CN1596299A - Process for the treatment of textile fibre materials - Google Patents

Abstract

Detergent compositions comprising at least one compound of formula 1, wherein R1 and R2 are, independently of each other, hydrogen or unsubstituted or substituted C1-C8alkyl, X1, X2, X3 and X4 are, independently of each other, -NR3R4 or -OR5, wherein R3 and R4 are hydrogen, cyano, unsubstituted or substituted C1-C8alkyl or C5-C7cycloalkyl, or R3 and R4, together with the nitrogen atom linking them, form a heterocyclic ring, and R5 is unsubstituted or substituted C1-C8alkyl, and M is hydrogen or a cation, together with at least one compound of formula 2, wherein R6 and R7, independently of each other, are hydrogen, C1-C8alkyl, C1-C8alkoxy or halogen, and M is as defined above under formula 1, the novel mixtures of compounds of formulae 1 and 2 and detergent compositions containing compounds embraced by formula 1.

Description

Processing methods of textile fiber materials

The present invention relates to detergent formulations comprising certain fluorescers or mixtures of fluorescers, and to mixtures of fluorescers.

In general, optical brighteners are known for use in detergent formulations. During processing, they are released onto the material being washed, eliminating the yellow tinge by virtue of their special light absorption/emission properties.

However, there is still a need to find improved optical brighteners for this application. It has now been found that a mixture of compounds of the following formulas (1) and (2), or a compound of formula (1a) has superior properties such as solubility, buildability, white light fastness, and has excellent white exterior. Whiteness properties such as whiteness retention can even be increased by using a mixture of compounds of formula (1) and (2) or a compound of formula (1a) in detergents comprising cellulase, protease, amylase or lipase. Satisfactory results can be obtained even at low wash temperatures.

Thus, in one aspect, the present invention provides a detergent composition comprising at least one compound of the formula

in

R ₁ and R ₂ are independently of each other hydrogen or unsubstituted or substituted C ₁ -C ₈ alkyl,

X ₁ , X ₂ , X ₃ and X ₄ are independently -N(R ₃ )R ₄ or -OR ₅ , wherein R ₃ and R ₄ are hydrogen, cyano, unsubstituted or substituted C ₁ - C ₈ alkyl or C ₅ -C ₇ cycloalkyl, or R ₃ and R ₄ together with the nitrogen atom to which they are attached form a heterocycle, and R ₅ is unsubstituted or substituted C ₁ -C ₈ alkyl, and

M is hydrogen or a cation,

and at least one compound of the formula

wherein R ₆ and R ₇ are independently hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy or halogen, and M is as defined in the above formula (1).

Within the scope of the above definition, C ₁ -C ₈ alkyl can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, or straight-chain or branched Pentyl, hexyl, heptyl or octyl. Preference is given to C ₁ -C ₄ alkyl. If the alkyl group is substituted, examples of possible substituents are hydroxy, halogen such as fluorine, chlorine or bromine, sulfo, sulfato, carboxyl and C ₁ -C ₄ alkoxy such as methoxy and ethoxy. Other substituents of such alkyl groups are eg cyano, _-CONH2 and phenyl. Preferred substituents are hydroxyl, carboxyl, cyano, _-CONH2 and phenyl, especially hydroxyl and carboxyl. Furthermore, very preferred substituents are hydroxy and C ₁ -C ₄ alkoxy, especially hydroxy. The alkyl group can also be uninterrupted or interrupted by -O- (when the alkyl group contains two or more carbon atoms).

An example of C ₅ -C ₇ cycloalkyl is cyclopentyl, especially cyclohexyl. These groups may be unsubstituted or substituted eg by C ₁ -C ₄ alkyl such as methyl. Corresponding unsubstituted cycloalkyl groups are preferred.

Within the scope of the above definition, C ₁ -C ₈ alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy group, or a straight-chain or branched higher alkoxy group. Preference is given to C ₁ -C ₄ alkoxy, especially methoxy or ethoxy. Very preferred is methoxy.

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

If R ₃ and R ₄ together with the nitrogen atom form a heterocyclic ring, such a ring system may be, for example, a morpholine, piperidine or pyrrolidine ring. Heterocycles can be unsubstituted or substituted. Examples of such substituents are C ₁ -C ₄ alkyl, especially methyl.

The cation M is preferably an alkali metal atom, an alkaline earth metal atom, ammonium or a cation derived from an amine. Preferably Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-(C ₁ -C ₄ alkyl) ammonium, mono-, di- or tri-(C ₂ -C ₄ -hydroxyl Alkyl) ammonium, or ammonium di- or tri-substituted by a mixture of C ₁ -C ₄ -alkyl and C ₂ -C ₄ -hydroxyalkyl. Sodium is very preferred.

R ₁ and R ₂ are preferably hydrogen or C ₁ -C ₄ alkyl, especially hydrogen.

R ₃ and R ₄ are preferably hydrogen; cyano; C ₁ -C ₈ alkyl unsubstituted or substituted by hydroxyl, carboxyl, cyano, -CONH ₂ or phenyl, especially substituted by hydroxyl or carboxyl, And wherein C ₁ -C ₈ alkyl is uninterrupted or interrupted by -O-; C ₅ -C ₇ cycloalkyl, especially cyclohexyl, which is unsubstituted or substituted by C ₁ -C ₄ alkyl; Or R ₃ and R ₄ together with the nitrogen atom to which they are attached form an unsubstituted or C ₁ -C ₄ alkyl substituted morpholine, piperidine, or pyrrolidine ring.

R ₃ and R ₄ are more preferably hydrogen, C ₁ -C ₈ alkyl unsubstituted or substituted by hydroxy, C ₅ -C ₇ cycloalkyl unsubstituted or substituted by C ₁ -C ₄ alkyl , or R ₃ and R ₄ together with their attached nitrogen atoms form an unsubstituted or C ₁ -C ₄ alkyl substituted morpholine, piperidine or pyrrolidine ring. R ₃ and R ₄ are very preferably hydrogen, unsubstituted or substituted by hydroxy C ₁ -C ₈ alkyl, or R ₃ and R ₄ together with the nitrogen atom to which they are attached form unsubstituted or substituted by C ₁ -C ₄ Alkyl-substituted morpholine, piperidine or pyrrolidine rings. Most preferred are unsubstituted or C _{1 -C 4} alkyl-substituted morpholine, piperidine or pyrrolidine rings, especially morpholine rings formed by R and R together _with the nitrogen atom to which they are attached .

Examples of -N(R ₃ )R ₄ groups are -NH ₂ , -NHCH ₃ , -NHC ₂ H ₅ , -NH(nC ₃ H ₇ ), -NH(iC ₃ H ₇ ), -NH(iC ₄ H ₉ ), -N(CH ₃ ) ₂ , -N(C ₂ H ₅ ) ₂ , -N(iC 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(CH ₃ )(CH ₂ CH ₂ OH), -N(C ₂ H ₅ )(CH ₂ CH ₂ OH), -N( iC ₃ H ₇ )(CH ₂ CH ₂ CH ₂ OH), -NH(CH ₂ CH(OH)CH ₃ ), -N(C ₂ H ₅ )(CH ₂ CH(OH)CH ₃ ), -NH( CH ₂ CH ₂ OCH ₃ ), -NH(CH ₂ CH ₂ OCH ₂ CH ₂ OH), -NH(CH ₂ COOH), -NH(CH ₂ CH ₂ COOH), -N(CH ₃ )(CH ₂ COOH ), -NH(CN),

R ₅ is preferably C ₁ -C ₈ alkyl, especially C ₁ -C ₄ alkyl, which is unsubstituted or substituted by C ₁ -C ₄ alkoxy or especially hydroxy. R ₅ is very preferably methyl or ethyl, especially methyl.

X ₁ , X ₂ , X ₃ and X ₄ are preferably groups of formula —N(R ₃ )R ₄ .

_X1 and _X3 preferably have the same meaning. In addition, _X2 and _X4 preferably have the same meaning. In addition, it is preferred that the four groups X ₁ , X ₂ , X ₃ and X ₄ do not have the same meaning.

Compounds of formula (1) are preferred, wherein

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

R ₃ and R ₄ are hydrogen; cyano; _C 1 -C 8 alkyl unsubstituted or substituted by hydroxyl, carboxyl, cyano, -CONH ₂ or phenyl, and wherein the C _{1 -C 8} alkyl is Uninterrupted or interrupted by -O-; C ₅ -C ₇ cycloalkyl unsubstituted or substituted by C ₁ -C ₄ alkyl; or R ₃ and R ₄ together with their attached nitrogen atom form an unsubstituted A morpholine, piperidine, or pyrrolidine ring that is substituted or substituted by C ₁ -C ₄ alkyl; and

R ₅ is unsubstituted or hydroxy-substituted C ₁ -C ₈ alkyl.

As for R ₃ , R ₄ and R ₅ the above-mentioned preferred ranges apply.

Very preferred are compounds of formula (1), wherein

_X1 and _X3 are amino, and

X ₂ and X ₄ are groups of formula -N(R ₃ )R ₄ , wherein R ₃ and R ₄ are hydrogen; cyano; C ₁ -C ₈ alkyl unsubstituted or substituted by hydroxyl or carboxyl, and wherein C ₁ -C ₈ alkyl is uninterrupted or interrupted by -O- _; unsubstituted or substituted by C ₁ -C ₄ alkyl cyclohexyl; or the nitrogen to which _R and R are attached The atoms together form an unsubstituted or C ₁ -C ₄ alkyl substituted morpholine, piperidine, or pyrrolidine ring.

As regards _R3 and _R4 the above-mentioned preferred definitions apply.

Of particular interest are compounds of formula (1), wherein X _{and X} are amino _, and X and _X are groups of formula -N( _R )R, wherein _{R and R} are hydrogen, C ₁ -C ₈ alkyl unsubstituted or substituted by hydroxy, cyclopentyl or cyclohexyl unsubstituted or substituted by C ₁ -C ₄ alkyl, or the nitrogen to which R ₃ and R ₄ are attached The atoms together form an unsubstituted or C ₁ -C ₄ alkyl substituted morpholine, piperidine, or pyrrolidine ring. Compounds of formula (1) of most interest are those in which R _and R together with the nitrogen atom to which they are attached form an unsubstituted or C ₁ -C ₄ alkyl substituted morpholine, piperidine _or pyrrolidine ring compound. As regards _R3 and _R4 the above-mentioned preferred definitions apply.

Other compounds of formula (1) of interest are compounds of formula (1a) given below.

_R6 and _R7 are preferably hydrogen. Each sulfo group in formula (2) is preferably attached at the ortho position. Compounds of formula (2) of interest are those wherein _R6 and _R7 are hydrogen and each sulfo group in formula (2) is attached in an ortho position.

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

In the mixture of compounds of formula (1) and (2), the molar ratio of compound (1) to compound (2) is usually in the range of 0.1:99.9-99.9:0.1, preferably 1:99-99:1 In the range, more preferably in the range of 5:95-95:5. The molar ratio is very preferably in the range from 10:90 to 90:10, especially in the range from 20:80 to 80:20. The most important molar ratios are in the range from 30:70 to 70:30, especially in the range from 40:60 to 60:40.

The compounds of formulas (1) and (2) are known or can be prepared by methods analogous to known methods.

It can be obtained by reacting cyanuric chloride sequentially, in any desired order, with 4,4'-diaminostilbene-2,2'-disulfonic acid and capable of introducing groups X ₁ , X ₂ , Amino compounds of _X3 and _X4 are reacted to prepare compounds of formula (1). Preferably, initially, 2 moles of cyanuric chloride are reacted with 1 mole of 4,4'-diaminostilbene-2,2'-disulfonic acid, and the intermediates obtained are then reacted in any order with _1. Reaction of amino compounds of X ₂ , X ₃ and X ₄ . For the preparation of compounds in which _X1 and _X3 have the same meaning and _X2 and _X4 have the same meaning, it is preferred to first react the obtained intermediate with an amino compound capable of introducing _X1 and _X3 groups, and finally with an amino compound capable of introducing X ₂ reacts with an amino compound of the X ₄ group. The reaction with amino compounds can also be carried out in one step by reacting the intermediate with a mixture of amino compounds; in this case, the corresponding mixture of compounds of formula (1) is generally obtained.

Compounds of formula (1) comprising a group of formula -OR ₅ can be prepared, for example, by first reacting cyanuric chloride with the corresponding alcohol HOR ₅ such that the resulting product is reacted with 4,4'-diaminostilbene-2 , 2'-disulfonic acid reaction, and then the intermediate is further reacted with a compound capable of introducing the remaining groups of _X1 , _X2 , _X3 and _X4 . The final reaction is preferably carried out with the corresponding amine.

Furthermore, the invention relates to mixtures of compounds of the formulas (1) and (2). As far as the compounds of the formulas (1) and (2) are concerned, the preferred definitions given above apply. Compounds of formula (2) are preferred wherein _R6 and _R7 are hydrogen and each sulfo group in formula (2) is attached in an ortho position. In such a mixture, the molar ratio of compound (1) to compound (2) is usually in the range of 0.1:99.9-99.9:0.1, preferably in the range of 1:99-99:1, more preferably in the range of 5:95 In the range of -95:5. Very preferably the molar ratio is in the range from 10:90 to 90:10, especially in the range from 20:80 to 80:20. The most important molar ratios are in the range from 30:70 to 70:30, especially in the range from 40:60 to 60:40.

The detergent composition used preferably comprises

i) 1-70% of anionic surfactant and/or nonionic surfactant;

ii) 0-75% builder;

iii) 0-30% peroxide;

iv) 0-10% peroxide activator; and

v) 0.001-5% of mixtures of compounds of formulas (1) and (2), each component is calculated by weight and based on the total weight of the detergent.

The detergent composition used more preferably comprises

i) 5-70% of anionic surfactant and/or nonionic surfactant;

ii) 5-70% builder;

iii) 0.5-30% peroxide;

iv) 0.5-10% peroxide activator and/or 0.1-2% bleach catalyst; and

v) 0.01-5% of mixtures of compounds of formulas (1) and (2), each component is calculated by weight and based on the total weight of the detergent.

In general, the amount of the mixture of compounds of formula (1) and (2) is 0.001-5%, especially 0.01-5%. Very preferred amounts are in the range of 0.05-5%, especially in the range of 0.05-2%. Generally, amounts given in percentages are to be understood as weight percentages based on the total weight, unless otherwise indicated.

The detergent can be formulated as a solid, aqueous solution comprising, for example, 5-50%, preferably 10-35%, of water, or a non-aqueous liquid detergent comprising up to 5, preferably 0-1 wt%, of water, and based on a non-ionic surface Suspensions of builders in active agents, such as those described in GB-A-2158454.

Anionic surfactant components can be, for example, alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, alkylsulfonates, fatty acid salts, alkyl or alkenyl ether carboxylates, acid salt or α-sulfo fatty acid salt or its ester. Preferred are alkylbenzene sulfonates having 10-20 carbon atoms in the alkyl moiety, alkyl sulfates having 8-18 carbon atoms, alkyl ether sulfates having 8-18 carbon atoms, and Fatty acid salts derived from oil or tallow and having 8-18 carbon atoms. The average number of moles of ethylene oxide added to the alkyl ether sulfate is 1-20, preferably 1-10. These salts are preferably derived from alkali metals such as sodium and potassium, especially sodium. A very preferred carboxylate is the alkali metal sarcosine salt of the formula R—CO(R ¹ )CH ₂ COOM ¹ , wherein R is an alkyl group having 9 to 17 carbon atoms in the alkyl or alkenyl moiety or Alkenyl, R ¹ is C ₁ -C ₄ alkyl and M ¹ is alkali metal, especially sodium.

The nonionic surfactant component may be, for example, primary and secondary alcohol ethoxylates, especially _C8 - _C20 aliphatic alcohols ethoxylated with an average of 1-20 moles per mole of ethylene oxide, More especially C ₁₀ -C ₁₅ primary and secondary fatty alcohols ethoxylated with an average of 1 to 10 moles per mole of ethylene oxide. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamides).

The total amount of anionic surfactant and nonionic surfactant is preferably 5-50 wt%, preferably 5-40 wt%, more preferably 5-30 wt%. The lower limit of these surfactants is preferably 10% by weight.

Builder components may be alkali metal phosphates, especially tripolyphosphates; carbonates or bicarbonates, especially their sodium salts; silicates or disilicates; aluminosilicates; polycarboxylic acids salts; polycarboxylic acids; organic phosphonates; or aminoalkylene poly(alkylene phosphonates); or mixtures of these compounds. A preferred silicate is a crystalline layered sodium silicate of the formula NaHSimO _2m+1 .pH ₂ O or Na ₂ SimO _2m+1 .pH ₂ O, where m is a number from 1.9-4 and p is 0-20. Preferred aluminosilicates are commercially available synthetic materials known as zeolites A, B, X and HS, or mixtures of these. Zeolite A is preferred. Preferred polycarboxylates include hydroxypolycarboxylates, especially citrates, polyacrylates and their copolymers with maleic anhydride. Preferred polycarboxylic acids include nitrilotriacetic acid and ethylenediaminetetraacetic acid.

Preferred organic phosphonates or aminoalkylene poly(alkylene phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilotrimethylene phosphonates, ethylenediaminetetramethylene base phosphonate and diethylenetriaminepentamethylene phosphonate.

The amount of builder is 5-70wt%, preferably 5-60wt%, more preferably 10-60wt%. A preferred lower limit for builders is 15 wt%, especially 20 wt%.

Suitable peroxide components include, for example, known in the literature and commercially available organic and inorganic peroxides (such as sodium peroxide) which are capable of bleaching textile materials at conventional washing temperatures, for example at 5-95° C. . Of particular interest are organic peroxides, such as monoperoxides or polyperoxides with an alkyl chain of at least 3 carbon atoms, preferably with 6 to 20 carbon atoms; especially with 6 to 12 carbon atoms Diperoxydicarboxylates such as diperoxyperazelaate, diperoxypersebacate, diperoxyphthalate and/or diperoxydodecanedioate, especially are their corresponding free acids. However, preference is given to using very reactive inorganic peroxides, such as persulfates, perborates and/or percarbonates. Of course, it is also possible to use mixtures of organic and/or inorganic peroxides.

The amount of peroxide used is 0.5-30 wt%, preferably 1-20 wt%, more preferably 1-15 wt%. When peroxides are used, the lower limit is preferably 2 wt%, especially 5 wt%.

Peroxides, especially inorganic peroxides, are preferably activated by doping with a bleach activator. Preference is given to unsubstituted or substituted perbenzene- and/or peroxy-carboxylic acid compounds having 1 to 10 carbon atoms, especially 2 to 4 carbon atoms, under perhydrolysis conditions. Suitable compounds include those bearing O- and/or N-acyl groups and/or unsubstituted or substituted benzoyl groups having the stated number of carbon atoms. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycolurils (TAGU), N,N-diacetyl-N , N-dimethyl-urea (DDU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxahexahydro-1,3,5-triazine (DADHT), Compounds of the formula

wherein R is a sulfonate group, a carboxylic acid group, or a carboxylate group, and wherein R' is a linear or branched (C ₇ -C ₁₅ ) alkyl group; activators are also known, under the name For SNOBS, SLOBS, NOBS, and DOBA, acylated polyols, 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, As well as acetylated, optionally N-alkylated glucosamine and gluconolactone. Combinations of the conventional bleach activators disclosed in DE-A-44 43 177 may also be used. Nitrile compounds which form peroxyimidic acids with peroxides are also suitable as bleach activators. Preference is given to tetraacetylethylenediamine and nonanoyloxybenzenesulfonate.

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

Bleach catalysts which may be added include, for example, enzyme peroxide precursors and/or metal complexes. Preferred metal complexes are manganese, cobalt or iron complexes, for example manganese or iron phthalocyanine complexes or the complexes described in EP-A-0509787. In the case of using a bleach catalyst, it is preferably used in an amount of 0.005-2 wt%, more preferably 0.01-2 wt%, especially 0.05-2 wt%. Very preferred is 0.1-2 wt%.

Examples of bleach catalysts which may be mentioned are the following:

- WO-A-95/30681 (see definition of formula (I) et seq. page 1 lines 7-30; especially formula (I) et seq. page 2 line 29 - page 11 line definition given on line 11). Preferred ligands are those given on page 13, line 12 - page 26, line 11.

- WO-A-01/09276 (ie see formulas (1), (2) and (3) and definitions given on pages 2 and 3 below).

- WO-A-01/05925 (i.e. see formula (1) and the definitions given below in the last paragraph of page 1 - first paragraph of page 2. Metal complexes are preferred, especially see page 3 those of formula (2) and formula (3) on page 4).

- WO-A-02/088289 (ie see formula (1) and definitions on page 2 below. Metal complexes are preferred, especially see ligands of formula (3), and page 3, page 4 paragraph - the definition in paragraph 7 on page 4 is preferred).

Furthermore, the detergent may optionally contain enzymes. Enzymes can be added to detergents to remove stains. Enzymes generally improve performance on protein or starch based stains such as those caused by blood, milk, grass or fruit juices. The enzymes are preferably cellulases, proteases, amylases and lipases. Enzymes are preferably cellulases and proteases, especially proteases. Cellulase is an enzyme that acts on cellulose and its derivatives and hydrolyzes them into glucose, cellobiose, cellooligosaccharide. Cellulase removes soil and has a roughness-reducing effect to the touch. Examples of enzymes used include, but are not limited in any way to the following enzymes:

Proteases given in US 6,242,405, column 14, lines 21-32;

Lipases given in US 6,242,405, column 14, lines 33-46;

Amylases given in US 6,242,405, column 14, lines 47-56;

Cellulases given in US 6,242,405, column 14, lines 57-64.

Enzymes may optionally be present in the detergent. When used, the amount of enzyme is generally 0.01-5 wt%, preferably 0.05-5 wt%, more preferably 0.1-4 wt%, based on the total weight of the detergent.

In the detergents of the present invention, other preferred additives are polymers which, during washing of textiles, inhibit stains caused by dyes in the wash liquor which are removed from textiles under washing conditions (fixing agent , dye transfer inhibitors). Such polymers are preferably polyvinylpyrrolidone, polyvinylimidazole or polyvinylpyridine N-oxide, which may be modified by introducing anionic or cationic substituents, especially in the molecular weight range of 5000-60000, more especially in the molecular weight range of 10 000-50 000 range of those polymers. Such polymers are generally used in an amount of 0.01-5 wt%, preferably 0.05-5 wt%, especially 0.1-2 wt%, 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).

Detergents used usually contain one or more auxiliaries such as soil suspending agents, such as sodium carboxymethylcellulose; salts to adjust pH, such as alkali or alkaline earth metal silicates; suds regulators, such as soaps; Salts of a spray-drying and granulating nature, such as sodium sulphate; perfumes; and, if appropriate, antistatic and softening agents; such as smectite clays; photobleaches; pigments; and/or shading agents. Of course, these components should be stable in any bleaching system employed. Such adjuvants are used, for example, in an amount of 0.1-20 wt%, preferably 0.5-10 wt%, especially 0.5-5 wt%, based on the total weight of the detergent.

Detergent compositions can take a variety of physical forms including powders, granules, tablets and liquids. Examples of this are conventional super-detergent powders, concentrated and super-concentrated super-detergents and tablets such as super-detergent tablets. An important form are so-called concentrated granules, which are suitable for incorporation into washing machines.

So-called concentrated (or super concentrated) detergents are also important. A recently developed trend in the field of detergent preparations is to prepare concentrated detergent products which contain increased amounts of active substances. In order to minimize energy consumption during the washing process, concentrated detergents are required to operate efficiently at temperatures below 40°C, even at room temperature such as 25°C. Such detergents usually contain only small amounts of fillers or process aids, such as sodium sulfate or sodium chloride. Such fillers are generally used in an amount of 0-10 wt%, preferably 0-5 wt%, especially 0-1 wt%, based on the total weight of the detergent. Such detergents generally have a bulk density of 650-1000 g/l, preferably 700-1000 g/l, especially 750-1000 g/l.

The detergent can also be present in the form of small tablets. Corresponding properties of small tablets are ease of formulation and ease of handling. Tablets are the most compactly administered form of solid detergent with a bulk density of eg 0.9-1.3 kg/litre. To disintegrate quickly, laundry detergent tablets often contain special disintegrants:

- effervescent agents such as carbonates/bicarbonates/citric acid;

- bulking agents such as cellulose, carboxymethylcellulose, cross-linked poly(N-vinylpyrrolidone);

- fast dissolving materials such as sodium acetate (potassium acetate), or sodium citrate (or potassium citrate);

- Rapidly dissolving water soluble hard coatings such as dicarboxylic acid compounds.

The minitablets may also contain any combination of the above disintegrants.

The detergent may also be formulated as an aqueous liquid comprising 5-50% water, preferably 10-35% water, or as a non-aqueous liquid wash containing no more than 5% by weight water, preferably 0-1% by weight water agent. The non-aqueous liquid detergent compositions may contain other solvents as carriers. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. For soluble surfactants, monohydric alcohols are preferred, but polyhydric alcohols such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol, glycerol, and Propylene glycol) can also be used. The composition may contain from 5% to 90%, usually from 10% to 50%, of such carriers. Detergents may also be presented in so-called "unit liquid doses".

Treating textiles with these detergents can be done at home in a regular washing machine.

The textile fibers to be treated can be natural or synthetic fibers or mixtures thereof. Examples of natural fibers include vegetable fibers such as cotton, viscose, linen, rayon or linen, preferably cotton, and animal fibers such as wool, mohair, cashmere, angora and silk, preferably wool. Synthetic fibers include polyester, polyamide and acrylic fibers. Preferred textile fibers are cotton, polyamide and wool fibres, especially cotton fibres. The textile fibers treated by the method according to the invention preferably have a density of less than 200 g/cm ³ .

According to this method, the mixture of compounds of the formulas (1) and (2) is generally used in an amount of 0.01-3.0 wt.-%, especially 0.05-3.0 wt.-%, based on the weight of the textile fiber material.

The method is generally carried out at a temperature of 5-100°C, especially at a temperature of 5-60°C. It is preferably carried out at a temperature of 5-40°C, especially at a temperature of 5-35°C, more preferably at a temperature of 5-30°C.

The detergent compositions herein are preferably formulated such that the wash water has a pH of between about 6.5 and about 11, preferably between about 7.5 and 11, during use in an aqueous laundering operation. Laundry products have a pH of 9-11. Techniques for controlling pH at recommended levels include the use of buffers, bases, acids, etc., and those well known to those skilled in the art.

Machine laundry methods 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 wash detergent composition according to the present invention. An effective amount of detergent composition means, for example, that 20g-300g of product (as a typical product dosage) is dissolved or dispersed in a volume of 5-85 liters of washing solution (as a common washing solution volume) in a conventional machine washing method. )middle. example is

- Top detergent, vertical axis American type automatic washing machine, using about 45-83 liters of water in the tub, a wash cycle of about 10-about 14 minutes, and a wash water temperature of about 10-about 50°C;

- Front detergent, horizontal axis European type automatic washing machine, using about 8-15 liters of water in the washing bucket, washing cycle about 10-about 60 minutes, washing water temperature about 30-about 95°C;

- Front load detergent, vertical shaft Japanese type automatic washing machine, use about 26-52 liters of water in the wash tub, wash cycle about 8-about 15 minutes, wash water temperature about 5-about 25°C.

The liquor ratio is preferably 1:4-1:40, especially 1:4-1:15. The bath ratio is very preferably from 1:4 to 1:10, especially from 1:5 to 1:9.

Furthermore, the present invention relates to a detergent composition comprising at least one compound of the formula

wherein R and _R are independently _of each other hydrogen or unsubstituted or substituted C ₁ -C ₈ alkyl,

X ₁ , X ₂ , X ₃ and X ₄ are each independently -N(R ₃ )R ₄ or -OR ₅ , wherein R ₃ and R ₄ are hydrogen; cyano; unsubstituted or replaced by hydroxyl, carboxyl, C ₁ -C ₈ alkyl substituted by cyano, -CONH ₂ or phenyl, and wherein C ₁ -C ₈ alkyl is uninterrupted or interrupted by -O-; unsubstituted or by C ₁ -C ₄ Alkyl substituted C ₅ -C ₇ cycloalkyl; or R ₃ and R ₄ together with the nitrogen atom to which they are attached form unsubstituted or C ₁ -C ₄ alkyl substituted morpholine, piperidine, or pyrrolidine ring;

_R is C ₁ -C ₈ alkyl unsubstituted or substituted by hydroxy, and

M is hydrogen or a cation,

And wherein the detergent comprises at least one enzyme selected from cellulase, protease, amylase and lipase.

As regards the compounds of the formula (1a) and their substituents, the above definitions and preferred ranges for the compounds of the formula (1) apply.

Compounds of formula (1a) of interest are: wherein R and _R are independently _of each other hydrogen or unsubstituted or substituted C ₁ -C ₈ alkyl,

X ₄ , X ₂ , X ₃ and X ₄ are each independently -N(R ₃ )R ₄ or -OR ₅ , wherein R ₃ and R ₄ are hydrogen, unsubstituted or hydroxyl-substituted C ₁ -C ₈ alkyl, unsubstituted or C ₅ -C ₇ cycloalkyl substituted by C ₁ -C ₄ alkyl, or R ₃ and R ₄ together with the nitrogen atom to which they are attached form a morpholine, piperidine or pyrrolidine ring , and R ₅ is unsubstituted or hydroxy-substituted C ₁ -C ₈ alkyl, and

M is hydrogen or a cation.

Corresponding detergent compositions comprising enzymes and peroxides, peroxide activators and/or bleach catalysts are very preferred.

Preferred detergent compositions include

i) 1-70% of anionic surfactant and/or nonionic surfactant;

ii) 0-75% builder;

iii) 0-30% peroxide;

iv) 0-10% peroxide activator;

v) 0.001-5% of a compound of formula (1a); and

vi) 0.05-5% of at least one enzyme selected from cellulases, proteases, amylases and lipases, especially proteases.

Highly preferred detergent compositions include

i) 5-70% of anionic surfactant and/or nonionic surfactant;

ii) 5-70% builder;

iii) 0.5-30% peroxide;

iv) 0.5-10% peroxide activator and/or 0.1-2% bleach catalyst;

v) 0.01-5% of a compound of formula (1a); and

vi) 0.05-5% of at least one enzyme selected from cellulases, proteases, amylases and lipases, especially proteases.

With regard to enzymes, detergents and components thereof, the definitions and preferred ranges given above apply. The compounds of formula (1a) can be used in the same manner as the mixtures of compounds of formulas (1) and (2) given above.

A further object of the present invention is to provide a method for the domestic laundering treatment of textile fiber materials, wherein the textile fiber materials are brought into contact with an aqueous detergent solution comprising a compound of formula (1a) as defined above, and wherein the detergent comprises at least one compound selected from the group consisting of fiber Sulfase, protease, amylase and lipase enzymes, and wherein the temperature of the solution is between 5°C and 40°C, preferably between 5°C and 30°C throughout the treatment process.

With regard to the compounds of the formula (1a) and detergents and washing processes, the definitions and preferred ranges given above apply.

The abovementioned washing treatment of textile fibers can also be carried out using mixtures of compounds of the formulas (1) and (2).

The compounds and mixtures used according to the invention are particularly advantageous because they not only exhibit a very high bleaching power but also in many cases a very good water solubility and an excellent white appearance in the solid state. An additional advantage of the present invention is that the detergent composition improves whiteness performance and fabric feel. Furthermore, these compounds and especially mixtures show very good effects on energy consumption properties.

These compounds have the advantage that they are also effective in the presence of active chlorine donors, such as hypochlorite, and can be used in the laundry tub with nonionic detergents, such as alkylphenol polyglycol ethers, while The effect is basically no loss. Furthermore, these compounds and mixtures of compounds are stable both in powdered detergents and in the laundry tub in the presence of perborates or peracids and activators such as tetraacetyl glycoluril or ethylenediaminetetraacetic acid. In addition, they give an attractive appearance in daylight.

It has also been found that compounds of the formula (1) and mixtures of compounds of the formulas (1) and (2) can be used effectively for the fluorescent bleaching of textile materials, of which those relating to polyamides, wool and cotton should be particularly selected. According to an embodiment of the present invention, the treated textile fibers may be natural or synthetic fibers or mixtures thereof. Examples of natural fibers include vegetable fibers such as cotton, viscose, linen, rayon or linen, preferably cotton, and animal fibers such as wool, mohair, cashmere, angora and silk, preferably wool. Synthetic fibers include polyester, polyamide and acrylic fibers. Preferred textile fibers are cotton, polyamide and wool fibres. Preferably, the density of the textile fibers treated according to the invention is less than 1000 g/m ² , especially less than 500 g/m ² , most preferably less than 250 g/m ² .

The following examples serve to illustrate the invention; parts and percentages are by weight unless otherwise indicated.

Preparation Example 1:

In a 1 liter flask, 0.05 moles of a compound of the formula

Mix with 600ml of water and heat to 60°C. Then 9.2 g of 2-ethylaminoethanol were added, and the reaction mixture was heated to 98° C.; during the heating, the pH was maintained between 8.5 and 9 by adding 4-molar aqueous sodium hydroxide. The reaction mixture was cooled to 50°C and the pH was adjusted to 4.5 by the addition of 6-molar aqueous hydrochloric acid. The precipitate was filtered off, washed with 100 ml of 10% aqueous sodium chloride and dried in vacuo. In this way, 30.5 g of a pale yellow product are obtained.

Preparation Examples 2-15:

Compounds of the formula can be prepared in a manner similar to that given in Preparative Example 1,

9.2 g of 2-ethylaminoethanol were replaced by an equimolar amount of the corresponding amine. X is as defined in Table 1 below. The precipitated compound after cooling to 50°C can be directly isolated in the form of sodium salt without adding hydrochloric acid, and then dried in vacuum.

Table 1

Preparation Example 16:

In a 1 liter flask, 0.05 moles of a compound of the formula

Mix with 600ml of water and heat to 60°C. Then 9.5 g of morpholine were added, and the reaction mixture was heated to 98° C.; during the heating, the pH was maintained between 8.5 and 9 by adding 4-molar aqueous sodium hydroxide solution. The reaction mixture was cooled to 40°C, the precipitate was filtered off, washed with 100 ml of 10% aqueous sodium chloride and dried in vacuo. In this way, 30 g of a yellow product are obtained.

Preparation Examples 17-19:

Compounds of the formula can be prepared in a manner similar to that given in Preparative Example 16,

9.5 g of morpholine were replaced by an equimolar amount of the corresponding amine. X is defined in Table 2 below. Compounds with high solubility were treated with 6-molar aqueous hydrochloric acid to adjust the pH to 4.5 before cooling to 50°C.

Table 2

Preparation Example 20:

In a 2 liter flask, mix 130 ml of methyl ethyl ketone, 80 ml of deionized water, 150 g of ice and 18.5 g of cyanuric fluoride. Within 30 minutes, 185ml of 4,4'-diaminostilbene-2,2'-disulfonic acid (in the form of disodium salt) was added dropwise in an aqueous solution (concentration of 100g/l), and the temperature was maintained at - Between 8 and +5°C. The pH was maintained between 4.5 and 5 by adding aqueous sodium carbonate. A pale yellow suspension is obtained. Then, using a dropping funnel, 27.2 g of ethanolamine (99%) were added. The pH increased to 10, then dropped to a lower value, and the temperature increased to 10-15°C. The reaction mixture was then warmed to 45°C and maintained at this temperature for 20 minutes. During heating to 98° C., a mixture of methyl ethyl ketone and water was distilled off within 30 minutes; the pH was maintained between 8.5-9 by adding aqueous sodium hydroxide solution. After the pH was maintained at a constant value without additional addition of aqueous sodium hydroxide solution, the reaction mixture was cooled to 50°C. The pH value was adjusted to 5.5, and the pale yellow crystalline precipitate was filtered off. After drying, 29 g of a pale yellow product are obtained.

Preparation Example 21:

In a 1-liter pressure vessel, 0.037 moles of N,N'-bis-(4-morpholinyl-6-chloro-1,3,5-triazin-2-yl)-4,4'-diamino Stilbene-2,2'-disulfonic acid (as the disodium salt) was suspended in 500 ml of water. 15 g of ethylamine (70%) in water were added and the reaction mixture was heated to 100-105°C and stirred for 4.5 hours. The reaction mixture was cooled to 25°C, the precipitate was filtered off, washed with 100 ml of 10% aqueous sodium chloride and dried in vacuo at 70°C. In this way, 25.8 g of a pale yellow powder are obtained.

Preparation Example 22:

Compounds of formula (107) can be prepared in a similar manner to Preparative Example 21 by replacing 15 g of ethylamine (70%) aqueous solution with the corresponding solution containing diethylamine in equimolar amounts.

Preparation Example 23:

In a 1-liter flask, 0.05 moles of N,N'-bis-(4-morpholinyl-6-chloro-1,3,5-triazin-2-yl)-4,4'-diaminostilbene - 2,2'-disulfonic acid (as the disodium salt) was suspended in 600 ml of water, which was then heated to 60°C. 6.4 g of ethanolamine were added and the reaction mixture was heated to 98°C. The pH was maintained between 8.9 and 9 by adding 4-molar aqueous sodium hydroxide solution. The reaction mixture was cooled to 25°C, and 10% by volume of sodium chloride was added. The precipitate was filtered off, washed with 100 ml of 10% aqueous sodium chloride and dried in vacuo at 70°C. In this way, 41.8 g of a pale yellow powder are obtained.

Application Example 1:

General method:

Dissolve 0.8g of washing powder in 200ml of tap water to prepare a washing solution. 10 g of bleached cotton cloth was added to the tank, washed at 40°C for 15 minutes, rinsed, spin dried, and ironed at 160°C.

The following laundry detergents A and B were used (quantities in g are given in Tables 3a and 3b):

Table 3a (Components of laundry detergent A and B) A B Sodium dodecylbenzenesulfonate (LAS) 10g 10g Sodium Laureth Sulfate (AES) 3g 3g Dobanol 23-6.5 (nonionic fatty alcohol ethoxylate) 4g 4g sodium tripolyphosphate 30g ---- Zeolite A ---- 20g Sodium carbonate 15g 15g Sodium silicate 5g 5g sodium sulfate 11g 11g cellulase 1.5g ---- protease ---- 1.5g Polycarboxylate (co-builder) ---- 4g carboxymethyl cellulose 2g 2g spices 0.1g 0.1g water 5g 5g Optical brightener or mixture of optical brighteners xg xg

Table 3b (laundry powder used) Amount of optical brightener or mixture of optical brighteners used washing powder Preparation of the compound of Example 1 0.2g A Preparation of the compound of Example 2 0.1g B Preparation of the compound of Example 3 0.3g A Preparation of the compound of Example 4 0.2g A Preparation of the compound of Example 5 0.4g A Preparation of the compound of Example 12 0.15g B Preparation of the compound of Example 13 0.1g B Preparation of the compound of Example 16 0.3g B The mixture of the compound of preparation embodiment 6 and the compound of formula (109) [weight ratio is 7: 3] 0.2g A The mixture of the compound of preparation embodiment 12 and the compound of formula (109) [weight ratio is 7: 3] 0.4g B The mixture of the compound of preparation embodiment 14 and the compound of formula (109) [weight ratio is 7: 3] 0.3g A The mixture of the compound of preparation embodiment 17 and the compound of formula (109) [weight ratio is 1: 1] 0.2g B The mixture of the compound of preparation embodiment 18 and the compound of formula (109) [weight ratio is 1: 2] 0.5g B The mixture of the compound of preparation embodiment 1 and the compound of formula (109) [weight ratio is 1: 5] 0.3g B The mixture of the compound of preparation embodiment 2 and the compound of formula (109) [weight ratio is 5: 1] 0.2g B The mixture of the compound of preparation embodiment 3 and the compound of formula (109) [weight ratio is 1: 1] 0.2g B The mixture of the compound of preparation embodiment 20 and the compound of formula (109) [weight ratio is 3: 7] 0.1g A The mixture of the compound of preparation embodiment 21 and the compound of formula (109) [weight ratio is 1: 9] 0.1g B The mixture of the compound of preparation embodiment 22 and the compound of formula (109) [weight ratio is 9: 1] 0.2g B The mixture of the compound of preparation embodiment 23 and the compound of formula (109) [weight ratio is 1: 1] 0.4g B The mixture of the compound of formula (110) and the compound of formula (109) [weight ratio is 1: 1] 0.3g B

The structure of the compound of formula (109):

The structure of the compound of formula (110):

Cotton fabrics were generally laundered with the detergents given in Table 3b and showed good whiteness properties.

Application Example 2:

General method:

Dissolve 0.8g of washing powder in 200ml of tap water to prepare a washing solution. 10 g of bleached cotton cloth was added to the tank, washed at 30°C for 15 minutes, rinsed, spin dried and ironed at 160°C.

The following laundry powders were used (quantities are given in Tables 4a and 4b in percent by weight, based on the total weight of the detergent):

Table 4a (Components of laundry detergent C and D) C D. Sodium dodecylbenzenesulfonate (LAS) 8% 8% Sodium Laureth Sulfate (AES) 3% 3% Dobanol 23-6.5 (nonionic fatty alcohol ethoxylate) 5% 5% Zeolite A 20% 20% Polycarboxylates (co-builders) 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% carboxymethyl cellulose 1% 1% Sodium perborate monohydrate 15% 15% TAED 5% 5% Soap 2% 2% Optical brightener or mixture of optical brighteners used X% X%

In the above detergent, use enough water to add to 100%.

Table 4b (laundry powder used) Amount of optical brightener or mixture of optical brighteners used washing powder Preparation of the compound of Example 1 0.2% C Preparation of the compound of Example 3 0.2% C Preparation of the compound of Example 7 0.2% D. Preparation of the compound of Example 8 0.2% C Preparation of the compound of Example 9 0.4% C Preparation of the compound of Example 10 0.2% C Preparation of the compound of Example 11 0.2% C Preparation of the compound of Example 17 0.4% C Preparation of the compound of Example 20 0.5% C Compound of formula (110) 0.3% D. The mixture of the compound of preparation embodiment 1 and the compound of formula (109) [weight ratio is 10: 1] 0.2% D. The mixture of the compound of preparation embodiment 3 and the compound of formula (109) [weight ratio is 5: 1] 0.4% C The mixture of the compound of preparation embodiment 5 and the compound of formula (109) [weight ratio is 1: 5] 0.15% C The mixture of the compound of preparation embodiment 11 and the compound of formula (109) [weight ratio is 1: 1] 0.2% C The mixture of the compound of preparation embodiment 15 and the compound of formula (109) [weight ratio is 1: 9] 0.4% C The mixture [weight ratio is 9: 1] of the compound of preparation embodiment 16 and the compound of formula (109) 0.3% D. The mixture of the compound of preparation embodiment 19 and the compound of formula (109) [weight ratio is 1: 5] 0.2% D.

As for the structures of the compounds of the formulas (109) and (110), see Application Example 1.

Cotton cloths were laundered in the usual manner with the detergents given in Table 4b and showed good whiteness properties.

Claims (32)

1. detergent composition comprises the compound of at least a following formula

Wherein

R ₁And R ₂Be hydrogen or C unsubstituted or that replace with being mutually independent ₁-C ₈Alkyl,

X ₁, X ₂, X ₃And X ₄Be independently each other-N (R ₃) R ₄Or-OR ₅, R wherein ₃And R ₄Be hydrogen, cyano group, the unsubstituted or C that replaces ₁-C ₈Alkyl or C ₅-C ₇Cycloalkyl, perhaps R ₃And R ₄The nitrogen-atoms that connects with them forms heterocycle, and R ₅Be C unsubstituted or that replace ₁-C ₈Alkyl, and

M is hydrogen or positively charged ion,

Compound with at least a following formula

R wherein ₆And R ₇Be hydrogen, C each other independently ₁-C ₈Alkyl, C ₁-C ₈Alkoxy or halogen, and M in the above-mentioned formula (1) definition.

2. according to the composition of claim 1, wherein

R ₁And R ₂Be hydrogen or C ₁-C ₄Alkyl,

R ₃And R ₄Be hydrogen; Cyano group; Unsubstituted or by hydroxyl, carboxyl, cyano group ,-CONH ₂Or the C of phenyl replacement ₁-C ₈Alkyl, and C wherein ₁-C ₈Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C ₁-C ₄The C that alkyl replaces ₅-C ₇Cycloalkyl; Perhaps R ₃And R ₄The nitrogen that connects with their is former in forming unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces; With

R ₅Be C unsubstituted or that replaced by hydroxyl ₁-C ₈Alkyl.

3. according to the composition of claim 1 or 2, wherein

X ₁, X ₂, X ₃And X ₄Be formula-N (R ₃) R ₄Group.

4. the composition any according to claim 1-3, wherein

X ₁And X ₃Be amino and

X ₂And X ₄Be formula-N (R ₃) R ₄Group, R wherein ₃And R ₄Be hydrogen; Cyano group; Unsubstituted or by the C of hydroxyl or carboxyl substituted ₁-C ₈Alkyl, and C wherein ₁-C ₈Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C ₁-C ₄The cyclohexyl that alkyl replaces; Perhaps R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces.

5. according to the composition of claim 4, wherein

R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces, preferred morpholine ring.

6. the composition any according to claim 1-5, wherein

R ₆And R ₇Be that each sulfo group in hydrogen and the formula (2) is connected the ortho position.

7. the composition any according to claim 1-6, wherein

M is a hydrogen, basic metal or alkaline-earth metal, or ammonium, preferably sodium.

8. the composition any according to claim 1-7 comprises

I) anion surfactant of 1-70% and/or nonionogenic tenside;

The ii) washing assistant of 0-75%;

The iii) superoxide of 0-30%;

The iv) peroxide activator of 0-10%; With

The v) mixture of the formula of 0.001-5% (1) and (2) compound.

9. composition according to Claim 8 comprises

I) anion surfactant of 5-70% and/or nonionogenic tenside;

The ii) washing assistant of 5-70%;

The iii) superoxide of 0.5-30%;

The iv) bleaching catalyst of the peroxide activator of 0.5-10% and/or 0.1-2%; With

The v) mixture of the formula of 0.01-5% (1) and (2) compound.

10. the composition any according to claim 1-9, wherein detergent composition comprises at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase, preferably proteolytic enzyme.

11. a detergent composition comprises

The compound of at least a following formula

Wherein

R ₁And R ₂Be hydrogen or C unsubstituted or that replace each other independently ₁-C ₈Alkyl,

X ₁, X ₂, X ₃And X ₄Be independently each other-N (R ₃) R ₄Or-OR ₅, R wherein ₃And R ₄Be hydrogen; Cyano group; Unsubstituted or by hydroxyl, carboxyl, cyano group ,-CONH ₂Or the C of phenyl replacement ₁-C ₈Alkyl, and C wherein ₁-C ₈Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C ₁-C ₄The C that alkyl replaces ₅-C ₇Cycloalkyl; Perhaps R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces;

R ₅Be C unsubstituted or that replaced by hydroxyl ₁-C ₈Alkyl and

M is hydrogen or positively charged ion,

And wherein washing composition comprises at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase.

12. according to the composition of claim 11, wherein

X ₁, X ₂, X ₃And X ₄Be formula-N (R ₃) R ₄Group.

13. according to claim 11 and 12 any one compositions, wherein

X ₁And X ₃Be amino,

X ₂And X ₄Be formula-N (R ₃) R ₄Group, R wherein ₃And R ₄Be hydrogen; Cyano group or unsubstituted or by the C of hydroxyl or carboxyl substituted ₁-C ₈Alkyl, and C wherein ₁-C ₈Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C ₁-C ₄The cyclohexyl that alkyl replaces; Perhaps R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or the pyrrolidine ring that alkyl replaces and

M is a hydrogen, basic metal or alkaline-earth metal, or ammonium, preferably sodium.

14. according to the composition of claim 13, wherein

R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces, preferred morpholine ring.

15. the composition any according to claim 11-14, wherein said composition comprises superoxide, peroxide activator and/or bleaching catalyst.

16. the composition any according to claim 11-15 comprises

I) anion surfactant of 1-70% and/or nonionogenic tenside;

The ii) washing assistant of 0-75%;

The iii) superoxide of 0-30%;

The iv) peroxide activator of 0-10%;

The v) compound of the formula of 0.001-5% (1a); With

The vi) at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase of 0.05-5%.

17. the composition any according to claim 11-16 comprises

I) anion surfactant of 5-70% and/or nonionogenic tenside;

The ii) washing assistant of 5-70%;

The iii) superoxide of 0.5-30%;

The iv) bleaching catalyst of the peroxide activator of 0.5-10% and/or 0.1-2%;

The v) compound of the formula of 0.01-5% (1a); With

The vi) at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase of 0.05-5%.

18. the composition any according to claim 11-17, wherein enzyme is a proteolytic enzyme.

19. a home washings is handled the method for textile fiber material, and textile fiber material is contacted with the aqueous solution of the washing composition of the compound that comprises following formula

Wherein

R ₁And R ₂Be hydrogen or C unsubstituted or that replace each other independently ₁-C ₈Alkyl,

X ₁, X ₂, X ₃And X ₄Be independently each other-N (R ₃) R ₄Or-OR ₅, R wherein ₃And R ₄Be hydrogen; Cyano group; Unsubstituted or by hydroxyl, carboxyl, cyano group ,-CONH ₂Or the C of phenyl replacement ₁-C ₈Alkyl, and C wherein ₁-C ₈Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C ₁-C ₄The C that alkyl replaces ₅-C ₇Cycloalkyl; Perhaps R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces;

R ₅Be C unsubstituted or that replaced by hydroxyl ₁-C ₈Alkyl and

M is hydrogen or positively charged ion,

And wherein washing composition comprises at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase, and wherein in the entire treatment process, the temperature of solution is between 5 ℃-40 ℃, preferably between 5 ℃-30 ℃.

20. according to the method for claim 19, wherein

X ₁, X ₂, X ₃And X ₄Be formula-N (R ₃) R ₄Group.

21. according to claim 19 and 20 any one methods, wherein

X ₁And X ₃Be amino,

X ₂And X ₄Be formula-N (R ₃) R ₄Group, R wherein ₃And R ₄Be hydrogen; Cyano group or unsubstituted or by the C of hydroxyl or carboxyl substituted ₁-C ₈Alkyl, and C wherein ₁-C ₈Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C ₁-C ₄The cyclohexyl that alkyl replaces; Perhaps R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or the pyrrolidine ring that alkyl replaces and

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

22. according to the method for claim 21, wherein

R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces, preferred morpholine ring.

23. the method any according to claim 19-22 wherein used formula (1a) the compound treatment textile fiber material based on the weight 0.05-3.0wt% of textile fiber material.

24. the mixture of compound comprises the compound of at least a following formula

Wherein

R ₁And R ₂Be hydrogen or C unsubstituted or that replace with being mutually independent ₁-C ₈Alkyl,

X ₁, X ₂, X ₃And X ₄Be independently each other-N (R ₃) R ₄Or-OR ₅, R wherein ₃And R ₄Be hydrogen, cyano group, the unsubstituted or C that replaces ₁-C ₈Alkyl or C ₅-C ₇Cycloalkyl, perhaps R ₃And R ₄The nitrogen-atoms that connects with them forms heterocycle, and R ₅Be C unsubstituted or that replace ₁-C ₈Alkyl and

M is hydrogen or positively charged ion,

Compound with at least a following formula

Wherein, R ₆And R ₇Be hydrogen with being mutually independent, C ₁-C ₈Alkyl, C ₁-C ₈Alkoxy or halogen and M are as being defined so that following formula (1) is middle.

25. according to the mixture of the compound of claim 24, wherein

R ₁And R ₂Be hydrogen or C ₁-C ₄Alkyl,

R ₃And R ₄Be hydrogen; Cyano group; Unsubstituted or by hydroxyl, carboxyl, cyano group ,-CONH ₂Or the C of phenyl replacement ₁-C ₈Alkyl, and C wherein ₁-C ₈Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C ₁-C ₄The C that alkyl replaces ₅-C ₇Cycloalkyl; Perhaps R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces; With

R ₅Come C substituted or that replaced by hydroxyl ₁-C ₈Alkyl.

26. according to claim 24 and 25 each the mixtures of compound, wherein

X ₁, X ₂, X ₃And X ₄Be formula-N (R ₃) R ₄Group.

27. according to the mixture of any one compound of claim 24-26, wherein

X ₁And X ₃Be amino and

X ₂And X ₄Be formula-N (R ₃) R ₄Group, R wherein ₃And R ₄Be hydrogen; Cyano group or unsubstituted or by the C of hydroxyl or carboxyl substituted ₁-C ₈Alkyl, and C wherein ₁-C ₈Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C ₁-C ₄The cyclohexyl that alkyl replaces; Perhaps R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces.

28. according to the mixture of the compound of claim 27, wherein

R ₃And R ₄The nitrogen-atoms that connects with their forms unsubstituted or by C ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces, preferred morpholine ring.

29. according to the mixture of any one compound of claim 24-28, wherein

R ₆And R ₇Be that each sulfo group in hydrogen and the formula (2) is connected the ortho position.

30. according to the mixture of any one compound of claim 24-29, wherein

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

31. the method for optically brightening of a textile materials comprises that the formula (1) that makes definition in textile materials and the claim 1 and the mixture of (2) compound contact.

32. according to the method for claim 31, wherein textile materials is polymeric amide, wool or cotton.