the lower limit is 15% by weight, especially 20% by weight.

Suitable peroxide components include, for example, the organic and inorganic peroxides (like sodium peroxides) known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 5 to 950C.

In particular, the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest. It is preferred, however, to employ very active inorganic peroxides, such as persulphate, perborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides.

The amount of peroxide is preferably 0.5-30% by weight, preferably 1-20% by weight and more preferably 1-15% by weight. In case a peroxide is used, the lower limit is preferably 2% by weight, especially 5% by weight.

The peroxides, especially the inorganic peroxides, are preferably activated by the inclusion of a bleach activator. Preferred are such compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to carbon atoms, especially from 2 to 4 carbon atoms. Suitable compounds include those that carry 0- and/or N-acyl groups having the said number of carbon atoms and/or unsubstituted or substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N-dimethyl-urea (DDU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), compounds of formula

R'R

wherein R is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R' is linear or branched (C 7

-C

15 )alkyl; also activators that are known under the names WO 03/070869 PCT/EP03/01618 SNOBS, SLOBS, NOBS and DOBA, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated, glucamine and gluconolactone. The combinations of conventional bleach activators disclosed in German Patent Application DE-A-44 43 177 may also be used. Nitrile compounds that form peroxyimidic acids with peroxides are also suitable as bleach activators. Preferred are tetraacetyl ethylenediamine and nonoyloxybenzene sulfonate.

The amount of bleach activator is preferably 0-10% by weight, preferably 0-8% by weight. In case a bleach activator is used, the lower limit is preferably 0.5% by weight, especially 1% by weight.

Bleaching catalysts, which may be added, include, enzymatic peroxide precursors and/or metal complexes. Preferred metal complexes are manganese, cobalt or iron complexes such as manganese or iron phthalocyanines or the complexes described in EP-A- 0509787. In case a bleaching catalyst is used the amount is preferably 0.005 to 2% by weight, more preferably 0.01 to 2% by weight, especially 0.05 to 2% by weight. Highly preferred is an amount of 0.1-2% by weight.

As examples for bleaching catalysts the following are mentioned: WO-A-95/30681 (see i.e. formula and the following definition on page 1, lines 7 to especially formula and the following definitions given on page 2, lines 29 to page 11, line 11). Preferred ligands are those given on page 13, line 12 to. page 26, line 11.

WO-A-01/09276 (see i.e. formulae and and the following definitions given on pages 2 and 3).

WO-A-01/05925 (see i.e. formula and the following definition on page 1, last paragraph to page 2, first paragraph. The preferences given for the metal complexes apply, see especially those of formula on page 3 and those of formula on page 4).

WO-A-02/088289 (see i.e. formula and the following definition on page 2. The preferences given for the metal complexes apply, see especially the ligands of formula (3) and also the preferences given on page 3, fourth paragraph to page 4, paragraph 7).

WO 03/070869 PCT/EP03/01618 -11 Furthermore, the detergent can optionally contain enzymes. Enzymes can be added to detergents for stain removal. The enzymes usually improve the performance on stains that are either protein- or starch-based, such as those caused by blood, milk, grass or fruit juices.

Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases. Cellulases are enzymes which act on cellulose and its derivatives and hydrolyze them into glucose, cellobiose, cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating the roughness to the touch. Examples of enzymes to be used include, but are by no means limited to, the following: proteases as given in US-B-6,242,405, column 14, lines 21 to 32; lipases as given in US-B-6,242,405, column 14, lines 33 to 46; amylases as given in US-B-6,242,405, column 14, lines 47 to 56; and cellulases as given in US-B-6,242,405, column 14, lines 57 to 64.

The enzymes can optionally be present in the detergent. When used, the enzymes are usually present in an amount of 0.01-5% by weight, preferably 0.05-5% and more preferably 0.1-4% by weight, based on the total weight of the detergent.

Further preferred additives for the detergents according to the invention are polymers that, during the washing of textiles, inhibit staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions (dye fixing agents, dye transfer inhibitors). Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine N-oxides which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000. Such polymers are usually used in an amount of from 0.01 to 5 preferably 0.05 to 5 by weight, especially 0.1 to 2 by weight, based on the total weight of the detergent. Preferred polymers are those given in WO-A-02/02865 (see especially page 1, last paragraph and page 2, first paragraph).

The detergents used will usually contain one or more auxiliaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; photobleaching WO 03/070869 PCT/EP03/01618 -12agents; pigments; and/or shading agents. These constituents should, of course, be stable to any bleaching system employed. Such auxiliaries can be present in an amount of, for example, 0.1 to 20% by weight, preferably 0.5 to 10 by weight, especially 0.5 to 5 by weight, based on the total weight of the detergent.

The detergent compositions can take a variety of physical forms including powder, granular, tablet and liquid forms. Examples thereof are conventional powder heavy-duty detergents, compact and supercompact heavy-duty detergents and tablets, like heavy-duty detergent tablets. One important physical form is the so-called concentrated granular form adapted to be added to a washing machine.

Of importance are also the so-called compact (or supercompact) detergents. In the field of detergent manufacture, a trend has developed recently towards the production of compact detergents, which contain increased amounts of active substance. In order to minimize energy expenditure during the washing process, the compact detergents are required to operate efficiently at temperatures as low as 40'C, or even at room temperatures, e.g. at 0 C. Such detergents usually contain only low amounts of fillers or processing aids, like sodium sulfate or sodium chloride. The amount of such fillers is usually 0-10% by weight, preferably 0-5 by weight, especially 0-1 by weight, based on the total weight of the detergent. Such detergents usually have a bulk density of 650-1000 g/l, preferably 700- 1000 g/l and especially 750-1000 g/l.

The detergents can also be present in the form of tablets. Relevant characteristics of tablets are ease of dispensing and convenience in handling. Tablets are the most compact delivery of solid detergents and have a bulk density of, for example, 0.9 to 1.3 kg/litre. To enable fast disintegration laundry detergent tablets generally contain special disintegrants: Effervescents such as carbonate/hydrogencarbonate/citric acid; swelling agents like cellulose, carboxymethyl cellulose, cross-linked poly(Nvinylpyrrollidone); quickly dissolving materials such as Na acetate, or Na citrate; rapidly dissolving water-soluble rigid coating such as dicarboxy acids.

The tablets can also contain combinations of any of the above disintegrants.

WO 03/070869 PCT/EP03/01618 -13- The detergent may also be formulated as an aqueous liquid comprising 5-50, preferably water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water. Non-aqueous liiquid detergent compositions can contain other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may contain from 5% to typically 10% to 50% of such carriers. The detergents can also be present as the so-called "unit liquid dose" form.

This detergent treatment of textiles can be conducted as a domestic treatment in normal washing machines.

The textile fibres treated may be natural or synthetic fibres or mixtures thereof. Examples of natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora and silk, preferably wool.

Synthetic fibres include polyester, polyamide and polyacrylonitrile fibres. Preferred textile fibres are cotton, polyamide and wool fibres, especially cotton fibres. Preferably, textile fibres treated according to the method of the present invention have a density of less than 200 g/m 2 According to this process usually an amount of 0.01 to 3.0% by weight, especially 0.05 to by weight, based on the weight of the textile fibre material, of a mixture of compounds of formulae and is used.

The process is usually conducted in the temperature range of from 5 to 1000C, especially to 60C. Preferred is a temperature range of 5 to 40°C, especially 5 to 35 0 C and more preferably 5 to 300C.

The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11. Laundry products are typically at pH 9-11.

WO 03/070869 PCT/EP03/01618 -14- Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accordance with the invention. By an effective amount of the detergent composition it is meant, from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 85 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Examples are top-loading, vertical axis U.S.-type automatic washing machines using about 45 to 83 liters of water in the wash bath, a wash cycle of about 10 to about 14 minutes and a wash water temperature of about 10 to about front-loading, horizontal-axis European-type automatic washing machine using about 8 to liters of water in the wash bath, a wash cycle of about 10 to about 60 minutes and a wash water temperature of about 30 to about 95 0

C;

top-loading, vertical-axis Japanese-type automatic washing machine using about 26 to 52 liters of water in the wash bath, a wash cycle of about 8 to about 15 minutes and a wash water temperature of about 5 to about 250C.

The liquor ratio is preferably 1:4 to 1:40, especially 1:4 to 1:15. Highly preferred is a liquor ratio of 1:4 to 1:10, especially 1:5 to 1:9.

Furthermore, the present invention is directed to a detergent composition comprising at least one compound of formula N X 2

N

N- MOZS (a) So 3 M N N N

N

X

4 wherein

R

1 and R 2 are, independently of each other, hydrogen or unsubstituted or substituted WO 03/070869 PCT/EP03/01618 C,-Caalkyl,

X

2

X

3 and X 4 are, independently of each other, -N(R 3

)R

4 or -ORs, wherein R 3 and R 4 are hydrogen; cyano; C 1 -Calkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl and wherein the Cl-CBalkyl group is uninterrupted or interrupted by unsubstituted or C 1

-C

4 alkyl-substituted Cs-C 7 cycloalkyl; or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1

-C

4 alkyl-substituted morpholino, piperidine or pyrrolidine ring; Rs is CI-Csalkyl which is unsubstitued or substituted by hydroxy, and M is hydrogen or a cation, and wherein the detergent contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.

As to the compounds of formula (la) as well as to the substituents thereof the meanings and preferences given above for compounds of formula apply.

Of interest are compounds of formula wherein R 1 and R 2 are, independently of each other, hydrogen or unsubstituted or substituted C 1

-C

8 alkyl,

X

1

X

2

X

3 and X 4 are, independently of each other, -N(R 3

)R

4 or -ORs, wherein R 3 and R 4 are hydrogen, unsubstituted or hydroxy-substituted Ci-C 8 alkyl, unsubstituted or C 1

-C

4 alkylsubstituted Cs-C 7 cycloalkyl, or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1

-C

4 alkyl-substitued morpholino, piperidine or pyrrolidine ring, and R 5 is unsubstituted or hydroxy-substituted Ci-Calkyl, and M is hydrogen or a cation.

Highly preferred are corresponding detergent compositions which contain enzymes as well as peroxide, peroxide activator and/or bleaching catalyst.

Preferred are detergent compositions comprising i) 1-70% of an anionic surfactant and/or a nonionic surfactant; ii) 0-75% of a builder; iii) 0-30% of a peroxide; iv) 0-10% of a peroxide activator; v) 0.001-5% of a compound of formula and vi) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, especially protease.

WO 03/070869 PCT/EP03/01618 -16- Highly preferred are detergent compositions comprising i) 5-70% of an anionic surfactant and/or a nonionic surfactant; ii) 5-70% of a builder; iii) 0.5-30% of a peroxide; iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; v) 0.01-5% of a compound of formula (1 and vi) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, especially protease.

As to the enzymes, the detergents and the ingredients thereof the definitions and preferences given above apply. The compounds of formula (1 a) can be used in the same way as given above for the mixture of compounds of formulae and A further object of the present invention is to provide a process for the domestic washing treatment of a textile fibre material wherein the textile fibre material is contacted with an aqueous solution of a detergent comprising a compound of formula (la) as defined above, and wherein the detergent contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, and wherein the temperature of the solution is between 50C and 400C, preferably between and 300C, throughout the process.

As to the compounds of formula (la) as well as for the detergents and the washing process the definitions and preferences given above apply.

The above washing treatment of textile fibers can also be conducted with the mixture of compounds of formulae and The compounds and mixtures used according to the present invention are particularly advantageous in that they exhibit not only extremely high whitening ability, but, in addition, in many cases highly desirable water solubilities and also possess excellent white aspects in the solid state. A further advantage of the present invention is that the detergent composition delivers improved whiteness performance and fabric feel. Furthermore the compounds and especially the mixtures show very good results with respect to exhaustion properties.

WO 03/070869 PCT/EP03/01618 -17- The compounds have the advantage that they are also effective in the presence of active chlorine donors, such as, for example, hypochlorite and can be used without substantial loss of the effects in washing baths with non-ionic washing agents, for example alkylphenol polyglycol ethers. Also in the presence of perborate or peracids and activators, for example tetraacetylglycoluril or ethylenediamine-tetraacetic acid are the compounds and mixtures of compounds stable both in pulverulent washing agent and in washing baths. In addition, they impart a brilliant appearance in daylight.

Compounds of the formula and mixtures of compounds of formulae and have also been found to be useful for the fluorescent whitening of textile materials, in which connection polyamides, wool and cotton should be singled out particularly. The textile fibres treated according to this embodiment of the present invention may be natural or synthetic fibres or mixtures thereof. Examples of natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora and silk, preferably wool. Synthetic fibres include polyester, polyamide and polyacrylonitrile fibres. Preferred textile fibres are cotton, polyamide and wool fibres.

Preferably, textile fibres treated according to the present invention have a density of less than 1000 g/m 2 especially less than 500 g/m 2 and most preferred less than 250 g/m 2 The following Examples serve to illustrate the invention; parts and percentages are by weight, unless otherwise stated.

Preparation Example 1:

CH

2

CH

3 Na H 0

HOCH

2 CH N NO=S-O

NH

-Y o s -O NH N -N N (101)

NH

2 0-S=O 10 N N N- HCH 2

OH

SNaH

HH

Na

CHCH,

In a 1 liter flask 0.05 mole of the compound of formula WO 03/070869 PCT/EP03/01618 -18- Na H 0 GI N II C N rO=S-0o NH( N NO 1 N (52205-59-1) (102)

NH

2 O-=0 N A ClI O H Na' are mixed with 600ml of water and heated to a temperature of 60°C. Then 9.2g of 2ethylaminoethanol are added and the reaction mixture is heated to a temperature of 98°C; during heating the pH is maintained at a value between 8.5 and 9 by addition of a 4-molar aqueous solution of sodium hydroxide. The reaction mixture is cooled to 50 0 C and the pH is adjusted to a value of 4.5 by addition a 6-molar aqueous solution of hydrochloric acid. The precipitate is filtered off, washed with 100ml of a 10% aqueous sodium chloride solution and dried in vacuum. In this way, there are obtained 30.5g of a yellowish product.

Preparation Examples 2 to The following compounds of formula Na H 0 NN NNHN.

NH2 80-S=0 2 II =O N N X o H Na can be prepared in analogy to the process given in Preparation Example 1, by replacing 9.2 g of 2-ethylaminoethanol with an equimolar amount of the corresponding amine. X is as defined in the following Table 1. Compounds which precipitate after cooling to 500C are isolated directly as sodium salts without addition of hydrochloric acid and then dried in vaccuum.

WO 03/070869 WO 03/70869PCT/EPO3/01618 -19- Table 1 Example X 4 -N(C2H)C 2

OH

NH

6 -NHCH3)CH 2 7 -~NHCHOH 8 -NHOH 2

CH

2 00H 9 -NHCH 2

CH

3

-N(CH

3

)CH

2 000H 11 -N(CH 2

CH

2 0H)2 12

N

14 -NHCH 2

COOH

-NH-H-COOH

N

CH

2

CH

2

H~NH-C-NH

2 WO 03/070869 PCT/EP03/01618 Preparation Example 16: 0H

H

O

N

1 N

N

(103) In a 1 litre flask 0.05 mole of the compound of formula (27076-29-5) (104) Na are mixed with 600ml of water and heated to a temperature of 600C. Then 9.5g of morpholine are added and the reaction mixture is heated to a temperature of 980C; during heating the pH is maintained at a value between 8.5 and 9 by addition of a 4-molar aqueous solution of sodium hydroxide. The reaction mixture is cooled to 40°C and the precipitate is filtered off, washed with 100ml of a 10% aqueous sodium chloride solution and dried in vacuum. In this way, there are obtained 30g of a yellow product.

Preparation Examples 17 to 19: The following compounds of formula

H

X N N N- N

OCH

3

OCH

3 Na can be prepared in analogy to the process given in Preparation Example 16, by replacing g of morpholine with an equimolar amount of the corresponding amine. X is as defined in the WO 03/070869 PCT/EP03/01618 -21 following Table 2. Compounds having high solubility are treated with a 6-molar aqueous solution of hydrochloric acid in order to adjusted the pH to a value of 4.5 before cooling to 0

C.

Table 2 Example X 17 -N(CH 2

CH

3

)CH

2

CH

2 0H 18 Q 19 -N(CH 2

CH

2 0H) 2 Preparation Example Na H O HOCHCHHN. .Ny II_ H' N O=S--O NHCH 2

CH

2 0OH NYN N N (105) II N N NHCH 2 CH OH

HOCH

2

CH

2 HN O Na

H

In a 2 litre flask 130ml of methylethylketone, 80ml of deionised water, 150g of ice and 18.5g cyanuric chloride are mixed. Over a period of 30 minutes 185 ml of a solution of 4,4'diaminostilbene-2,2'-disulfonic acid (as disodium salt) in water (concentration of 100g/) are added dropwise, the temperature being between -8 und The pH is maintained at a value between 4.5 and 5 by addition of an aqueous sodium carbonate solution. A yellowish suspension is obtained. Then, by use of a dropping funnel, 27.2g of ethanolamine are added. The pH increases to a value of 10 and then drops to a lower value, whereby the temperature increases to 10 to 15°C. Then the reaction mixture is warmed to a temperature of 45°C and held at this temperature for 20 minutes. During heating to 98°C within minutes a mixture of methylethylketone and water is distilled off; the pH is maintained at a value between 8.5 and 9 by addition of an aqueous sodium hydroxide solution. After no further addition of aqueous sodium hydroxide solution is necessary in order to maintain the pH at a constant value the reaction mixture is cooled to 50°C. The pH is adjusted to a value WO 03/070869 PCT/EP03/01618 -22of 5.5 and a yellowish crystalline precipitate can be filtered off. After drying 29g of a yellowish product are obtained.

Preparation Example 21: 0 S I H 0 Na N N N O= -N NHCH S-r =S-O NHC2Hs N N N N N (106) HsC 2 HN O- =0 In a 1 litre pressure vessel 0.037 mole of N,N'-bis-(4-morpholino-6-chloro-1,3,5-triazine-2-yl)- 4,4'-diaminostilbene-2,2'-disulfonic acid (as disodium salt) are suspended in 500 ml of water.

g of an aqueous solution of ethylamine are added and the reaction mixture is heated to a temperature of 100 to 105°C and stirred for 4.5 hours. The reaction mixture is cooled to 25°C and the precipitate is filtered off, washed with 100ml of a 10% aqueous sodium chloride solution and dried in vacuum at 70 0 C. In this way there are obtained 25.8g of a yellowish powder.

Preparation Example 22: 0 0 Na N N N 11

S

O

S--O N(C 2

H

5 2 N N (107)

'N

oD The compound of formula (107) can be prepared in analogy to the process given in Preparation Example 21, by replacing 15 g of an aqueous solution of ethylamine with a corresponding solution containing an equimolar amount of diethylamine.

WO 03/070869 PCT/EP03/01618 -23- Preparation Example 23: 0 O N H N N N

IHCH

2

CH

2

OH

(108)

C°

In a 1 liter flask 0.05 mole of N,N'-bis-(4-morpholino-6-chloro-1,3,5-triazine-2-yl)-4,4'diaminostilbene-2,2'-disulfonic acid (as disodium salt) are suspended in 600ml of water and heated to a temperature of 600C. 6.4g of ethanolamine are added and the reaction mixture is heated to a temperature of 98°C. The pH is maintained at a value between 8.5 and 9 by addition of a 4-molar aqueous sodium hydroxide solution. The reaction mixture is cooled to and 10% by volume of sodium chloride are added. The precipitate is filtered off, washed with 100ml of a 10% aqueous sodium chloride solution and dried in vacuum at In this way there are obtained 41.8g of a yellowish powder.

Application Example 1: General procedure: A wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. g of bleached cotton fabric is added to the bath and washed at 400C over 15 minutes and then rinsed, spin-dried and ironed at 160°C.

The following washing powders A and B are used (amounts given in the following Tables 3a and 3b are in g): Table 3a (Ingredients of washing powders A and B) A B Sodium laurylbenzene-sulfonate (LAS) 10g Sodium lauryl ether sulfate (AES) 3g 3g Dobanol 23-6.5 (nonionic alcoholethoxylate) 4g 4g Sodium tripolyphosphate 30g Zeolite A WO 03/070869 PCT/EP03/01618 -24- Sodium carbonate 15g Sodium silicate 5g Sodium sulfate 11g 17g Cellulase 1.5g Protease Polycarboxylate (co-builder) 4g Carboxymethylcellulose 2g 2g Perfume 0.1g 0.1g Water 5g Fluorescent whitener or mixture of fluorescent whitener Xg Xg used Table 3b (Washing powders used) Amount of fluorescent Washing powder whitener or mixture of fluorescent whitener used Compound of Prep. Ex. 1 0.2g A Compound of Prep. Ex. 2 0.1g B Compound of Prep. Ex. 3 0.3g A Compound of Prep. Ex. 4 0.2g A Compound of Prep. Ex. 5 0.4g A Compound of Prep. Ex. 12 0.15g B Compound of Prep. Ex. 13 0.1g B Compound of Prep. Ex. 16 0.3g B Mixture of compound of 0.2g A Prep. Ex. 6 and compound of formula (109) [7:3 weight ratio] Mixture of compound of 0.4g B Prep. Ex. 12 and compound of formula (109) [7:3 weight ratio] Mixture of compound of 0.3g A Prep. Ex. 14 and compound of formula (109) [7:3 weight ratio] Mixture of compound of 0.2g B Prep. Ex. 17 and compound of formula (109) [1:1 weight ratio] WO 03/070869 PCT/EP03/01618 Mixture of compound of 0.5g B Prep. Ex. 18 and compound of formula (109) [1:2 weight ratio] Mixture of compound of 0.3g B Prep. Ex. 1 and compound of formula (109) weight ratio] Mixture of compound of 0.2g B Prep. Ex. 2 and compound of formula (109) [5:1 weight ratio] Mixture of compound of 0.2g B Prep. Ex. 3 and compound of formula (109) [1:1 weight ratio] Mixture of compound of 0.1g A Prep. Ex. 20 and compound of formula (109) [3:7 weight ratio] Mixture of compound of 0.1g B Prep. Ex. 21 and compound of formula (109) [1:9 weight ratio] Mixture of compound of 0.2g B Prep. Ex. 22 and compound of formula (109) [9:1 weight ratio] Mixture of compound of 0.4g B Prep. Ex. 23 and compound of formula (109) [1:1 weight ratio] Mixture of compound of 0.3g B formula (110) and compound of formula (109) [1:1 weight ratio] Constitution of compound of formula (109): (109) Constitution of compound of formula (110): WO 03/070869 PCT/EP03/01618 -26- (110) The cotton fabrics washed with the detergents given in Table 3b according to the general procedure show good whiteness properties.

Application Example 2: General procedure: A wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. g of bleached cotton fabric is added to the bath and washed at 30°C over 15 minutes and then rinsed, spin-dried and ironed at 1600C.

The following washing powders are used (amounts given in the following Tables 4a and 4b are percent by weight, based on the total weight of the detergent): Table 4a (Ingredients of washing powders C and D) C D Sodium laurylbenzene-sulfonate (LAS) 8% 8% Sodium lauryl ether sulfate (AES) 3% 3% Dobanol 23-6.5 (nonionic alcoholethoxylate) 5% Zeolite A 20% Polycarboxylate (co-builder) 5% Soda ash 18% 18% Sodium silicate 4% 4% Sodium sulfate 5% Hydroxyethanediphosphonic acid (complexing agent) 0.5% Cellulase 1.5% Protease Carboxymethylcellulose 1% 1% WO 03/070869 PCT/EP03/01618 -27- Sodium perborate monohydrate 15% TAED 5% Soap 2% 2% Fluorescent whitener or mixture of fluorescent whitener X% X% used In each of the above detergents a sufficient amount of water is used to give 100%.

Table 4b (Washing powders used) Amount of fluorescent Washing powder whitener or mixture of fluorescent whitener used Compound of Prep. Ex. 1 0.2% C Compound of Prep. Ex. 3 0.2% C Compound of Prep. Ex. 7 0.2% D Compound of Prep. Ex. 8 0.2% C Compound of Prep. Ex. 9 0.4% C Compound of Prep. Ex. 10 0.2% C Compound of Prep. Ex.11 0.2% C Compound of Prep. Ex. 17 0.4% C Compound of Prep. Ex. 20 0.5% C Compound of formula (110) 0.3% D Mixture of compound of 0.2% D Prep. Ex. 1 and compound of formula (109) [10:1 weight ratio] Mixture of compound of 0.4% C Prep. Ex. 3 and compound of formula (109) [5:1 weight ratio] Mixture of compound of 0.15% C Prep. Ex. 5 and compound of formula (109) [1:5 weight ratio] Mixture of compound of 0.2% C Prep. Ex. 11 and compound of formula (109) [11 weight ratio] Mixture of compound of 0.4% C Prep. Ex. 15 and compound of formula (109) [1:9 weight ratio] Mixture of compound of 0.3% D Prep. Ex. 16 and WO 03/070869 PCT/EP03/01618 -28compound of formula (109) [9:1 weight ratio] Mixture of compound of 0.2% D Prep. Ex. 19 and compound of formula (109) weight ratio] As to the constitution of compounds of formulae (109) and (110) see Application Example 1.

The cotton fabrices washed with the detergents given in Table 4b according to the general procedure show good whiteness properties.

Claims (16)

1. A detergent composition comprising at least one compound of formula X 2 _x N N= MO 3 S N R2 SR (1) SO 3 M N N /-X3 O wherein R 1 and R 2 are, independently of each other, hydrogen or unsubstituted or substituted Ci-Cgalkyl, XI and X 3 are amino, and X 3 and X 4 are a radical of formula -N(R 3 )R 4 wherein R 3 and R 4 are hydrogen, cyano; Ci-Csalkyl which is unsubstituted or substituted by hydroxy or carboxy, and wherein the Ci-Csalkyl group is uninterrupted or interrupted by unsubstituted or C 1 C 4 alkyl-substituted cyclohexyl; or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or Ci-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, M is hydrogen or a cation, together with at least one compound of formula SO 3 M SO 3 M R6 I R 7 wherein R 6 and R 7 independently of each other, are hydrogen, Ci-Csalkyl, C 1 -Csalkoxy or halogen, and M is as defined above under formula

2. A composition according to claim 1, wherein RI and R 2 are hydrogen or Ci-C 4 alkyl.

3. A composition according to any one of claims 1 to 2, wherein AH21(1064931_1):JJP 00 o R 3 and R4, together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, preferably a morpholino ring. DO 4. A composition according to any of claims 1 to 3, wherein R 6 and R 7 are hydrogen and each of the sulfo groups indicated in formula are bonded in ortho position. A process according to any of claims 1 to 4, wherein M is hydrogen, an alkaline- or alkaline earth-metal, or ammonium, preferably Ssodium.

6. A composition according to any of claims 1 to 5, comprising i) 1-70% of an anionic surfactant and/or a nonionic surfactant; ii) 0-75% of a builder; iii) 0-30% of a peroxide; iv) 0-10% of a peroxide activator; and v) 0.001-5% of a mixture of compounds of formulae and

7. A composition according to claim 6, comprising i) 5-70% of an anionic surfactant and/or a nonionic surfactant; ii) 5-70% of a builder; iii) 0.5-30% of a peroxide; iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; and v) 0.01-5% of a mixture of compounds of formulae and

8. A composition according to any of claims 1 to 7 in which the detergent composition comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, preferably protease.

9. A detergent composition comprising at least one compound of formula X 2 N- X N N= MO 3 S Ri S N (1 a) SO 3 M -N N -X3 wN X4 wherein AH21(1064931_1) JJP -31 00 R and R 2 are, independently of each other, hydrogen or unsubstituted or substituted C 1 -Csalkyl, C t X1 and X3 are amino, IN X 2 and X 4 are a radical of formula -N(R 3 )R 4 wherein R 3 and R 4 are hydrogen; cyano or Ci-Csalkyl which is unsubstituted or substituted by hydroxy or carboxy, and wherein the Ci-C 8 alkyl group is uninterrupted or interrupted by unsubstituted or C 1 -C 4 alkyl- substituted cyclohexyl; or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, M is hydrogen, an alkaline- or alkaline earth-metal, or ammonium, preferably S 10 sodium, and wherein the detergent contains at least one enzyme selected from the group consisting of cellulose, protease, amylase and lipase. A composition according to claim 9, wherein R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or CI-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, preferably a morpholino ring.

11. A composition according to any of claims 9 to 10, wherein the composition comprises a peroxide, a peroxide activator and/or a bleaching catalyst.

12. A composition according to any of claims 9 to 11, comprising i) 1-70% of an anionic surfactant and/or a nonionic surfactant; ii) 0-75% of a builder; iii) 0-30% of a peroxide; iv) 0-10% of a peroxide activator; v) 0.001-5% of a compound of formula and vi) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.

13. A composition according to any of claims 9 to 12, comprising i) 5-70% of an anionic surfactant and/or a nonionic surfactant; ii) 5-70% of a builder; iii) 0.5-30% of a peroxide; iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; v) 0.01-5% of a compound of formula and vi) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. AH21(1064931_1):JJP -32- 00 S14. A composition according to any of claims 9 to 13, wherein the enzyme is a protease enzyme. A process for the domestic washing treatment of a textile fibre material IND wherein the textile fibre material contacted with an aqueous solution of a detergent comprising a compound of formula X 2 N R2 c-i N= MO 3 S SN (la) S0 3 M N N X3 N X 4 wherein RI and R2 are, independently of each other, hydrogen or unsubstituted or substituted Ci-Csalkyl, X 1 and X 3 are amino, X 2 and X 4 are a radical of formula -N(R 3 )R4, wherein R 3 andR 4 are hydrogen; cyano or Ci-Csalkyl which is unsubstituted or substituted by hydroxy or carboxy, and wherein the Ci-Cgalkyl group is uninterrupted or interrupted by unsubstituted or Ci-C 4 alkyl- substituted cyclohexyl; or R3 and R4, together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, M is hydrogen, an alkaline- or alkaline earth-metal, or ammonium, preferably sodium, and wherein the detergent contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, and wherein the temperature of the solution is between 5°C and 40 0 C, preferably between 5°C and 30 0 C, throughout the process.

16. A process according to claim 15, wherein R3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or CI-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, preferably a morpholino ring.

17. A process according to any of claims 15 to 16, wherein the textile fibre materials are treated with 0.05 to 3.0% by weight, based on the weight of the textile fibre material, of the compound of formula (la). AH21(1064931_1):JJP -33- 00

18. A mixture of compounds comprising at least one compound of formula X 2 N ID-s N MO 3 S N R 2 RI N (1) SO 3 M N N /-X 3 N X 4 rn wherein RI and R 2 are, independently of each other, hydrogen or unsubstituted or substituted Ci-Cgalkyl, XI and X 3 are amino, X 2 and X 4 are a radical of formula -N(R 3 )R 4 wherein R 3 and R 4 are hydrogen; cyano or C 1 -Csalkyl which is unsubstituted or substituted by hydroxy or carboxy, and to wherein the C 1 -Csalkyl group is uninterrupted or interrupted by unsubstituted or Ci- C 4 alkyl-substituted cyclohexyl; or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, and M is hydrogen or a cation, together with at least one compound of formula SO 3 M SO 3 M R 6 R7 wherein R 6 and R 7 independently of each other, are hydrogen, Ci-C 8 alkyl, Ci-Csalkoxy or halogen, and M is as defined above under formula

19. A mixture of compounds according to claim 18, wherein R 1 and R 2 are hydrogen or Ci-C 4 alkyl. A mixture of compounds according to any one of claims 18 to 19, wherein R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or Ci-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, preferably a morpholino ring. AH21(1064931 1):JJP -34- 00 0 21. A mixture of compounds according to any of claims 18 to 20, wherein R 6 and R 7 are hydrogen and each of the sulfo groups indicated in formula are bonded in ortho position. IO 22. A mixture of compounds according to any of claims 18 to 21, wherein M is s hydrogen, an alkaline- or alkaline earth-metal, or ammonium, preferably sodium.

23. A process for the fluorescent whitening of textile materials comprising contacting the textile materials with a mixture of compounds of formulae and as defined in claim 1.

24. A process according to claim 23 in which the textile materials are polyamides, S to wool or cotton. Dated 7 January, 2008 Ciba Specialty Chemicals Holdings Inc. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON AH21(1064931_1):JJP