AU2003208870B2 - Process for the treatment of textile fibre materials - Google Patents

Description

r 1 PROCESS FOR THE TREATMENT OF TEXTILE FIBRE MATERIALS o The present invention is directed to detergent formulations containing certain Z fluorescent whitening agents and a peroxide, a peroxide activator and/or a bleaching catalyst.

It is commonly known to use fluorescent whitening agents in detergent 0formulations. They exhaust during the treatment on to the material to be washed and, by 00 virtue of their special light absorption/emission property, result in elimination of the 00 O yellowish shades.

2C However there is still a need to find improved fluorescent whitening agents for S 10o this application. It has now been found that the following compounds of formula (1) 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 compounds of formula in detergents containing a peroxide, a peroxide activator and/or a bleaching catalyst. Favourable results are even obtained at low washing temperatures.

According to a first aspect of the present invention, there is provided a detergent composition comprising at least one compound of formula

X

2

N

N R2 X-N N MO3S

I

N SO 3 M N (1) N /-X3

N

X

4 wherein RI and R 2 are, independently of each other, hydrogen or unsubstituted or substituted CI-Csalkyl, X, and X 3 are amino,

X

2 and X 4 are a, independently of each other, -N(R 3 )R4, wherein R 3 and R 4 are hydrogen; cyano; Ci-C 8 alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl and wherein the C 1

-C

8 alkyl group is uninterrupted or interrupted by unsubstituted or C 1

-C

4 alkyl-substituted C 6

-C

7 cycloalkyl; or R 3 and (1019837_1):KZA la 00

O

0 R 4 together with the nitrogen atom linking them, form an unsubstituted or Ci-C 4 alkyl- N substituted morpholino, piperidine or pyrrolidino ring; and M is hydrogen; or an alkaline- or alkaline earth-metal, or ammonium; and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst.

According to a second aspect of the present invention, there is provided a Sprocess for the domestic washing treatment of a textile fibre material wherein the textile 00 fibre material is contacted with an aqueous solution of a detergent comprising a C N compound of formula O X X2 XC N MO 3

S

N N I R2 SSO03M N N 3

\N

X

4 wherein Ri and R 2 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, independently of each other, -N(R 3

)R

4 wherein R 3 and R 4 are hydrogen; cyano; Ci-Csalkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl and wherein the Ci-Csalkyl group is uninterrupted or interrupted by unsubstituted or Ci-C 4 alkyl-subsitututed C 6

-C

7 cycloalkyl; or R 3 and

R

4 together with the nitrogen atom linking them, form an unsubstituted or CI-C 4 alkylsubstituted morpholino, piperidine or pyrrolidine ring; Rs is Ci-Csalkyl which is unsubstituted or substituted by hydroxy; and M is hydrogen, or an alkaline- or alkaline earth-metal, or ammonium; and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst, and wherein the temperature of the solution is between 5 0 C and 40 0 C, throughout the process.

There is disclosed herein, a detergent composition comprising at least one compound of formula (1019837 I):KZA

X

2 XT4 N M0 3

S

S0 3 M N(1 N i N

X

4 wherein 00 00 R, and R 2 are, independently of each other, hydrogen or unsubstituted or N substituted C I-Csalkyl, XI, X 2

X

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

)R

4 or -OR 5 wherein c-i R 3 and R 4 are hydrogen; cyano; C 1

-C

8 alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CON- 2 or phenyl and wherein the C -Csalkyl group is uninterrupted or interrupted by unsubstituted or substituted or C 1

-C

4 alkyl-substituted

C

5

-C

7 cycloalkyl; or R 3 and R 4 together with the (1019837_1):KZA WO 03/070870 PCT/EP03/01619 -2nitrogen atom linking them, form an unsubstituted or Cl-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring; Rs is Cl-C 8 alkyl which is unsubstituted or substituted by hydroxy, and M is hydrogen or a cation, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst.

Within the scope of the above definitions, Ci-Caalkyl may be methyl, ethyl, n- or isopropyl, n-, sec.- or t-butyl, or linear or branched pentyl, hexyl, heptyl or octyl. Preferred are C1-C 4 alkyl groups. In case the alkyl groups given for R, and R 2 are substituted examples of possible substituents are hydroxyl, halogen, like fluorine, chlorine or bromine, sulfo, sulfato, carboxy and C1-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 Cl-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 substituted by Cl-C 4 -alkyl, like methyl. Preferred are the corresponding unsubstituted cycloalkyl groups.

Within the scope of the above definitions, C 1

-C

4 alkyl may be methyl, ethyl, n- or isopropyl, n-, sec.- or t-butyl, especially methyl.

If R 3 and R 4 together with the nitrogen atom form a morpholino, piperidine or pyrrolidine ring such a ring system can be unsubstituted or substituted by C 1

-C

4 alkyl, especially methyl.

Preferred are the unsubstituted ring systems.

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 Cl-C 4 -alkyl and C 2

-C

4 -hydroxyalkyl groups. Highly preferred is sodium.

WO 03/070870 PCT/EP03/01619 -3- R, and R 2 are preferably hydrogen or 0 1

-C

4 alkyl, especially hydrogen.

R

3 and R 4 are preferably hydrogen; cyano; Cj-G 8 alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl, especially by hydroxy or carboxy, and wherein the Cj-C 8 alkyl group is uninterrupted or interrupted by unsubstituted or Cl-C 4 alkyIsubstituted C 5

-C

7 CYCloalkyl, especially 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.

More preferably, R 3 and R 4 are hydrogen, unsubstituted or hydroxy-substituted Cl-C 8 alkyl, unsubstituted or 0 1

-C

4 alky-substituted 0 5

-C

7 cycloalkyl, 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. Highly preferred meanings for R 3 and R 4 are hydrogen, unsubstituted or hydroxy-substituted Cl-CBalkyl, or R 3 and R 4 together with the nitrogen atom linking them, form an unsubstituted or C 1

-C

4 alky-substituted morpholino, piperidine or pyrrolidine ring. Most preferred are unsubstituted or Cl-C 4 alky-substituted morpholino, piperidine or pyrrolidline 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 H6, -NH(n-C 3

H

7 -NH(i-C3H 7 -NH(i-C 4

H

9 -N(0H 3 2

-N(C

2

H

5 2 -N(i-C 3

H

7 2

-NH(CH

2

CH

2 OH), -N(CH 2

CH

2

OH)

2

-N(CH

2

CH(OH)CH

3 2 -N(0H 3

)(GH

2

CH

2 OH), -N(C 2

H

5

)(CH

2

CH

2

OH),

-N(i-C 3

H

7

)(CH

2

CH

2

CH

2 OH), -NH(CH 2

CH(OH)CH

3 -N(0 2

H

5

)(CH

2

CH(OH)CH

3

-NH(CH

2

CH

2 00H 3

-NH(CH

2

CH

2 0CH 2

CH

2 0H), -NH(CH 2 C00H), -NH(CH 2

CH

2 000H),

-N(GH

3

)(CH

2 000H), -NH(ON),

OH

3 CH 3 -NH- Hi-OH -NH-C-CH 2

H

3 -NH 0

OH

3 OH 3 (0 H3, C N N N NC

O

3 N 3

N

WO 03/070870 PCT/EP03/01619 -4-

CH

3 N VHHC OHH

N

3 NH CH N N H 3 0 N OH 3 N J NH H I/ I I

-NH-CH-COOH

-NH-CH-COOH

CH-C-NH,

NH

II II O CH 2

CHCH,-NH-C-NH

2 Rs is preferably C,-Csalkyl, especially Cl-C 4 alkyl, which is unsubstituted or substituted by hydroxy. Highly preferred for R 5 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

1 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

1 and R 2 are hydrogen or C1-C 4 alkyl,

R

3 and R 4 are hydrogen; cyano; C1-Cealkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl and wherein the C1-Caalkyl 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 Ci-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring; and Rs is C1-C 8 alkyl 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 R 3 and R 4 are hydrogen; cyano; C1- Csalkyl which is unsubstituted or substituted by hydroxy or carboxy, and wherein the C1- Csalkyl group is uninterrupted or interrupted by unsubstituted or Ci-C 4 alkyl-substituted WO 03/070870 PCT/EP03/01619 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.

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

Of particular interest are compounds of formula wherein X, and X 3 are amino, and

X

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

)R

4 wherein R 3 and R 4 are hydrogen, unsubstituted or hydroxy-substituted Cl-Cealkyl, 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 1

-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.

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

Compounds of formula may be produced by reacting, under known reaction conditions, cyanuric chloride, successively, in any desired sequence, with each of 4,4'-diaminostilbene-2,2'- disulfonic acid, and amino compounds capable of introducing the groups X 1

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 Xi, 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, 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.

WO 03/070870 PCT/EP03/01619 -6- 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) 0.5-30% of a peroxide; iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; v) 0.001-5% of a compound of formula and vi) 0-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.

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; 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.

In general, an amount of compounds of formula 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 WO 03/070870 PCT/EP03/01619 -7being 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 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

1

)CH

2

COOM

1 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 1 is alkali metal, especially sodium.

The nonionic surfactant component may be, primary and secondary alcohol ethoxylates, especially the C8-C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Co 1 -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 03/070870 PCT/EP03/01619 -8- 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 95 0

C.

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'

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 03/070870 PCT/EP03/01619 -9- 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 03/070870 PCT/EP03/01619 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 03/070870 PCT/EP03/01619 -11agents; 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 03/070870 PCT/EP03/01619 -12- The detergent may also be formulated as a an aqueous liquid comprising 5-50, preferably 10-35% 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 compound of formula is used.

The process is usually conducted in the temperature range of from 5 to 100°C, especially to 600C. Preferred is a temperature range of 5 to 40°C, especially 5 to 35°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 03/070870 PCT/EP03/01619 -13- 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 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 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.

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 as defined above, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst, and wherein the temperature of the solution is between 5°C and 400C, preferably between and 300C, throughout the process.

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

WO 03/070870 PCT/EP03/01619 -14- The compounds 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 show very good results with respect to exhaustion properties.

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 stable both in pulverulent washing agent and in washing baths. In addition, they impart a brilliant appearance in daylight.

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*

HOCH

2 CH--N N N oI=S-O

NH,

NN N (101) Na*

CHCH

In a 1 liter flask 0.05 mole of the compound of formula Na' H 0 01 N N II N O 520-0 NH, NNN (52205-59-1) (102) WO 03/070870 PCT/EP03/01619 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 500C 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 X 'N N N

NH

2 Na' NH2 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.

Table 1 Example X 2

-N(C

2

H

5 2 3 0

N

4 -N(CH3)CH2CH20H WO 03/070870 WO 03/70870PCT/EPO3/01619 -16-

NH

6 -NHCH 2

CH

2

OH

7 -NHCH 2

CH

2

OCH

3 8 -NHCH 2

CH

2 000H 9 -NHCH 2

CH

3

-N(CH

3

)CH

2 000H 11 -N(CH 2

CH

2

OH)

2 12 -Noj 13

C

14 -NHCH 2

COOH

-NH-CH-COOH

NH

1 11 2 CH iN-H 2 2 Preparation Example 16: (103)

'N

0 In a 1 litre flask 0.05 mole of the compound of formula WO 03/070870 PCT/EP03/01619 -17- H 0 C H N NN O=S-0 OCH 3 Y IN

N-N

OCH

3 0-=0 O-S O H Na (27076-29-5) (104) are mixed with 600ml of water and heated to a temperature of 60°C. 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 400C 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

OCH,

N N N X 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 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 500C.

WO 03/070870 PCT/EP03/01619 -18- Table 2 Example X 17 -N(CH 2

CH

3

)CH

2

CH

2

OH

18

I

19 -N(CH 2 CH20H) 2 Preparation Example Na' H 0

HOCH

2 CHHN., N N I NHCH 2 0=S-O NHCHCHOH N N (105) O N -SNHCHCHOH

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/l) 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 of 5.5 and a yellowish crystalline precipitate can be filtered off. After drying 29g of a yellowish product are obtained.

WO 03/070870 PCT/EP03/01619 -19- Preparation Example 21: HC2HN (106) 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 250C and the precipitate is filtered off, washed with 100ml of a 10% aqueous sodium chloride solution and dried in vacuum at 700C. In this way there are obtained 25.8g of a yellowish powder.

Preparation Example 22: 0 ION

H

N N Ns- (107) 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 03/070870 PCT/EP03/01619 Preparation Example 23: 0 S I H 0 Na' S/ O=S-0 NHCH 2 CH0OH N N N N (108)

HOCH

2

CH

2 HN O-S=0 N Na O H I 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 980C. 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 160C.

The following washing powders A and B are used (amounts given in the following Tables 3a and 3b are in g): WO 03/070870 PCT/EP03/01619 -21 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 Sodium carbonate 15g Sodium silicate 5g Sodium sulfate 11g 17g Sodium perborate monohydrate 10g TAED 3g 3g Polycarboxylate (co-builder) 4g Carboxymethylcellulose 2g 2g Perfume 0,1g .1g Water 5g Fluorescent whitener used Xg Xg Table 3b (Washing powders used) Amount of fluorescent Washing powder 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 Compound of Prep. Ex. 18 0.2g A Compound of Prep. Ex. 21 0.3g A Compound of Prep. Ex. 22 0.2g B Compound of Prep. Ex. 23 0.1g A Compound of Formula (109) 0.3g B WO 03/070870 PCT/EP03/01619 -22- Constitution of compound of formula (109): (109) 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 0 C over 15 minutes and then rinsed, spin-dried and ironed at 160 0

C.

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 on-ionic 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% WO 03/070870 PCT/EP03/01619 -23- Cellulase Protease Carboxymethylcellulose 1% 1% Sodium perborate monohydrate 15% TAED 5% Soap 2% 2% Fluorescent whitener used X% X% 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 used Compound of Prep. Ex. 1 0.2% C Compound of Prep. Ex. 3 0.2% C Compound of Prep. Ex. 6 0.3% 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% D Compound of Prep. Ex.11 0.2% C Compound of Prep. Ex. 14 0.3% D Compound of Prep. Ex. 15 0.2% C Compound of Prep. Ex. 17 0.4% C Compound of Prep. Ex. 19 0.3% C Compound of Prep. Ex. 20 0.5% C Compound of formula (109) 0.3% D As to the constitution of compound of formula (109) see Application Example 1.

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

Experimental Report The following fluorescent whitening agents were tested: Compound A: 0 Compound B:

CO

Compound C: NaO 3 S N 3 N H

H

The fluorescent whitening agents A, B and C were incorporated into a detergent to composition having the following ingredients: Ingredient Concentration by weight based on the weight of the detergent composition] Alkyl aryl sulfonate 15.7 Fatty alcohol sulfonate 3.7 Coconut acid monoethanolamide 2.7 (1023773_1):KZA Sodium tripolyphosphate 39.0 Sodium silicate Magnesium silicate Carboxymethyl cellulose Sodium ethylenediaminetetraacetate Water 6.7 Balance up to 100% with sodium sulfate The compounds A, B and C were incorporated in equimolar amounts. The concentration respectively of compound A, B, C, in the detergent composition was respectively 0.14%, 0.22%, 0.12% by weight based on the weight of the composition.

Application Test 1 s Pieces of bleached cotton having an initial degree of whiteness of 80 were washed in 1 Litre of tap water containing the detergent, then rinsed under cold water and spun for 30 second in a spin-dryer at a speed of approximately 1,000 revolutions/minute, The washing conditions were: Detergent dose: 40g per kg fabric; liquor ratio: to 1; water hardness: 100 German Hardness; wash time: 15 minutes; and wash temperature: 20 0

C.

The washing process was carried out five times. After each cycle the pieces of cotton were dried indoor, ie. without exposure, and outdoor, ie. with exposure to 300 Langley. The expose to 300 Langley was effected by illuminating the test fabrics in a weathering device.

The degree of whiteness was determined by the Ganz method using a colorimeter. The Ganz method is described in detail in the Ciba-Geigy review 1973/1, and also in the article "Whiteness Measurement", ISCC Conference on Fluorescence and the Colorimetry of Fluorescent Materials, Williamsburg, February 1972, published in the Journal of Color and Appearance 1972 1.

The results are shown in table 1: Compound Cycle 1 Cycle 3 Cycle W1a W2b AWc Wla W2b AWc W1a W2b AWc A 135 131 -4 177 159 -18 189 166 -23 C (control) 121 114 -7 157 137 -20 174 145 -29 (1023773_1):KZA 0 00 00

O

O

t-q

Z

O

t-q

O

oo oo

O

t-q ¢€3

O

O

t-q B (control) 136 122 -14 168 137 -31 190 137 -53 Table 1: aWl refer to the degree of whiteness of the bleached cotton without exposure to UV light. bW2 refers to the degree of whiteness of the bleached cotton with exposure to UV light. cAW refers to the loss in degree of whiteness.

The loss in degree of whiteness after one, three and five washing cycles is 5 respectively 4, 18, 23 using the detergent composition comprising fluorescent whitener A of the present invention. As comparison, the loss in degree of whiteness after one, three and five washing cycles is respectfully 7, 20, 29 using the detergent composition comprising fluorescent whitener C, and respectively 14, 31, 53 using detergent compositions comprising fluorescent whitener B.

Thus, the loss in whiteness is smaller when using the detergent composition of the present invention compared to the control detergent compositions.

Application Test 2 Since the whiteness loss is dependent on the initial whiteness level, textile prebrightened with compounds A, B, C respectively exposed to 300 Langley. The degree of whiteness is determined after respectively 2, 4, 5 hours of exposure as described in application test 1.

The results are shown in table 2: Compound Exposed for 2 h Exposed for 4 h Exposed for 6 h InitialW W AW W AW W AW A 199 194 -5 188 -11 183 -16 C 185 188 -9 180 -17 173 -24 B 185 184 -15 174 -25 168 -31 Table 2: W refers to the degree of whiteness. AW refers to the loss in degree of whiteness.

Table 2 also shows that the loss in degree of whiteness upon UV light exposure is smaller when the fabric is pre-treated with detergent compositions of the present invention comprising compound A compared to control detergent compositions comprising compounds B or C.

(1023773_1):KZA

Claims (18)

1. A detergent composition comprising at least one compound of formula X 2 N MO 3 S N= R2 00 R 1 SOM N C, X4 wherein RI and R 2 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, independently of each other, -N(R 3 )R 4 wherein R 3 and R4 are hydrogen; cyano; Ci-Csalkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl and wherein the Ci-Csalkyl group is uninterrupted or interrupted by unsubstituted or Ci-C 4 alkyl-substituted C 6 -C 7 cycloalkyl; 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 pyrrolidino ring; and M is hydrogen or an alkaline- or alkaline earth-metal, or ammonium; and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst.

2. A composition according to claim 1 wherein M is sodium.

3. A composition according to claim 1 or 2, 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.

4. A composition according to any one of claims 1 to 3 wherein R 3 and R4 together with the nitrogen atom linking them form a morpholino ring. A composition according to any one of claims 1 to 4, comprising i) 1-70% of an anionic surfactant and/or a non-ionic surfactant; ii) 0-75% of a builder; iii) 0.5-30% of a peroxide; (1019837 I):KZA 0iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; v) 0.001-5% of a compound of formula and O vi) 0-5% of at least one enzyme selected from the group consisting of Scellulase, protease, amylase and lipase.

6. A composition according to any one of claims 1 to 5, comprising i) 5-70% of an anionic surfactant and/or a non-ionic surfactant; ii) 5-70% of a builder; 00 00 iii) 0.5-30% of a peroxide; C iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; S 0t v) 0.01-5% of a compound of formula and C vii) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.

7. A composition according to any one of claims 1 to 6, wherein the composition comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.

8. A composition according to claim 7, wherein the enzyme is a protease enzyme.

9. A composition according to any one of claims 1 to 8, wherein the composition comprises a peroxide.

10. A composition according to any one of claims 1 to 9, wherein the composition comprises a peroxide and a peroxide activator.

11. A composition according to claim 10, wherein the peroxide activator is TAED.

12. A detergent composition as claimed in claim 1 and substantially as hereinbefore described with reference to any one of the examples but excluding the Experimental Report.

13. 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 (1019837_1):KZA Sx 2 N -TCX N MO 3 S N RN Q SO 3 M N c N /X _N X 4 wherein 00 00 RI and R 2 are, independently of each other, hydrogen or unsubstituted or N substituted C 1 -Csalkyl, Xi and X 3 are amino, C X 2 and X 4 are, independently of each other, -N(R 3 )R 4 wherein R 3 and R 4 are hydrogen; cyano; Ci-Csalkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl and wherein the C 1 -Calkyl group is uninterrupted or interrupted by unsubstituted or Ci-C 4 alkyl-subsitututed C 6 -C7 cycloalkyl; or R 3 and R4, together with the nitrogen atom linking them, form an unsubstituted or Ci-C 4 alkyl- substituted morpholino, piperidine or pyrrolidine ring; R 5 is Ci-Csalkyl which is unsubstituted or substituted by hydroxy; and M is hydrogen, or an alkaline- or alkaline earth-metal, or ammonium; and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst, and wherein the temperature of the solution is between 5 0 C and 40°C throughout the process.

14. A process according to claim 13, wherein M is sodium, A process according to claim 13 or 14, wherein the temperature of the solution is between 5 0 C and 30 °C.

16. A process according to any one of claims 13 to 15, wherein (1019837_1):KZA r- 0R 3 and R4, together with the nitrogen atom linking them, form an unsubstituted or Ci-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring. O 17. A process according to claim 16 wherein R 3 and R4, together with the Snitrogen atom linking them, form a morpholino ring.

18. A process according to any one of claims 13 to 17, 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 00 00 19. A process according to any one of claims 13 to 18, wherein the CN detergent comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. C 20. A process according to claim 19, wherein the enzyme is a protease enzyme.

21. A process according to any one of claims 13 to 20, wherein the detergent comprises a peroxide. 1s 22. A process according to any one of claims 13 to 21, wherein the detergent comprises a peroxide and a peroxide activator.

23. A process according to claim 22, wherein the peroxide activator is TAED.

24. A process for the domestic washing treatment of a textile fibre material, said process as claimed in claim 13 and substantially as hereinbefore described with reference to any one of the examples but excluding the Experimental Report. Dated 14 November 2007 Ciba Specialty Chemicals Holding Inc. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON (1019837_1):KZA