It is commonly known to use fluorescent whitening agents in detergent compositions. 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 (2), possess superior properties with regard to, for examp ! e, sotubitity, buiid-up properties, light-fastness degree of whiteness, and also possess excellent white aspects in the solid stata. Favourable results are even obtained at low washing temperatures.

Accordingly, the present invention provides, as a first aspect, a detergent composition D comprising at least one compound of formula (1) wherein X1, X2, X3 and X4 are-N (R1) R2, wherein R, and R2 are independently from each other hydrogen; cyano; methyl ; substituted methyl ; CH2CH20H or Ce-Cycydoatky), or R and R2, together with the nitrogen atom linking them, form a heterocyclic ring, and M is hydrogen or a cation, together with at least one compound of formula (2)

wherein R3 and Rs, independently from each other, are hydrogen; unsubstituted C,-Csalkyl or substituted C1-C8alkyl, R4 and R8, independently from each other, are hydrogen ; unsubstituted phenyl ; unsubstituted C1-C8alkyl or substituted C1-C8alkyl, or NR3R4 and/or NR5R6 form an unsusbtited or substituted morpholino ring, and M is hydrogen or a cation.

Within the scope of the above definitions, C1-C8alkyl may be methyl, ethyl, n-or isopropyl, n-, sec.-or t-butyl, or linear or branched pentyl, hexyl, heptyl or octyl. Preferred are C,-C4alkyl groups. In case the alkyl groups are substituted examples of possible substituents are hydroxyl, phenyl, halogen, like fluorine, chlorine or bromine, sulfo, sulfao, carboxy and C1- Caikoxy, like methoxy and ethoxy. Other substituents of such al cyl groups are, for emple, cyano and-CONH2. Preferred substituents are hydroxy, carboxy, cyano, -CONH2 and phenyl, especially hydroxy, phenyl and carboxy. Furthermore, highly preferred substituents are hydroxy, phenyl and C,-C4alkoxy, especially hydroxy and phenyl. The alkyl groups can also be uninterrupted or interrupted by-0- (in case of alkyl groups containing two or more carbon atoms).

Examples for Cs-C7cycloalkyl groups are cyclopentyl and especially cydohexyl. These groups can be unsubstituted or substituted by, for example, C1-C4-alkyl, like methyl.

Preferred are the corresponding unsubstituted cycloalkyl groups.

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

If Ra and R2 together with the nitrogen atom form a heterocyclic ring such a ring system can be, for example, morpholino, piperidine or pynrolidine. The heterocyclic ring can be

unsubstituted or substituted. An example for such substituents is C,-C4alkyl, 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,-C4alkylammonium, mono-, di-or tri-C2-C4-hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of C-C¢alkyl and CrC4-hydroxyalkyl groups. Highly preferred is sodium.

R, and R2 are preferably independently from each other hydrogen; cyano; methyl ; methyl which is substituted by hydroxy, cyano, -CONH2, COOH or phenyl, especially by COOH ; CH2CH2OH ; unsubstituted or C1-C4alkyl-substituted C5-C7cycloalkyl, especially cyclohexyl ; or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl- substituted morpholino, piperidine or pyrrolidine ring.

More preferably, R, and R2 are independently from each other hydrogen ; methyl ; COOH- substituted methyl ; CH2CH2OH ; unsubstituted or C1-C4alkyl-substituted C5-C7cycloalkyl, or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl- subsumed morpholino, piperidine or pyrrolidine ring. Highly praferred meanings for Ri and R2 are hydrogen, methyl or -CH2CH2OH, or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl-substituted morpholino, piparidine or pyrrolidine ring. Most preferred are unsubstituted or C1-C4-alkyl-substituted morpholino, piperidine or pyrrolidine rings, especially morpholino, formed by Ri and R2 together with the nitrogen atom linking them.

Examples of-N (Ri) R$ groups are -NH2, -NHCH3, -N(CH3)2, -NH(CH2CH2OH),

Xi and X3 have preferably the same meanings. In addition it is preferred that X2 and X4 have the same meanings. Furthermore, it is preferred that the four radicals X1, X2, X3 and X4 do not have identical meanings.

Preferred are detergent compositions D comprising at least one compound of formula (1), wherein Ri and R2 are independently from each other hydrogen; cyano; methyl which is unsubstituted or substituted by hydroxy, cyano,-CONH2,-COOH or phenyl ; CH2CH20H ; unsubstituted or C1-C4alkyl-substituted C5-C7cycloalkyl ; or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl- substituted morpholino, piperidine or pyrrolidine ring.

Of particular interest are detergent compositions D comprising at least one compound of formula (1), wherein X, and X3 are amino, and X2 and X4 are a radical of formula -N(R1)R2, wherein Ri and R2 are independently from each other hydrogen; unsubstituted or COOH or CN substituted methyl ; CH2CH20H ; unsubstituted or C1-C4alkyl-substituted cyclopentyl or cyclohexyl, or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or C,- C4alkyl-substituted morpholino, piperidine or pyrrolidine ring.

Preferred are detergent compositions D comprising at least one compound of formula (2) wherein R3 and R5, independently of each other, are hydrogen; unsubstituted C,-C4alkyl or substituted C1-C4alkyl,

R4 and Ro, independently of each other, are unsubstituted phenyl ; unsubstituted C1-C4alkyl or substituted C1-C4alkyl, or NR3R4 and/or NRsRe form a morpholino ring, and M is hydrogen or an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine.

More preferred are detergent compositions D comprising at least one compound of formula (2) wherein R3 and R5, independently of each other, are hydrogen; unsubstituted C1-C2alkyl or C,- C4aliyl, which is substituted by hydroxy or C,-C4alkoxy, Rt and R6, independently of each other, are unsubstituted phenyl ; unsubstituted C1-C2alkyl or C1-C4alkyl, which is substituted by hydroxy or C1-C4alkoxy, r NR3R4 and/or NR5R8 form a morpholino ring, and M is hydrogen or an alkali metal atom.

Especially preferred are detergent compositions D comprising at least one compound of formula (2a) wherein R3 is hydrogen ; unsubstituted C,-C2alkyl or C,-C4alkyl, which is substituted by hydroxy or C1-C4alkoxy, R4 is unsubstituted phenyl ; unsubstituted C,-C2alkyl or C1-C4alkyl, which is substituted by hydroxy or C1-C4alkoxy, or NR3R4 forms a morpholino ring, and M is hydrogen or an alkali metal atom, preferably sodium.

Example of such preferred compounds of formula (2a) are those of formula (2b)- (2f)

An especially preferred detergent composition D comprises at least one compound of formula (1') wherein Ri and and are independently from each other hydrogen ; unsubstituted or COOH or CM substituted methyl ; CH2CHzOH ; unsubstituted or C1-C4alkyl-substituted cyclopentyl or cyclohexyl, or R, and R2, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl- substituted morpholino, piperidine or pyrrolidine ring, and at least one compound of formulae (2b)

In the mixtures of compounds of formulae (1) or (1') and (2) or (2a) or (2b)- (2f) the molar ratio of compound (1) or (1') to compound (2) or (2a) or (2b)-(2f) 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.

The compounds of formulae (1) and (2) are known or can be prepared in analogy to known processes.

Compounds of formula (1) 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, X2, X3 and X4. 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 X1, X2, X3 and X4. For the preparation of compounds wherein X, and X3 having the same meaning, and also X2 and X4 have the same meaning, it is preferred to react the intermediate obtained first with an amino compound capable of introducing X, and X3, and, finally with an amino compound capaale of introducing X2 and X4. It is also possible to carry out the reaction with the amino compounds in one step by reacting the intermediate with a mixture ofsmino compounds ; in such a case usually corresponding mixtures of compounds of formula (9) are obtained.

The detergent compositions used preferably comprise i) 1-70 weight-% (wt-%) of at ieast one anionic surfactant and/or at ieast one nonionio surFactant ; ii) 0-75 wt-% of at least one builder, iii) 0-30 wt-% of at least one peroxide ; iv) 0-10 wt-% of at least one peroxide activator; and v) 0. 001-5 wt-% of a mixture comprising at least one compound of formula (1) and at least one compound of formula (2), each by weight, based on the total weight of the detergent composition.

More preferably the detergent compositions used comprise i) 5-70 wt-% of at least one anionic surfactant and/or at least one nonionic surfactant ; ii) 5-70 wt-% of at least one builder ; iii) 0. 5-30 wt-% of at least one peroxide; iv) 0.5-10 wt-% of at least one peroxide activator and/or 0.1-2% of a bleaching catalyst; and v) 0.01-5 wt-% of a mixture comprising at least one compound of formula (1) and at least one compound of formula (2), each by weight, based on the total weight of the detergent composition.

All preferences for the compounds of formula (1) and for the compounds of formula (2) defined above apply also for component v) of the detergent composition.

In general, an amount of a mixture comprising at least one compound of formula (1) and comprising at least one compound of formula (2) of 0. 001-5 wt-%, especially an amount of 0.01-5 wt-% is used. Highly preferred is an amount of 0. 05-5 wt-%, especially 0.05 to 2%. In general, amounts given in percent are to be understood as being percent by weight, based on the total weight of the detergent composition, unless otherwise stated.

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

The anionic surfactant component may be, e.g., an alkylbenzenesulfonate, an alkylsulfate, an alkylethersulfate, an olefinsulfonate, an alkanesulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or an o-suifofatty acid salt or an ester thereof. Preferred are allylbenzenesulfonats having 10 to 20 carbon atoms in the aikyi group, aikyisuifates having 8 to 18 carbon atoms, alkylethersulfates having 8 to 1S carbon atoms, and fatty acid saits being derived from palm oil or tallow and having 8 to 18 carbon atoms. The average molar number of ethylene oxide added in the aikyiethersuifate is preferably 1 to 20, preferably 1 to 10. 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 (R1)CH2COOM1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4 alkyl and M1 is an alkali metal, especially sodium.

The nonionic surfactant component may be, e. g. , primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Cl-cive 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 wt-%, preferably 540 wt-% and more preferably 5-30 wt-%. As to these surfactants it is preferred that the lower limit is 10 wt-%, based on the total weight of the detergent composition.

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 (alkylen phosphonate); or a mixture of these.

Preferred silicates are crystalline layered sodium silicates of the formula NaHSimO2m+1.pH2O or Na2SLO »,. pH20 in which m is a number from 1.9 to 4 and p is 0 to 20.

Preferred aluminosilicates are the commercially-available synthetic materials designated as Zeclites A, B, X, and HS, or mixtures of these. these. Zeolite A is preferred.

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

Preferred poycarboxylic acids include nitrilotriacetic acid and ethylens diamine tetraecaüc acid.

Preferred organic phosphonates or aminoalkylene poly (alkylen phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimthyiene phosphonates, ethylens diamins tetra mathylene phosphonates and diethyiene triamine penta methytone phosphonates.

The amount of builders is preferably 5-70 wt-%, preferably 5-60 wt-% and more preferably 10-60 wt-%. As to the builders it is preferred that the lower limit is 15 wt-%, especially 20 wt- %, based on the total weight of the detergent composition.

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°C.

In particular, the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 1, preferably 2 to 20, carbon atoms; in particular peroxyacetic acid or 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 wt-%, preferably 1-20 wt-% and more preferably 1-15 wt-%. In case a peroxide is used, the lower limit is preferably 2 wt-%, especially 5 wt-%, based on the total weight of the detergent composition.

The peroxides, especially the inorganic peroxides, are preferably activated by the indusion 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 10 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 tetraacetyietnyianediamine (TAED), acrylate-d gtycoiurits, especially etraacetylglycoluril (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 wherein R is a sulfonate group, a caroxylic acid group or a carboxylate group, and wherein R'is ! inear or branched (C7-C15)alkyl ; ; also activators that are known under the names 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), pentaacetyifructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated, glucamine and gluconolactone. The combinations of conventional bleach activators disdosed 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 wt-%, preferably 0-8 wt-%. In case a bleach activator is used, the lower limit is preferably 0.5 wt-%, especially 1 wt-%, based on the total weight of the detergent composition.

Bleaching catalysts, which may be added, include, e. g., 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 wt-%, more preferably 0.01 to 2 wt-%, especially 0.05 to 2 wt-%. Highly preferred is an amount of 0.1-2 wt-%, based on the total weight of the detergent composition.

As examples for bleaching catalysts the following are mentioned: - WO-A-95/30681 (see i. e. formula (I) and the following definition on page 1, lines 7 to 30; especially formula (I) 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 (1), (2) and (3) and the following definitions given on pages 2 and 3).

- WO-A-01/05925 (see i.e. formula (1) 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 (2) on page 3 and those of formula (3) on page 4).

- WO-A-02/088269 (see i.e. formula (1) 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).

Furthermore, the detergent compositions can optionally contain enzymes. Enzymes can be added to detergent compositions fior stain removal. Tha 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 protease. 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 compositions. When used, the enzymes are usually present in an amount of 0.01-5 wt-%, preferably 0.05-5 wt-% and more preferably 0. 1-4 wt-%, based on the total weight of the detergent composition.

Further preferred additives for the detergent compositions 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 50 008. Such polymers are usually used in'an amount of from 0. 01 to 5 wt-%, preferably 0.05 to 5 wt-%, especially 0.1 to 2 wt-%, based on the total weight of the detergent composition. Preferred polymers are those given in WO-A-02/02865 (see especlally page 1, last paragraph and page 2, first paragraph).

The detergent compositions used will usually contain one or more auxiliaries such as soil suspending agents, for exampia sodium carboxymethyicaiiuiose ; salts for adjusting the pH, for example alkali or alkaline earth metal silicates ; foam regulators, for example soap ; salt$ for adjusting the spray drying and granulating properties, for exsmpie sodium sulphate ; perfumes ; and also, if appropriate, antistatic and softening agents ; such as smectite days ; photobleaching agents ; 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 wt-%, preferably 0.5 to 10 wt-%, especially 0.5 to 5 wt-%, based on the total weight of the detergent composition.

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 25°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 wt-%, preferably 0-5 wt-%, especially 0-1 wt-%, based on the total weight of the detergent composition. Such detergent compositions usually have a bulk density of 650-1000 g/l, preferably 700-1000 glu and especially 750-1000 g/i.

The detergent compositions can also be present in the form of tablets. Relevant characteristics of tablets ara 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 kgAitre. To enable fast disintegratiowlaundry detergent tablets generally contain special disintegrants : -Efkrve$cent$ such as carbonate/hydscg@ncarbonate/citrie acid ; - swelling agents like cellulose, carboxymethyl cellulose, cross-linked poly (N- vinylpyrrollidone) ; -quickly dissolving materials such as Na (K) acetats, or Na (K) citrate ; - rapidly dissolving water-soluble rigid costing such as dicarboxy acide.

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

The detergent composition may also be formulated as an aqueous liquid comprising 5-50 wt-%, preferably 10-35 wt-% or as a non-aqueous liquid detergent, containing not more than 5 wt-%, preferably 0-1 wt-% of water, based on the total weight of the detergent composition. Non-aqueous liquid 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 (e. g. , 1, 3-propanediol, ethylene glycol, glycerine, and 1, 2-propanediol) can also be used. The compositions may contain from 5 to 90 wt-%, typically 10 to 50 wt-% of such carriers, based on the total weight of the detergent composition. The detergent compositions can also be present as the so-called"unit liquid dose"form.

An especially preferred detergent composition comprises i) 5-70 wt-% of at least one anionic surfactant and/or at least one nonionic surfactant ; ii) 5-70 wt-% of at least one builder; iii) 0.5-30 wt-% of at least one peroxide ; iv) 0. 5-10 wt-% of at least one peroxide activator and/or 0. 1-2% of a bleaching catalyst; and v) 0. 01-5 wt-% of a mixture comprising at least one compound of formula (1') wherein Ri and R2 are hydrogen ; unsubstituted or COOH or CM substituted methyt ; CH2CH20H ; unsubstituted or C1-C4alkyl-substituted cyclopentyl or cyclohexyl, or R, and R2, together with the nitrogen atom linking them, form an unsubstituted or C1- C4alkyl-substituted morpholino, piperidine or pyrrolidine ring, and at least one compound of formulae (2b)- (20

each by weight, based on the total weight of the detergent composition.

In the mixbjres of compounds of formulae (1) or (1') and (2) or (2a) or (2b)- (20 the molar ratio of compound (1) or (1') to compound (2) or (2a) or (2b (2f) 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.

Furthermore, the present invention is directed to a detergent composition D'comprising at least one compound of formula (1)

wherein Xi, X2, X3 and X4 are, independently of each other,-N (Ri) R2, wherein Ri and R2 are independently from each other hydrogen ; cyano ; methyl which is unsubstituted or substituted by hydroxy, cyano, -CONH2 cor phenyl ; CH2CH2OH ; unsubstituted or C1-C4alkyl-substituted C5-C7cycloalkyl ; or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or Cl- C4alkyl-substituted morpholino, piperidine or pyrrolidine ring ; and M is hydrogen or a cation, together with at least one compound of formula (2) wherein R3 and Ru, independently from each other, are hydrogen; unsubstituted C1-C8alkyl or substituted C1-C8alkyl, R4 and Re, independently from each other, are hydrogen ; unsubstituted phenyl ; unsubstituted Ci-Csaikyi or substituted C1-CBalkyl, or NR3R4 and/or NR5Rs form an unsubstituted or substituted morpholino ring, and M is hydrogen or a cation, and wherein the detergent composition contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.

As to the compounds of formula (1) and (2) as well as to the substituents thereof the meanings and preferences given above apply.

Preferred are detergent compositions D'comprising at least one compound of formula (1), wherein Ri and R2 are independently from each other hydrogen; cyano; methyl which is unsubstituted or substituted by hydroxy, cyano,-CONH2,-COOH or phenyl ; CH2CH20H ; unsubstituted or CrC4alkyl-substituted Cs-C7cycloalkyl ; or Ra and R2, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl- substituted morpholino, piperidine or pyrrolidine ring.

Of particular interest are detergent compositions D'comprising at least one compound of formula (1), wherein Xi and X3 are amino, and X2 and X4 are a radical of formula -N(R1)R2, wherein R1 and R2 are independently from each other hydrogen ; unsubstituted or COOH or CM substituted methyl ; CH2CH2OH ; unsubstituted or C1-C4alkyl-substituted cyciopantyt or cyclohexy, or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or C1- C4alkyl-substituted morpholino, piperidine or pyrrolidine ring.

Of interest are detergent composition D'comprising at least one compound of formula (2), wherein Ra and Rs, independently of each other, are hydrogen ; unsubstituted or substituted methyl, Rs and R7, independently of each other, are unsubstituted phenyl ; unsubstituted or substituted methyl, or NR3R4 and/or NR5R6 form a morpholino ring, and M is hydrogen or a cation.

Of preferred interest are detergent composition D'comprising at least one compound of formula (2), wherein R3 and Rs, independently of each other, are hydrogen; unsubstituted C1-C2alkyl or Ci- C4alkyl, which is substituted by hydroxy or C1-C4alkoxy, R4 and R6, independently of each other, are unsubstituted phenyl ; unsubstituted C1-C2alkyl or C1-Caalkyl, which is substituted by hydroxy or C1-C4alkoxy, or NR3R4 and/or NRsRe form an unsubstituted or substituted morpholino ring, and M is hydrogen or a cation.

Of more preferred interest are detergent compositions D'comprising at least one compound of formula (2a) wherein R3 is hydrogen ; unsubstituted C1-C2alkyl or C1-C4alkyl, which is substituted by hydroxy or C1-C4alkoxy, R4 is unsubstituted phenyl; unsubstituted C1-C2alkyl or C1-C4alkyl, which is substituted by hydroxy or C'-Caalkoxy, or NR3R4 forms a morphoiino ring, and M is hydrogen or an alkali metal atom, preferably sodium.

Of special interest are compounds of formula (2a) are those of formula (2b)- (2f)

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

Preferred are detergent compositions comprising i) 1-70 wt-% of at least one anionic surfactant and/or a nonionic surfactant; ii) 0-75 wt-% of at least one builder ; iii) 0-30 wt-% of at least one peroxide; iv) 0-10 wt-% of at least one peroxide activator ; v) 0. 001-5 wt-% of a mixture comprising at least one compound of formula (1) and at least one compound of formula (2); and vi) 0. 05-5 wt-% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, especially protease.

Highly preferred are detergent compositions comprising i) 5-70 wt-% of at least one anionic surfactant and/or a nonionic surfactant ; ii) 5-70 wt-% of at least one builder ; iii) 0. 5-30 wt-% of at least one peroxide; iv) 0.5-10 wt-% of at least one peroxide activator and/or 0.1-2 wt-% of a bleaching catalyst; v) 0.01-5 wt-% of a mixture comprising at least one compound of formula (1) and at least one compound of formula (2); and vi) 0.05-5 wt-% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, especially protease.

All preferences for the compounds of formula (1) and for the compounds of formula (2) defined above apply also for componentv) of the detergent composition.

Very highly preferred are detergent composifions comprising i) 5-70 wi-°X0 of at least one anionic surfactant and/or a nonionic surfactant ; ii) 5-70 wt-% of at least one builder ; iii) 0. 5-30 wt-% of at least one peroxide; iv) 0. 5-10 wt-% of at least one peroxide activator and/or 0.1-2 wt-% of a bleaching catalyst ; v) 0. 01-5 wt-% of a mixture comprising at least one compound of formula (1') wherein Ra and R2 are hydrogen; unsubstituted or COOH or CN substituted methyl ; CH2CH20H ; unsubstituted or C1-C4alkylffubstituted cydopentyl or cyclohexyl, or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or C,- C4alkyl-substituted morpholino, piperidine or pyrrolidine ring, and at least one compound of formulae (2b) - (2f)

vi) 0.05-5 wt-% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, especially protease.

In the mixtures of compounds of formulae (1) or (1') and (2) or (2a) or (2boy (2f) the molar ratio of compound (1) or (1') to compound (2) or (2a) or (2boy (20 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 raüo of from 30: 70 to 70 : 30, especially 40 : eo to 60 : 40.

As to the enzymes, the detergents and the ingredients thereof the definitions and preferences given above apply.

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 1000 g/m2, especially less than 500 g/m2 and most preferred less than 250 g/m2.

According to this process usually an amount of 0.01 to 3.0 wt-%, especially 0.05 to 3.0 wt-%, based on the weight of the textile fibre material, of a mixture comprising at least one compound of formula (1) and at least one compound of formula (2) is used.

The process is usually conducted in the temperature range of from 5 to 100°C, especially 5 to 60°C. Preferred is a temperature range of 5 to 40°C, especially 5 to 35°C and more preferably 5 to 30°C.

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.

Techniques for controlling pH at recommended usage levels indude 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, e. g., from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 85 litre. 9, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Examples are -top-loading, vertical axis U. S.-typa automatic washing machines using about 45 to 83 iitars 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 50°C ; - front-loading, horizontal-axis European-type automatic washing machine using about 8 to 15 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°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 25°C.

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 (P) wherein the textile fibre material is contacted with an aqueous solution of a detergent composition comprising a mixture comprising at least one compound of formula (1)

X1, X2, X3 and X4 are, independently of each other,-N (R,) R2, wherein R, and R2 are hydrogen ; cyano ; methyl which is unsubstituted or substituted by hydroxy, cyano,-CONH2 or phenyi ; CHzCHzOH ; unsubstituted or C1-C4alkyl-substituted C6- C7Cycloalkyl ; or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or Cl.

C4alkyl-substituted morpholino, piperidine or pyrrolidine ring ; and M is hydrogen or a cation,. together with at least one compound of formula (2) wherein Ra and Rs, independently from each other, are hydrogen; unsubstituted Ci-Ceaikyi or substituted Cr-Caalicy, R4 and R6, independently from each other, are hydrogen; unsubstituted phenyl ; unsubstituted C1-C8alkyl or substituted Cl-Csalkyl, or NR3R4 and/or NRsRe form an unsubstituted or substituted morpholino ring, and M is hydrogen or a cation, and wherein the detergent composition 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°C, preferably between 5°C and 30°C, throughout the process.

As to the compounds of formula (1) and (2) as well as to the substituents thereof the meanings and preferences given above apply.

Of interest is a process (P) using a detergent composition comprising at least one compound of formula (1), wherein X1, X2, X3 and X4 are, independently of each other,-N (R,) R2, wherein R, and Ra are hydrogen; unsubstituted or CN or COOH-substituted C,-Cealkyl ; CH2CH2OH ; unsubstituted or C1-C4alkyl-substituted Cs-C7cycloalkyl, or R, and R2, together with the nitrogen atom linking them, form an unsubstituted or C,- C4alkyl-substitued morpholino, piperidine or pyrrolidine ring, and M is hydrogen or a cation.

Of particular interest is a process (P) using a detergent composition comprising at least one compound of formula formula (1), wherein Xi and and are amino, and X2 and X4 are a radical of formula -N(R1)R2, wherein R, and R2 are hydrogen; unsubstituted or COOH or CN substituted methyl ; CH2CH20H ; unsubstituted or C1-C4alkyl-substituted cyclopentyl or cyclohexyl, or Ri and R2, together with the nitrogen atom linking them, form an unsubstitued or Cl- C4alkyl-subdstituted morpholino, piperidine or pyrrolidine ring.

Of interest is a process (P) using a detergent composition comprising at least one compound of formula (2), wherein R3 and R5, independently of each other, are hydrogen; unsubstituted C,-C4alkyl or substituted Cl-C4alkyl, R4 and Re, independently of each other, are unsubstituted phenyl ; unsubstitued C1-C4alkyl or substituted Chalky), or NR3R4 and/or NRsRa form a morpholino ring, and M is hydrogen or a cation.

Of preferred interest is a process (P) using a detergent composition comprising at least one compound of formula (2), wherein R3 and R5, independently of each other, are hydrogen; unsubstituted C1-C2alkyl or C,- C4alkyl, which is substituted by hydroxy or C1-C4alkoxy,

R4 and R6, independently of each other, are unsubstituted phenyl ; unsubstituted C-C2alkyl or C1-C4alkyl, which is substituted by hydroxy or C,-C4alkoxy, or NR3R4 and/or NR5R6 form a morpholino ring, and M is hydrogen or a cation.

Of more preferred interest is a process (P) using a detergent composition comprising at least one compound of formula (2a) wherein R3 is hydrogen ; unsubstituted C1-C2alky or C1-C4alkyl, which is substituted by hydroxy or C1-C4alkoxy, R4 is unsubstituted phenyl ; unsubstituted C,-C2alkyl or C,-C4alkyl, which is substituted by hydroxy or C1-C4alkoxy, or MR3R, forms an unsubstituted or substituted morpholino ring, and M is hydrogen or an alkali metal atom, preferably sodium.

Of special interest is a process (P) using a detergent composition comprising at least one compound of formulae (2b) - (2f)

An especially preferred process for the domestic washing treatment of a textile fibre material (P) wherein the textile fibre material is contacted with an aqueous solution of a detergent composition comprising a mixture comprising at least one compound of formula (1') wherein R, and R2 independently from each other are hydrogen; unsubstituted or COOH or CN substituted methyl ; CH2CH2OH ; unsubstituted or C1-C4alkyl-substituted cyclopentyl or cydohet, or- R, and R2, together with the nitrogen, atom linking them, from an unsubstituted or C1-C4alkyl- substituted morpholina, piperidine or pyrrolidine ring, and at least one compound of formulae (2b) - (2f)

and wherein the detergent composition contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, and wherein the temperature of the sclution is between 5°C and 40°C, preferably between 5OC and 30°C, throughout the process.

According to this process usually an amount of 0.01 to 3.0 wt-%, especially 0. 05 to 3.0 wt-%, based on the weight of the textile fibre material, of the mixture comprising at least one compound of formula (1) or (1') and at least one compound of formula (2), (2a) or (2b> (20 is used.

In the mixtures of compounds of formulae (1) or (1') and (2) or (2a) or (2b)- (2f) the molar ratio of compound (1) or (1') to compound (2) or (2a) or (2boy (2f) 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.

The 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 mixtures show very good results with respect to exhaustion properties.

A further embodiment of the present invention are mixtures M comprising at least one compound of formula (1) wherein Xi, X2, X3 and X4 are, independently of each other,-N (R,) R2, wherein R and R2 are hydrogen; cyano; unsubstituted or substituted methyl, ; CH2CH20H or C5- C7cycloalkyl, or Ri and R2, together with the nitrogen atom linking them, form a heterocyclic ring, and M is hydrogen or a cation, together with at least one compound of formula (2) wherein R3 and R5, independently from each other, are hydrogen; unsubstituted C1-C8alkyl or substituted C,-C8aliyi, R4 and RB, independently from each other, are hydrogen, unsubstituted phenyl ; unsubstituted Ci-Csatky) or substituted C1-C8alkyl, or NR3R4 and/or NR5R6 form an unsubstituted or substituted morpholino ring, and M is hydrogen or a cation.

Of interest are mixtures M comprising at least one compound of formula (1), wherein Ri and R2 are independently from each other hydrogen; cyano; methyl which is unsubstituted or substituted by hydroxy, cyano, -CONH2, -COOH or phenyl ; CH2CH2OH ; unsubstituted or C1-C4alkyl-substituted C5-C7cycloalkyl ; or R, and R2, together with the nitrogen atom linking them, form an unsubstituted or C,-C4alkyl- substituted morpholino, piperidine or pyrrolidine ring.

Of particular interest are mixtures M comprising at least one compound of formula (1), wherein Xi and X3 are amino, and X2 and X4 are a radical of formula-N (R1) R2, wherein R1 and R2 are independently from each other hydrogen ; unsubstituted or COOH or CN substituted methyl ; CH2CH2OH ; unsubstituted or C1-C4alkyl-substituted cyclopentyl or cyclohexyl, or R1 and R2, together with the nitrogen atom linking them, form an unsubstituted or C,- C4alkyl-substituted morpholino, piperidine or pyrrolidine ring.

Most interesting are mixtures M comprising at least one compound of formula (1), wherein Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl- substituted morpholino, piperidine or pyrrolidine ring.

Of interest are mixtures M comprising at least one compound of formula (2), wherein R3 and Rs, independently of each other, are hydrogen; unsubstituted C1-C4alkyl or substituted C1-C4alkyl, R4 and Re, independently of each other, are unsubstituted phenyl ; unsubstituted C,-C4alkyl or substituted C1-C4 alkyl, or NR3R4 and/or NRsRe form an unsubstituted or substituted morpholino ring, and M is hydrogen or a cation.

Of preferred interest are mixtures M comprising at least one compound of formula (2), wherein R3 and R5, independently of each other, are hydrogen; unsubstituted Cl-C2alkyl or C- C4alkyl, which is substituted by hydroxy or C1-C4alkoxy, R4 and R8, independently of each other, are unsubstituted phenyl ; unsubstituted C1-C2alkyl or C,-C4alkyl, which is substituted by hydroxy or C,-C4alkoxy, or NR3R4 and/or NR5R6 form an unsubstituted or substituted morpholino ring, and M is hydrogen or a cation.

Of more preferred interest are mixtures M comprising at least one compound of formula (2a)

wherein R3 is hydrogen ; unsubstituted C1-C2alkyl or C1-C4alkyl, which is substituted by hydroxy or C1-C4alkoxy, RL is is unsubstituted phanyi ; unsubstituted C1-C2alkyl or C1-C4alkyl, which is substituted by hydroxy or C aikoxy, or NR3R4 forms an unsubstituted or substituted morpholino ring, and M is hydrogen or an alkali metal atom, preferably sodium.

Of special interest are mixtures M comprising compounds of formula (2), wherein the compounds of formula (2) are those of formula (2b)- zu

Especially preferred mixtures M are those comprising at least one compound of formula (1') wherein R, and R2 independently from each other are hydrogen; unsubstituted or COOH or CN substituted methyl ; CH2CH20H ; unsubstituted or C,-C4alkyl-substituted cyclopentyl or cyclohexyl, or Ri and R2, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl- substituted morpholino, piperidine or pyrrolidine ring, and at least one compound of formulae (2b) - (2f)

In the mixtures of compounds of formulae (1) or (1') and (2) or (2a) or (2b)- (2f) the molar ratio of compound (1) or (1') to compound (2) or (2a) or (2b)-(2f) 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.

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 mixtures of these compounds stable both in pulverulent washing agent and in washing baths. In addition, they impart a brilliant appearan in daylight. The Mowing Examples serwe to illustrate the invention ; parts and percentages are by weight and the temperature is given in degree Celsius unless otherwise stated.

Preparation Example 1: In a 1 liter flask 0.05 mole of the compound of formula

are mixed with 600mi of water and heated to a temperature of 60°C. Then 7. 8g of methylethanolamine 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 30°C. 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 29. 3g of a yellowish product of the compound of formula (101) Preparation Examples 2 to 12 : The following compounds of formula can be prepared in analogy to the process given in Preparation Example 1, by replacing methylethanolamine with an equimolar amount of the corresponding amine. X is as defined in the following Table 1. Compounds which precipitate after cooling to 50°C are isolated directly as sodium salts without addition of hydrochloric acid and then dried in vaccuum.

Table 1 Example X N 1 nu NH -NHCH2COOH 5-NHCH2CH2OH '6-NHCHzCHzCOOH 7-M 8-N (CH2CH20H) 9-nô 10 I 7 (CH3) CH2COOHPreparation Example 11:

In a 2 litre flask 130moi of methylethylketone, 80ml of deionised water, 150g of ice and 18. 5g cyanuric chloride are mixed. Over a period of 30 minutes 185mi of a solution of 4, 4'- diaminostilbene-2, 2'-disulfonic acid (as disodium salt) in water (concentration of 100g/1) are added dropwise, the temperature being between-8 und +5°C. 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 (99%) 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 30 minutes a mixture of methylethylketon 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.

A yellowish crystalline precipitate can be filtered off. After drying 29g of a yellowish product of the compound of formula (103) are obtained.

Preparation Examoie 12 :' In a i lits3 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 500ml of water.

18g of an aqueous solution of methylamine (40%) 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°C. In this way there are obtained 21.2g of a yellowish powder of the compound of formula (104) are obtained.

Preparation Example 13 The compound of formula (104a) can be prepared in analogy to the process given in Preparation Example 12, by replacing N, N'-bis- (4-morpholino-6-chloro-1, 3, 5-triazine-2-yl)- 4, 4'-diaminostilbene-2, 2'-disulfonic acid with an equimolar amount of the compound of formula (101).

Preparation Example 14 The compound of formula (104b) can be prepared in analogy to the process given in Preparation Example 13, by methylamine with an equimolar amount of dimethylamine.

Preparation Example 15: The compound of formula (105) can be prepared in analogy to the process given in Preparation Example 14, by replacing 18g of an aqueous solution of methylamine (40%) with a corresponding solution containing an equimolar amount of dimethylamine.

Preparation Example 16:

In a 1 liter flask 0.05 mole of N,N'-bis-(4-morpholino-6-chloro-1, 3, 5-triazine-2-yl)-4, 4'- diaminostibene-2, 2'-disulfonic acid (as disodium salt) are suspended in 600ml of water and heated to a temperature of 60°C. 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 25°C and 10% by volume of sodium chloride are added. The precipitate is filtered off, washed with 100moi of a 10% aqueous sodium chloride solution and dried in vacuum at 70°C.

In this way there are obtained 41. 8g of a yellowish powder.

Application Example 1: General procedure : A wash liquor is prepared by dissolving 0.8g of a washing powder in 200ml of tap water. log of bleached cotton fabric is added to the bath and washed at 40°C 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 2a and 2b are in g) : Table 2a (Ingredients of washing powders A and B) Ingrediente A Sodium laurylbenzene-sulfonate (LAS) 10g 10g Sodium lauryl ether sulfate (AES) 3g 3g Dobanol 23-6. 5 (nonionic alcoholethoxylate) 4g 4g Sodium tripolyphosphate 30g- Zeolite A 20g Sodium carbonate 15g 15g Sodium silicate 59 59 Sodium sulfate 11g 17g Sodium perborate monohydrate log log TAED 3g 3g Polycarboxylate (co-builder) 4g Carboxymethylcellulose 2g 2g PerFume 0. 1g 0.1g Water 5g 5g Fluorescent whitener used Xg Xg Table 2b (Washing powders used) Amount of Washing powder fluorescent whitener Mixture of compound of Prep. Ex. 6 and 0. 2g A compound of formula (2b) [7 : 3 weight ratio] Mixture of compound of Prep. Ex. 12 and 0. 1g B compound of formula (2b) [7: 3 weight ratio] Mixture of compound of Prep. Ex. 14 and 0. 3g A compound of formula (2c) [7:3 weight ratio] Mixture of compound of Prep. Ex. 1 and 0.2g A compound of formula (2c) [1 : 1 weight ratio] Mixture of compound of Prep. Ex. 2 and 0. 4g A compound of formula (2d) [1 : 2 weight ratio] Mixture of compound of Prep. Ex. 3 and 0. 15g B compound of formula (2d) 1 : 5 weight ratiol Mixture of compound of Prep. Ex. 4 and 0. 1 B compound of formula (2e) [5 : 1 weight ratio] Mixture of compound of Prep. Ex.. 5 and 0. 3g B compound of formula (2e) [1 : 1 weight ratio Mixture of compound of Prep. Ex. 6 and 0. 2g A compound of formula (2f) [3 : 7 weight ratio] Mixture of compound of Prep. Ex. 7 and 0.3g A compound of formula (2f) [1 : 9 weight ratio Mixture of compound of Prep. Ex. 8 and 0. 2g B compound of formula (2f) [9 : 1 weight ratio] Mixture of compound of Prep. Ex. 9 and 0.1g compound of formula (2b) [1 : 9 weight ratio] Mixture of compound of formula (107) and 0. 3g B compound of formula (2b) [1 : 1 weight ratio]

Constitution of compound of formula (107): The cotton fabrics washed with the detergents given in Table 2b according to the general procedure show good whiteness properties.

Application Example 2: General procedure:

A wash liquor is prepared by dissolving 0. 8g of a washing powder in 200moi of tap water. lOg 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 160°C.

The following washing powders are used (amounts given in the following Tables 3a and 3b are percent by weight, based on the total weight of the detergent): Table 3a (Ingredients of washing powders C and D) Ingredients C D Sodium laurylbenzene-sulfbnate (LAS) 8% 8% Sodium lauryl ether sulfate (AES) 3% 3% Dobanol 23-6. 5 (non-ionic alcoholethoxylate) 5% 5% Zeclite A 20% 20% Polycarboxylate (co-builder) 5% 5% Soda ash 18% 18% Sodium silicate 4% 4% Sodium sulfate 5% 5% Hydroxyethanediphosphonic acid (complexing agent) 0.5% 0. 5% Cellulase 1.5% Protease-1. 5% Carboxymethylcellulose 1% 1% Sodium perborate monohydrate 15% 15% TAED 5% 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 3b (Washing powders used) Amount of Washing powder fluorescent whitener Mixture of compound of Prep. Ex. 13 and 0.2% C compound of formula (2b) : 3 weight ratio Mixture of compound of Prep. Ex. 10 and 0.2% C compound of formula (2b) 7 : 3 weight ratio] Mixture of compound of Prep. Ex. 11 and 0.3% C compound of formula (2c) [7 : 3 weight ratiol Mixture of compound of Prep. Ex. 1 and 0. 2% D compound of formula (2c) [1 : 1 wight ratio Amount of Washing powder fluorescent whitener Mixture of compound of Prep. Ex. 14 and 0.2% C compound of formula (2d) [1 : 2 weight ratio] Mixture of compound of Prep. Ex. 2 and 0.4% C compound of formula (2d) [1 : 5 weight ratio] Mixture of compound of Prep. Ex. 3 and 0.2% D compound of formula (2e) [5 : 1 weight ratio] Mixture of compound of Prep. Ex. 4 and 0.2% C compound of formula (2e) [1 : 1 weight ratio] Mixture of compound of Prep. Ex. 13 and 0.3% D compound of formula (2f) [3 : 7 wei ht ratio Mixture of compound of Prep. Ex. 5 and 0. 2% C compound of formula (2f) [1 : 9 weight ratio] Mixture of compound of Prep. Ex. 6 and 0. 4. % C compound of formula (2f) [9:1 weight ratio Mixture of compound of Prep. Ex. 7 and 0. 3% compound of formula (2b) [1:1 weight ratio Mixture of compound of formula (107) and 0. 5% C compound of formula (2c) [1:1 weight ratio Mi of compound of formula (107) and 0.3% compound of formula (2d) [1 : 1 weight ratio]

As to the constitution of compound of formula (109) see Application Example 1.

The cotton fabrics washed with the detergents given in Table 3b according to the general procedure show good whiteness properties.

Application Example 3: General procedure: A wash liquor is prepared by dissolving 0. 8g of a washing powder in 200moi of tap water. 10g of bleached cotton fabric is added to the bath and washed at 40°C 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 4a and 4b are in g) : Table 4a (ingredients of washing powders A and B) Ingredients A B Sodium laurylbenzene-sulfonate (LAS) log 10g Sodium lauryl ether sulfate (AES) 3g 3g Dobanol 23-6.5 (nonionic alcoholethoxylate) 4g 4g Ingredients A B Sodium tripolyphosphate 30g Zeolite A # 20g Sodium carbonate 15g 15g Sodium silicate 5g 5g Sodium sulfate lug 17g Cellulase 1. 5g Protease # 1.5g Polycarboxylate (co-builder) 4g Carboxymethylcellulose Perfume 0.1g 0.1g Water 5g 5g Fluorescent whitener or mixture of fluorescent whitener Xg Xg used Table 4b (Washing powders used) Amount of fluorescent Washing whitener powder Mixture of compound of Prep. Ex. 13 and 0.2g A compound of formula (2b) [7:3 weight ratio] Mixture of compound of Prep. Bs. 10 and 0. 19 B compound of formula (2b) [7 : 3 weight ratio] Mixture of compound of Prep. Ex. 11 and 0. 3g A compound of formula (2c) [7 : 3 weight ratio] Mixture of compound of Prep. Ex. 1 and 0. 2g A compound of formula (2c) [1 : 1 weight ratio] Mixture of compound of Prep. Ex. 14 and 0. 4g A compound of formula (2d) [1 : 2 weight ratio] Mixture of compound of Prep. Ex. 2 and 0. 15g B compound of formula (2d) [1 : 5 weight ratio Mixture of compound of Prep. Ex. 3 and 0.1g B compound of formula (2e) [5 : 1 weight ratio] Mixture of compound of Prep. Ex. 4 and 0. 3g B compound of formula (2e) [1 : 1 weight ratio] Mixture of compound of Prep. Ex. 13 and 0. 2g A com ound of formula 3 : 7 weight ratio] Mixture of compound of Prep. Ex. 5 and 0. 4g B compound of formula (2f) [1 : 9 weight ratio] Mixture of compound of Prep. Ex. 6 and 0. 3g A com ound of formula 2 9 : 1 weight ratio] Mixture of compound of Prep. Ex. 7 and 0. 2g B compound of formula (2b) [1: 1 weight ratio] Amount of fluorescent Washing whitener powder Mixture of compound of formula (107) and 0.5g B compound of formula (2b) [1 : 1 weight ratio] Mixture of compound of formula (107) and 0.3g B compound of formula 2c 11 : 1 weight ratio] Mixture of compound of formula (107) and 0. 2g compound offormuia (2b) [1 : 1 weight ratio] Mixture of compound of Prep. Ex. 2 and 0. 2g B compound of formula (2b) [1:1 weight ratio] Mixture of compound of Prep. Ex. 13 and 0.1g A compound of formula (2c) [1:1 weight ratio] Mixture of compound of Prep. Ex. 10 and 0.1g B compound of formula (2c) [1 : 1 weight ratio] Mixture of compound of Prep. Ex. 10 and 0. 19 B compound of formula 2d) [1 : 1 w9ight ratiol Mixture of compound of Prep. Ex. 2 and 0.2g compound of formula (2e) [1:1 weight ratio Mixture of compound of Prep. Ex. 13 and 0. 4g compound of formula (2f) [1: 1 weight ratio Mixture of compound of Prep. Ex. 13 and 03. g compound of formula (2b) [1 : 1 weight ratio As to the constitution of compound of formula (107) see Application Example 1.