WO2020074141A1

WO2020074141A1 - Use of transition metal-free tinting dyes in combination with catechol derivatives

Info

Publication number: WO2020074141A1
Application number: PCT/EP2019/065981
Authority: WO
Inventors: Mareile Job; Ulrich Pegelow; Frank Meier; Christian Kropf
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2018-10-11
Filing date: 2019-06-18
Publication date: 2020-04-16
Also published as: DE102018217397A1

Abstract

The invention relates to a liquid detergent which comprises at least one particular catechol compound, at least one surfactant, and at least one tinting dye and contains substantially no transition metal ions. The invention further relates to the use of said detergent for removing bleachable stains and to a method for washing fabrics using said detergent.

Description

"Use of transition metal-free tinting dyes in combination with catechol derivatives"

The present invention relates to a liquid detergent which has at least one

Catechol compound, at least one surfactant, and at least one tinting dye and is substantially free of transition metal ions. The present invention further relates to the use of the detergent for removing bleachable stains and a method for washing textiles using the detergent.

While the formulation of powdered detergents and cleaning agents containing bleach now no longer poses any problems, the formulation of stable liquid detergents and cleaning agents containing bleach continues to be a problem. Because of the usually lack of bleach in liquid detergents and cleaning agents, such Soiling, which is normally removed in particular due to the bleaching agent contained, is correspondingly frequently only removed in an inadequate manner. A similar problem also exists for bleach-free color detergents in which the bleach is omitted in order to protect the dyes in the textile and prevent them from fading. In the absence of bleach, it is aggravated that instead of removing the so-called bleachable stains, which are normally at least partially oxidatively decomposed through the use of peroxygen-based bleach, on the contrary, the washing process often leads to an intensification and / or deterioration in the removability of the stain , which should not least be attributed to initiated chemical reactions, which may consist, for example, in the polymerization of certain dyes contained in the soiling.

Such problems occur in particular with soiling that is polymerizable

Contain substances. The polymerizable substances are mainly polyphenolic dyes, preferably flavonoids, in particular from the class of anthocyanidins or anthocyanins. The soiling can in particular be caused by

Food products or beverages have been caused that contain appropriate colorants. The soiling can be, in particular, stains from fruits or vegetables or also red wine stains, which in particular contain polyphenolic dyes, especially those from the class of anthocyanidins or anthocyanins.

International patent application WO 201 1/023716 A1 describes the use of

Gallic acid esters such as propyl gallate in detergents and cleaning agents for improved removal of soils which contain polymerizable substances are known. The international patent application WO 2013/092263 A1 relates to the improvement of the performance of detergents and cleaning agents through the use of oligohydroxybenzoic acid amides.

The German patent applications DE 102016214660 A1 and DE 102014222833 relate to the use of dihydroxy terephthalic acid derivatives in detergents and cleaning agents to improve the washing or cleaning performance. The detergents and cleaning agents in these publications have an alkaline pH.

Tinting dyes can be used to achieve an even better washing result. Tinting dyes are shading dyes, these dyes pull during the

Washing process on the textile. Visually, the textile is perceived as white due to the color shift. It has been shown that when catechol compounds and tinting dyes are incorporated into liquid, in particular alkaline, aqueous compositions, a red to brown discoloration of the composition can form over time. This discoloration is undesirable. Furthermore, when combining

Catechol derivatives with tinting dyes come to weaken the desired effects.

The object of the present invention was to provide a liquid detergent which is color-stable, that is to say does not have any subsequently undesirable discoloration, and also has one

Contains tinting dye. Both components should have a good efficiency and an excellent washing result, in particular an excellent degree of whiteness, should be achieved.

In this regard, the inventors of the present invention have found that the negative properties described above result when tinting dyes are used which contain transition metal ions.

A first subject of the present invention is therefore a detergent, in particular a multi-component detergent, preferably with 2 to 6 compartments, particularly preferably 2 to 4 compartments, which

at least one catechol compound of the formula (I)

wherein X represents a sulfone group -SO2R ¹ or an amide group -C-NH-R ² ,

II

O

Y ¹ and Y ² stand for a hydrogen atom, for a sulfone group -SO2R ³ or

for an amide group -

wherein one of the radicals from Y ¹ and Y ^{2 represents} a hydrogen atom, and the other radical from Y ¹ and Y ^{2 is} selected with the proviso that if X is a sulfone group, this other radical is also selected from a sulfone group and if X represents an amide group, this other radical is selected from an amide group,

R ¹ and R ³ independently of one another represent a group -NR ^a ,

I.

R ^b

R ^a and R ^b independently of one another represent hydrogen or a cyclic or acyclic, straight-chain or branched-chain, aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms, the structure of which is broken through by one or more non-adjacent heteroatoms (in particular selected from O and / or N) and / or which can be substituted on the C atoms not connected to heteroatoms with OH groups or NH2 groups, where R ^a and R ^{b can} also be part of a heterocycle formed from them and the N atom bonded to them,

R ² and R ⁴ each independently represent a hydrocarbon radical having 1 to 20 carbon atoms, which is optionally substituted by at least one radical selected from hydroxy, carboxyl, (Ci-C4) alkoxy, (Ci-C4) alkoxy (CH2CH20 ) _n -, -NR ^' R ^" or -N ⁺ R ^' R ^" R ^"' A-, and n = 1 to 10, R ^' , R ^" and R ^" independently of one another represent H or a straight-chain or branched-chain aliphatic hydrocarbon radical with 1 to 3, preferably 1 to 2 carbon atoms and A- represent an anion;

at least one tinting dye which is substantially free of transition metal ions (based on the weight of the tinting dyes, transition metal ions in less than 0.01% by weight, preferably less than 0.001% by weight, more preferably less than 0.0001% by weight) , most preferably not at all, are contained in the tinting dye);

at least one surfactant, preferably in a total amount of 2 to 70% by weight, in particular 10 to 65% by weight, particularly preferably 15 to 60% by weight;

optionally other active substances; and

Water from 1 to 50% by weight, preferably 2 to 30% by weight, particularly preferably 3 to 25% by weight, very particularly preferably 5 to 25% by weight, in particular 5 to 35% by weight, preferably 5 to 30% by weight. %, particularly preferably 5 to 25% by weight, very particularly preferably comprises 8 to 15% by weight, based on the total weight of the detergent, or consists of

the detergent is preferably substantially free of transition metal ions (based on the weight of the composition transition metal ions in less than 0.01% by weight, preferably less than 0.001% by weight, more preferably less than 0.0001% by weight) most preferably not at all).

The water content as defined herein relates to the water content determined by means of the Karl Fischer titration (Angewandte Chemie 1935, 48, 394-396; ISBN 3-540-12846-8 Eugen Scholz).

“Liquid” as used herein in relation to compositions according to the invention includes all compositions which are flowable under standard conditions (20 ° C., 1013 mbar) in the form of liquids and in particular includes liquids, gels and pasty compositions. In particular, the term also includes non-Newtonian liquids which have a yield point. As is known, granular mixtures (flowable solids such as powders or granules) are not liquids and are therefore not included.

Unless otherwise stated, all the amounts stated in connection with the constituents of the detergent described herein relate to% by weight, based in each case on the total weight of the composition. Furthermore, such relate

Quantities that refer to at least one component, always to the

Total amount of this type of ingredient contained in the detergent, unless explicitly stated otherwise. This means that such quantities, for example in connection with “at least one nonionic surfactant”, refer to the total amount of nonionic surfactants contained in the detergent.

“At least one,” as used herein, refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of those described herein

For compositions, this information does not refer to the absolute amount of molecules but to the type of component. "At least one nonionic surfactant" therefore means, for example, one or more different nonionic surfactants, i.e. one or more different types of nonionic surfactants. Together with quantity information, the quantity information relates to the total quantity of the correspondingly designated type of constituent, as already defined above.

“Substantially free from” as used herein means that the particular compound (eg transition metal ion) concerned is less than 0.01% by weight, based on the weight of the component (eg tinting dyes) or composition (eg detergent) contained in the compound. , preferably 0.001% by weight, more preferably 0.0001% by weight, most preferably not contained in the respective component or composition.

If compounds are described as substituted in the present invention, the possible substituents are known to the person skilled in the art. Particularly preferred, unless explicitly stated otherwise, the substituents are selected from -F, -CI, -Br, -I, -OH, = 0, -OR ¹ , -NH2, -NHR ¹ , -NR ¹ 2 and -COOR ¹ , wherein R ^{1 is} an alkyl radical having 1 to 10 carbon atoms.

According to the present invention, several compositions, then referred to as components, can be spatially separated from one another.

In the present invention, the terms detergent and composition are used synonymously.

If the invention relates to a multi-component detergent, the further components can be customary cleaning agents or a composition according to the present invention, the further components can also be solid or in the form of granules. It is preferred that all components are liquid.

If other liquid components are present, they can be defined like K1 or K2.

If molecular weights or relative molecular weights or molecular weights are described in the present invention, it is the number average unless explicitly stated otherwise

Molecular weight MN, which can be determined by means of gel permeation chromatography using polystyrene standards.

It is particularly preferred according to the invention that if X is selected from said sulfone group according to formula (I), Y ^{1 is selected} from said sulfone group and Y ^{2 represents} a hydrogen atom.

If compounds of the general formula (I) X and Y ^{1 represent} a sulfonamide group, these compounds can be prepared from 1,2-dihydroxybenzene by chlorosulfonation with

Chlorosulfonic acid and subsequent reaction of the resulting 4,5-dihydroxybenzene-1,3-disulfonyldichloride with amines R ^a R ^b NH, in which R ^a and R ^{b have} the meaning given for formula (I), are prepared.

In the compounds of the general formula (I), R ^a and R ^b are preferably the same. The preferred compounds of the general formula (I) also include those in which R ^a and R ^b are selected independently of one another from hydrogen, the methyl group, the ethyl group, the n-propyl group and the iso-propyl group. If R ^a and R ^{b are} part of a heterocycle formed from them and the N atom, this is preferably a pyrrolidine, piperidine or morpholine ring.

It is particularly preferred according to the invention that when X is selected from said amide group according to formula (I), Y ^{1 stands} for a hydrogen atom and Y ^{2 is selected} from said amide group.

Very particularly preferred multi-component detergents of the first subject of the present invention contain at least one catechol compound of the formula (Ia) as the catechol compound of the formula (I)

wherein

R ² and R ⁴ independently of one another for a hydrocarbon radical having 1 to 20

Are carbon atoms, which is optionally substituted with at least one radical selected from hydroxy, (Ci-C4) alkoxy, (Ci-C4) alkoxy (CH2CH20) _n -, -NR ^' R ^“ or

-N ⁺ R ^' R ^" R ^"' X-, and n = 1 to 10, R ^' , R ^" and R ^" independently of one another represent H or a straight-chain or branched-chain aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2, carbon atoms and X stand for an anion.

Compounds of the general formulas (I) and (Ia) preferably have a solubility in demineralized water of pH 4 at 20 ° C. of at least 10 mg / l, in particular at least 20 mg / l.

It is preferred if, based on the total weight of the liquid composition, the at least one catechol compound according to formula (I) in a total amount of 0.2 to 90% by weight, preferably 1 to 85% by weight, in particular 2.5 to 75% by weight % by weight, preferably from 0.5% by weight to 50% by weight, more preferably from 1.0% by weight to 40% by weight, even more preferably from 2.5% by weight to 20 % By weight is included.

It is further preferred if, based on the total weight of the liquid composition, the at least one catechol compound according to formula (Ia) in a total amount of in particular from 0.2 to 90% by weight, preferably 1 to 85% by weight, in particular 2.5 to 75% by weight, more preferably from 0.5% by weight to 50% by weight, further preferably from 1 , 0 wt .-% to 40 wt .-%, more preferably from 2.5 wt .-% to 20 wt .-%, is included.

The hydrocarbon radicals having 1 to 20 carbon atoms according to formula (I) and formula (la) can be linear or branched, saturated or unsaturated, cyclic or alicyclic or aromatic.

Compositions which contain at least one catechol compound of the formula (I) or of the formula (Ia) in which the radicals R ² and R ⁴ independently of one another represent an alkyl group (such as methyl, ethyl, n-propyl or i- Propyl) an alkoxyalkyl group (such as methoxyethyl, methoxypropyl, (2-methoxy) ethoxyethyl, ethoxyethyl, ethoxypropyl or (2-ethoxy) ethoxyethyl), a hydroxyalkyl group (such as 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 1, 2-dihydroxypropyl), a hydroxyalkyloxyalkyl group (such as 2-hydroxyethoxyethyl), (N-hydroxyethyl) aminoethyl, (N-methoxyethyl) aminoethyl or (N-ethoxyethyl) aminoethyl, or an aromatic group (such as phenyl or benzyl) .

Preferred alkyl groups according to formula (I) or formula (la) are linear (C-i-C-io) alkyl groups or branched (C3-Cio) alkyl groups, Cs-Ce cycloalkyl.

It is preferred according to the invention if the radicals R ² and R ^{4 are the} same according to formulas (I) and (Ia).

Further preferred selected compounds from the group of catechols are at least one compound of the general formula (Ib)

in which m and n independently of one another represent 0 to 5 and A and B independently of one another represent a hydrogen atom, -NR ¹ R ² , -N ⁺ R ¹ R ² R ³ X, and R ¹ , R ² and R ³ independently of one another represents H or a straight-chain or branched-chain aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2, carbon atoms and X represents an anion.

Preferred compounds of the general formula (Ib) are those in which A and B are the same. A- is in the formulas (I) and (la) and X- in formula (Ib) is preferably from the group comprising lactate, citrate, tartrate, succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate , Hydrogen phosphate, phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, bromide, hydrogen carbonate and carbonate and mixtures of at least two of these are selected, the charge balancing in the presence of polyvalent anions by the presence of several cationic frameworks of the corresponding general formula or, if appropriate, by the presence of additional cations such as sodium or ammonium ions can be guaranteed.

It is preferred according to the invention if, according to formula (Ib), A and B represent a hydrogen atom.

Most preferred catechol compounds of the formula (I) are the compounds of the formulas (Ic)

Tinting dyes per se are known to the person skilled in the art. All tinting dyes are suitable in the present invention, provided that they are substantially free of

Are transition metals.

The tinting dyes are particularly preferably methine blue and violet dyes,

Azo dyes, azine dyes, oxazine dyes, and xanthene dyes or dyes based on anthraquinone, acridine, Benzodifuran, benzodifuranone, carotenoids, coumarin, cyanines, diazahemicyanines, diphenylmethane, formazan, Hemicyanide, indigoid, methine, naphthalimide, naphthoquinone, nitro and nitroso compounds, oxazines, Pyrazoles, polyethyleneimines, stilbenes, styrene, triarylmethanes, triphenylmethanes, xanthenes, triphenooxazines, and thiophenes or mixtures thereof.

Suitable tinting dyes are, for example, in WO 2006/004876 A1, WO 2014/089386 A1, WO 2015/1 10291 A1, WO2015 / 042209 A1, WO 2012/059363 A1, EP 2852639 A1, EP 2 440645 A1, EP 2 864 464 A1 and WO 2006/055787 A1. In preferred aspects, the at least one tinting dye is selected from compounds having the general formula H-1:

(H-1)

where R ¹ and R ^{2 are} independently selected from [(CH2CR'HO) x (CH2CR “HO) _y Qj, C1-12 alkyl, C6-10 aryl, C7-22 arylalkyl, with the proviso that at least one of R ¹ and R ^{2 is} [(CH2CR'HO) x (CH2CR “HO) _y Qj, where R 'is selected from the group consisting of H, C1-4 alkyl, CH ₂ 0 (CH ₂ CH ₂ 0) _Z Q, Phenyl and -CH2OR ⁵ ; wherein R "is selected from H, C1-4 alkyl, CH20 (CH2CH20) _Z Q, phenyl and -CH2OR ⁵ ; where 1 or 2 <x + y <50, preferably x + y <25, more preferably x + y <10; where y>; where z = o or 1 to 20, preferably 0 or 10 or 5; and wherein Q is selected from the group consisting of H and Y and wherein Y is as defined below; with the proviso that the dye comprises at least one radical Q which is Y; each R ^{5 is} selected from the group consisting of C1-16 linear or branched alkyl, C6-14 aryl and C7-16 arylalkyl; R ⁵ is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, phenyl, benzyl , 2-phenylethyl, naphthyl and mixtures thereof; and wherein Y is an organic radical represented by Formula H-2:

(H-2)

each independently being Y, M or H or a charge balancing cation; m is 0 to 5, preferably 0, 1, 2 or 3; n is 0 to 5, preferably 0, 1, 2 or 3; the sum of m + n is 1 to 10, preferably 1, 2 or 3; each R ^{8 is} independently selected from the group consisting of H and C3-18 or C4-18 or even C4-7 and / or C9-18 alkenyl and wherein at least one R ^{8 is} not H.

A preferred tinting dye based on antrachinone is a compound of the formula (H-3):

(H-3) wherein if ring A is substituted by a reactive radical, this radical is preferably selected from the group selected from: dichlorotriazinyl, difluorochloropyrimidine,

Monofluorotrazinyl, monofluorochlorotrazinyl, dichloroquinoxaline, difluorotriazine, monochlorotriazinyl, trichloropyrimidine-2-bromoprop-2-enamide; 2,3-dibromopropanamide; and sulfooxyethylsufonyl. The ring A can additionally be substituted by an organic radical selected from C1-8 alkyl or SOsNa.

Another preferred tinting dye based on antrachinone is a compound of the formula (H-4):

(H-4)

where R1, R4, R5 and R8 are independently selected from the radicals consisting of -H, -OH, -NH2, NHCOCH3 and -NO2, with the proviso that at most one radical is one -NO2 radical and at most two -H Residues are present as R1, R4, R5 and R8; and R2, R3, R6 and R7 are selected from -H, F, Br, CI or -NO2 and -O-aryl. 1-Hydroxy-4- (p-tolylamino) antraquinone, 1-hydroxy-4 - [(4-methylphenyl) amino] -9,10-anthracenedione and 1-hydroxy-4- (4-methylanilino) anthraquinone are particularly preferred .

Monoazo dyes of the formula (H-5) are also preferred:

wherein R3 and R4 are optionally substituted C2 to C12 alkyls which optionally contain an ether (-0-) or ester bridge in the chain, and the chain is optionally substituted by -CI, -Br, -CN, -NO ₂ , and -SO ₂ CH3, and D represents an aromatic or heteroaromatic radical which are optionally substituted by -CI, -Br, -CN, -NO ₂ , - SO2CH3 and -NHCOR, where R is selected from -CH3, -C2H5 and -CH2CI.

Compounds of the formulas H-6 and H-7 are particularly preferred:

wherein X and Y are selected from -CI, -Br, -CN, -NO2, -SO2CH3 and -NHCOR, where R is selected from -CH3, -C2H5 and -CH2CI. Preferably X is NHCOCH3 or NHCOCH2CI.

Formula H-8 has further preferred tinting dyes:

(H-8),

where Z is H or phenyl, ring A is preferably substituted with a methyl or methoxy radical at the positions indicated by the arrows, ring A also being a

Can be naphthyl ring, the radical Y is a phenyl or naphthyl ring which is substituted by a sulphate radical and can be mono- or disubstituted by two methyl radicals.

The tinting dyes according to formula H-9 are also preferred:

where at least two of the naphthyl rings A, B and C are substituted by a sulfonate residue, the ring C at the 5-position can be substituted by an NH2 or NHPh residue, X is a phenyl or naphthyl ring which is substituted by up to 2 sulfonate residues and which can be substituted at the 2-position with an -OH radical and which can also be substituted with an NH2 or NHPh radical.

Furthermore, the at least one tinting dye can have the following formula H-10:

(H-10)

where R _a , Rb, Rc and Rd are selected from: H, a branched or linear C1-C7 alkyl radical, benzyl, phenyl, and naphthyl, the dye having at least one radical -SO3 or -COO, preferably two -SO3 radicals, is substituted; ring B has no negatively charged residues or salts thereof; and ring A may be substituted to form naphthyl; wherein the dye may optionally be further substituted by radicals selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, CI, Br, I, F and NO2.

The formula H-11 has further preferred tinting dyes:

(H-1 1)

wherein, R1, R2, R3 and R4 are selected from the group consisting of: H, Me, Et, n-Pr and i-Pr; and the dye is optionally substituted by a methoxy group.

Formula H-12 has further preferred tinting dyes:

wherein R1, R2, R3 and R4 are selected from the group consisting of: H, Me, Et, n-Pr and i-Pr; and the dye is optionally substituted by a methoxy group.

Tinting dyes having the formula H-13 are also preferred:

(H-13)

wherein one or both rings A and B are substituted with a reactive radical, preferably with - SCbNa, and optionally also -CH3, -C2H5 and -OCH3.

Formula H-14 has further preferred tinting dyes:

wherein ring C are substituted with a reactive radical, preferably with -SCbNa, and

optionally further -CH3, -C2H5 and -OCH3.

Also preferred tinting dyes have the formula H-15:

(H-15),

wherein rings D and E are substituted with a reactive radical, preferably with -SCbNa.

Exemplary preferred compounds for the tinting dyes are

also known as Basic Blue 1,

also known as Basic Blue 15,

also known as Basic Blue 55 _; WO 2020/074141

16

also known as Basic Violet 16,

known as Basic Blue 47,

wherein in the above five compounds, n is an integer from 0 to 7 and m is an integer from 0 to 7.

The composition also contains at least one surfactant and can contain further surfactants in the further components. It is again particularly preferred if, based on the weight of the composition according to the invention, surfactant in a total amount of 10 to 70% by weight, in particular 20 to 65% by weight, very particularly preferably 30 to 65% by weight, in particular 30 to 60 wt .-% is included.

The group of surfactants includes the nonionic, anionic, cationic and amphoteric surfactants. According to the invention, the composition can comprise one or more of the surfactants mentioned. It particularly preferably comprises at least one or more anionic surfactants (anionic surfactants), preferably in a total amount of from 15 to 50% by weight, in particular from 20 to 40% by weight, in each case based on the weight of the

Composition, are included.

The at least one anionic surfactant is preferably selected from the group comprising C9-Ci3-alkylbenzenesulfonates, olefin sulfonates, Ci2-Ci8-alkanesulfonates, ester sulfonates,

Alk (en) yl sulfates, fatty alcohol ether sulfates and mixtures thereof. It has been shown that these sulfonate and sulfate surfactants are particularly good for producing stable liquid

Compositions with a yield point are suitable. Liquid compositions which comprise C9-Ci3-alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant have particularly good, dispersing properties. Preferred surfactants of the sulfonate type are C9-Ci3-alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and

Hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Ci2-Ci8 alkane sulfonates and the esters of a-sulfo fatty acids (ester sulfonates) are also suitable, for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

As alk (en) yl sulfates, the alkali and especially the sodium salts of

Sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol,

Tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cio-C2o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. The Ci2-Ci6-alkyl sulfates and Ci ₂ -Ci5-alkyl sulfates and Ci ₄ -Ci5-alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates are also suitable anionic surfactants.

Preferred alk (en) yl sulfates are the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the oxo alcohols with 10 to 20 carbon atoms and those half-esters of secondary alcohols of this chain length are preferred. For reasons of washing technology, the alkyl sulfates with 12 to 16 carbon atoms and alkyl sulfates with 12 to 15 carbon atoms and alkyl sulfates with 14 and 15 carbon atoms are preferred. 2,3-Alkyl sulfates are also suitable anionic surfactants.

Also fatty alcohol ether sulfates, such as the sulfuric acid monoesters of the straight-chain or branched C7-C _2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-1 1 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C12- 18-fatty alcohols with 1 to 4 EO are suitable. Alkyl ether sulfates having the formula (A-1) are preferred

R ¹ -0- (A0) _n -S0 ₃ X ⁺ (A-1)

In this formula (A-1), R ^{1 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ^{1 of} the formula (A-1) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,

Octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of carbon atoms being preferred. Particularly preferred radicals R ^{1 of} the formula (A-1) are derived from fatty alcohols with 12 to 18 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 20 carbon atoms .

AO in formula (A-1) represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n of the formula (A-1) is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n 2, 3, 4, 5, 6, 7 or 8 is very particularly preferred. X is a monovalent cation or the n-th part of an n-valent cation, preference being given to the alkali metal ions and among them Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X ⁺ can be selected from NH ₄ ⁺ , 1 Zn ²⁺ , 1 Mg ²⁺ , 1 Ca ²⁺ , 1 Mn ²⁺ , and mixtures thereof.

Particularly preferred detergents contain an alkyl ether sulfate selected from

Fatty alcohol ether sulfates of the formula A-2

(A-2) with k = 1 1 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na

Fatty alcohol ether sulfates with 12 to 18 carbon atoms and 2 EO (k = 1 1 to 13, n = 2 in formula A-1). The degree of ethoxylation indicated represents a statistical mean value, which can be an integer or a fraction for a specific product. The degrees of alkoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

It is preferred that the composition contain a mixture of sulfonate and sulfate surfactants. In a particularly preferred embodiment, the composition contains C9-13-alkylbenzenesulfonates and optionally additionally fatty alcohol ether sulfates as the anionic surfactant.

It is very particularly preferred if the composition contains at least one anionic surfactant of the formula (A-3)

so; Y

(A-3),

in the

R ^' and R ^"are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms, and Y ^{+ is} a monovalent cation or the nth part of an n-valent cation (in particular Na ⁺ ) mean.

In addition to the anionic surfactant, the composition can also contain soaps.

Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants and the soaps can be in the form of their sodium, potassium or

Magnesium or ammonium salts are present. The anionic surfactants are preferably in the form of their ammonium salts, the ammonium ion being derived from at least one (C2-C6) alkanolamine. Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine, monoethanolamine, triethanolamine or

Methylethylamine. The composition (preferably together with at least one anionic surfactant) can also have at least one nonionic surfactant. The nonionic surfactant includes alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated

Fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides,

Alkyl polyglucosides and mixtures thereof. It is again particularly preferred if, based on the weight of the composition according to the invention, nonionic surfactant is present in a total amount of 10 to 40% by weight, in particular 15 to 35% by weight.

The nonionic surfactant used is preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 5 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include

for example C12-14 alcohols with 4 EO or 7 EO, C9-1 1 alcohol with 7 EO, C13-15 alcohols with 5 EO, 7 EO or 8 EO, Ci2-Ci8 alcohols with 5 EO or 7 EO and Mixtures of these. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used.

Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO (propylene oxide) groups together in the molecule can also be used according to the invention. Also suitable are a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a Ci6-Ci8 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. The detergent particularly preferably contains a Ci2-Ci8 fatty alcohol with 7 EO or a Ci3-Ci5-oxo alcohol with 7 EO as a nonionic surfactant.

The composition particularly preferably contains at least one nonionic surfactant of the formula (N-1)

R ³ -0- (X0) mH, (N-1) in the

R ^{3 represents} a linear or branched Cs-C-is-alkyl radical, an aryl radical or alkylaryl radical,

XO independently of one another for an ethylene oxide (EO) or propylene oxide (PO) group, m stand for integers from 1 to 50.

In the above formula (N-1), R ^{1 represents} a linear or branched, substituted or unsubstituted alkyl group. In a preferred embodiment of the present invention, R ^{1 is} a linear or branched alkyl radical having 5 to 30 C atoms, preferably having 7 to 25 C atoms and in particular having 10 to 19 C atoms. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, the representatives with an even number of carbon atoms being preferred . Particularly preferred radicals R ¹ are derived from fatty alcohols with 12 to 19 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 19 carbon atoms.

AO of formula (N-1) is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index m of the formula (N-1) is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7. The composition according to the invention can be mixtures of nonionic surfactants contain different degrees of ethoxylation. Surfactants with degrees of alkoxylation / ethoxylation of at least 5 are preferred.

In summary, particularly preferred fatty alcohol alkoxylates are those of the formula

(N-2) with k = 9 to 17, m = 3, 4, 5, 6 or 7. Very particularly preferred representatives are fatty alcohols with 10 to 18 carbon atoms and with 7 EO (k = 1 1-17, m = 7 in formula N-2).

Such fatty alcohol or oxo alcohol ethoxylates are available under the trade names Dehydol LT7 ^® (BASF) Lutensol ^® A07 (BASF) Lutensol ^® M7 (BASF), and Neodol ^® 45-7 (Shell Chemicals).

The compositions according to the invention preferably additionally contain at least one further active substance. Active substances in the sense of the present invention are in particular:

- Textile care products such as plasticizers, water repellents and impregnants

Re-soiling, bleach activators, enzymes, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents,

Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, swelling and anti-slip agents, UV absorbers, cationic polymers, - skin care products or

- perfume (oil) or fragrances.

At least one active substance is preferably selected from enzymes, optical brighteners,

Builders, solvents, anti-redeposition agents, color transfer inhibitors,

Preservatives, perfume or mixtures of at least two of the aforementioned

Active substances.

The composition can also be one of the catechol compound according to formula (I)

contain various additional bleach. In a preferred embodiment, essentially no further bleaching agent is contained.

It is preferred if the composition according to the invention additionally contains at least one enzyme, in particular selected from protease, amylase, lipase, mannanase, cellulase, pectate lyase or mixtures thereof.

At the protein level, "variant" is the term corresponding to "mutant" at the nucleic acid level. The precursor or starting molecules can be wild-type enzymes, that is to say those which are obtainable from natural sources. They can also be enzymes that are already variants in themselves, that is, compared to the

Wild type molecules have already been changed. These include, for example, point mutants, those with changes in the amino acid sequence, over several positions or longer contiguous regions, or else hybrid molecules which are composed of mutually complementary sections of different wild-type enzymes.

Amino acid exchanges are substitutions of one amino acid for another

Understand amino acid. According to the invention, such substitutions, optionally designating the positions in which the exchange takes place, are combined with the relevant ones

Amino acids specified in the internationally used single-letter code. “Exchange in position 320” means, for example, that a variant in the position which has the position 320 in the sequence of a reference protein has a different amino acid. Such exchanges are usually carried out at the DNA level via mutations of individual base pairs (see above). “R320K” means, for example, that the reference enzyme at position 320 contains the amino acid arginine, while the variant under consideration at the position that can be homologated via the amino acid lysine "320K" means that any, that is to say usually a naturally prescribed, amino acid at a position which corresponds to position 320 is replaced by a lysine which is located at precisely this point in the present molecule. "R320K, L “means that the amino acid arginine at position 320 is replaced by lysine or leucine. And "R320X" means that the amino acid arginine in position 320 is replaced by any other amino acid. In principle, the amino acid exchanges according to the invention designated by the present application are not limited to the fact that they are the only exchanges in which the variant in question differs from the wild-type molecule. It is known in the prior art that the advantageous properties of individual point mutations can complement one another. Thus, embodiments of the present invention include all variants which, in addition to other exchanges with the wild-type molecule, also have the exchanges according to the invention.

Furthermore, in principle it does not matter in what order the amino acid exchanges in question have been carried out, that is to say whether a corresponding point mutant

is further developed according to the invention or, for example, a variant according to the invention is first generated from a wild-type molecule, which is further developed in accordance with other teachings found in the prior art. Several exchanges can also be carried out simultaneously in a mutagenesis approach, for example the invention and others together.

It is preferred according to the invention if at least one protease is contained as the enzyme. A protease is an enzyme that cleaves peptide bonds by hydrolysis. Each of the class E.C. 3.4 falls according to the invention (including each of the thirteen subclasses). The EC number corresponds to the Enzyme Nomenclature 1992 of the NC-IUBMB, Academic Press, San Diego, California, including supplements 1 to 5, published in Eur. J. Biochem. 1994, 223, 1-5; Eur. J. Biochem. 1995, 232, 1-6; Eur. J. Biochem. 1996, 237, 1-5; Eur. J. Biochem. 1997, 250, 1-6; and Eur. J. Biochem. 1999, 264, 610-650.

Subtilase names a subset of the serine proteases. The serine proteases or serine peptidases are a subset of the proteases that have serine in the active center of the enzyme that forms a covalent adduct with the substrate. Furthermore, the subtilases (and the

Serine proteases) characterized in that, in addition to said serine with histidine and aspartame, they have two further amino acid residues in the active center. The subtilases can be divided into 6 subclasses, namely the subtilisin family, the thermitase family, the proteinase K family, the family of lantibiotic peptidases, the kexin family and the pyrolysine family. The proteases which are preferably excluded or preferably contained in reduced amounts as part of the compositions according to the invention are endopeptidases (EC 3.4.21).

According to the invention, “protease activity” is present if the enzyme has proteolytic activity (EC 3.4). Different types of protease activity are known: The three main types are:

Trypsin-like, with cleavage of the amide substrate according to the amino acids Arg or Lys at P1; Chymotrypsin-like, with cleavage after one of the hydrophobic amino acids at P1; and elastase-like, with cleavage of the amide substrate according to Ala at P1. The protease activity can be determined by the method described in Tenside, Volume 7 (1970), pp. 125-132. Accordingly, it is given in PE (protease units). The protease activity of an enzyme can be determined according to standard methods, such as in particular using BSA as substrate (bovine albumin) and / or using the AAPF method.

Surprisingly, it was found that a protease of the type of the alkaline protease from Bacillus lentus DSM 5483 or a protease sufficiently similar to this (based on the sequence identity), which exhibits several of these changes in combination, is particularly suitable and advantageous in the composition according to the invention is stabilized better. There are thus advantages of using this protease

especially with regard to washing performance and / or stability.

The identity of nucleic acid or amino acid sequences is determined by a sequence comparison. This sequence comparison is based on the BLAST algorithm established and commonly used in the prior art (see, for example, Altschul, S.F., Gish, W., Miller,

W., Myers, E.W. & Lipman, D.J. (1990) "Basic local alignment search tool." J. Mol. Biol. 215: 403-410, and Altschul, Stephan F., Thomas L. Madden, Alejandro A. Schaffer, Jinghui Zhang, Hheng Zhang, Webb Miller, and David J. Lipman (1997): "Gapped BLAST and PSI-BLAST: a new generation of protein database search programs "; Nucleic Acids Res., 25, S.3389-3402) and happens principally in that similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences are assigned to one another. A tabular assignment of the relevant positions is called alignment. Another algorithm available in the prior art is the FASTA algorithm. Sequence comparisons (alignments), in particular multiple sequence comparisons, are created using computer programs. The Clustal series (cf. for example Chenna et al. (2003): Multiple sequence alignment with the Clustal series of programs. Nucleic Acid Research 31, 3497-3500), T-Coffee (cf. for example Notredame et al . (2000): T-Coffee: A novel method for multiple sequence alignments. J. Mol. Biol. 302, 205-217) or programs based on these programs or algorithms. In the present invention, all

Sequence comparisons (alignments) with the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the predefined ones

Standard parameters created, whose AlignX module for sequence comparisons is based on ClustalW.

Such a comparison also allows a statement about the similarity of the compared sequences to one another. It is usually given in percent identity, that is to say the proportion of identical nucleotides or amino acid residues in the same positions or in an alignment corresponding to one another. The broader concept of homology also includes conserved amino acid exchanges for amino acid sequences, i.e. amino acids Similar chemical activity, since they mostly have similar chemical activities within the protein. Therefore, the similarity of the compared sequences can also be given as percent homology or percent similarity. Identity and / or homology information can be made about entire polypeptides or genes or only over individual areas. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by matches in the sequences. Such areas often have identical functions. They can be small and contain only a few nucleotides or amino acids. Such small areas often have essential functions for the overall activity of the protein. It can therefore make sense to relate sequence matches only to individual, possibly small, areas. Unless otherwise stated, identity or homology information in the present application relates to the total length of the nucleic acid or amino acid sequence specified in each case.

The concentration of the protease in the composition is from 0.001-0.1% by weight, preferably from 0.01 to 0.06% by weight, based on active protein.

The compositions according to the invention (particularly preferably in addition to the protease) preferably contain as enzyme at least one enzyme selected from α-amylase, cellulase, mannanase, lipase, pectate lyase.

In general, the enzymes contained in a composition according to the invention can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation.

Compositions according to the invention can be added to the enzymes obtained in any form established according to the prior art. This includes in particular the through

Granulation, extrusion or lyophilization obtained solid preparations, advantageously concentrated as possible, low in water and / or mixed with stabilizers. In an alternative dosage form, the enzymes can also be encapsulated, for example by

Spray drying or extrusion of the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel, or in those of the core-shell type in which an enzyme-containing core with a Water, air and / or chemical impermeable protective layer is coated. Additional active ingredients, for example stabilizers, emulsifiers, pigments or dyes, can additionally be applied in the layers. Capsules of this type are applied by methods known per se, for example by churning or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating. The compositions preferably additionally contain at least one cellulase. A

Cellulase is an enzyme. Synonymous terms can be used for cellulases, in particular endoglucanase, endo-1, 4-beta-glucanase, carboxymethyl cellulase, endo-1, 4-beta-D-glucanase, beta-1, 4-glucanase, beta-1, 4-endoglucan hydrolase , Cellulose extrinase or avicelase. The decisive factor for whether an enzyme is a cellulase in the sense of the invention is its ability to hydrolize 1,4-β-D-glucosidic bonds in cellulose.

Ready-to-use cellulases (endoglucanases, EG) include, for example, the fungal cellulase preparation rich in endoglucanase (EG) or its preparation

Further developments by the Novozymes company under the trade name

Celluzyme® is offered. The products Endolase® and Carezyme®, which are also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from Humicola insolens DSM 1800. Other usable commercial products from this company are Cellusoft®, Renozyme® and Celluclean®. They can also be used, for example

Cellulases sold by AB Enzymes, Finland, under the trade names

Ecostone® and Biotouch® are available, and are based at least in part on the 20 kD EG from Melanocarpus. Other cellulases from AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, where the from Bacillus sp. CBS 670.93 is available from Danisco / Genencor under the trade name Puradax®. Other usable commercial products from Danisco / Genencor are “Genencor detergent cellulase L” and lndiAge®Neutra.

Variants of these enzymes obtainable by point mutations can also be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, which are disclosed in international patent publication WO 98/12307, made from cellulases

Melanocarpus, especially Melanocarpus albomyces, which is used in the international

Publication WO 97/14804 discloses cellulases of the EGIII type from Trichoderma reesei, which are disclosed in European patent application EP 1 305 432 or variants obtainable therefrom, in particular those which are disclosed in European ones

Patent applications EP 1240525 and EP 1305432, as well as cellulases, which are disclosed in the international patent applications WO 1992006165, WO 96/29397 and WO 02/099091. Reference is therefore expressly made to their respective disclosures, and their disclosure content in this regard is therefore expressly included in the present invention.

Compositions which are particularly preferred according to the invention are characterized in that at least one cellulase from Melanocarpus sp. or Myriococcum sp. available 20K cellulase or those which have a homology of over 80% (increasingly preferred of over 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90 , 5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98, 5%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99, 9%).

The from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase is from the

international patent application WO 97/14804 known. As described there, it has a molecular weight of about 20 kDa and has at least 80% of its maximum activity at 50 ° C. in the pH range from 4 to 9, with almost 50% of the maximum activity remaining at pH 10. As also described there, it can be isolated from Melanocarpus albomyces and produced in genetically engineered Trichoderma reseei transformants. Cellulases which have a homology of over 80% can also be used for the purposes of the present invention.

(increasingly preferred over 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92% , 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98 , 5%, 99.0%, 99, 1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99 , 9%) to 20K cellulase.

K20 cellulase is preferably used in amounts such that a composition according to the invention has a cellulolytic activity of 1 NCU / g to 500 NCU / g (can be determined by the hydrolysis of 1% by weight carboxymethyl cellulose at 50 ° C. and neutral pH and determination of the reducing substances released in the process Sugar using dinitrosalicylic acid, as described by MJBailey et al. In Enzyme Microb. Technol. 3: 153 (1981); 1 NCU defines the amount of enzyme that produces reducing sugars in an amount corresponding to 1 nmol glucose per second), especially of 2 NCU / g to 400 NCU / g and particularly preferably from 6 NCU / g to 200 NCU / g. In addition, the composition according to the invention can optionally contain further cellulases.

A composition according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of cellulolytic protein per gram of the total

Composition. The protein concentration can be determined using known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177 , 751 -766, 1948).

It is again particularly preferred according to the invention, in addition to at least one first cellulase from Melanocarpus sp. or Myriococcum sp. available 20K cellulase or those which have a homology of over 80% (increasingly preferred of over 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90 , 5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5 %, 97%, 97.5%, 98%, 98.5%, 99.0%, 99, 1%, 99.2%, 99.3%, 99.4%, 99.5%, 99, 6%, 99.7%, 99.8%, 99.9%) additionally has at least one more of the first cellulase

use different second cellulase. It is preferred according to the invention if the compositions according to the invention additionally contain at least one lipase. Lipase enzymes preferred according to the invention are selected from at least one enzyme from the group which is formed from triacylglycerol lipase (EC 3.1.1.3) and lipoprotein lipase (EC 3.1.1.34) and monoglyceride lipase (EC 3.1.1.23).

Furthermore, the lipase preferably contained in a composition according to the invention is naturally present in a microorganism of the species Thermomyces lanuginosus or Rhizopus oryzae or Mucor javanicus or is derived from the aforementioned naturally present lipases by mutagenesis. The compositions according to the invention particularly preferably comprise at least one lipase which is naturally present in a microorganism of the species Thermomyces lanuginosus or which is naturally different from the aforementioned

Thermomyces lanuginosus derives existing lipases by mutagenesis.

In this context, naturally present means that the lipase is a separate enzyme of the microorganism. The lipase can thus be expressed in the microorganism by a nucleic acid sequence that is part of the chromosomal DNA of the microorganism in its wild-type form. It or the nucleic acid sequence coding for it is consequently present in the wild-type form of the microorganism and / or can be derived from the wild-type form of the

Microorganism can be isolated from this. In contrast, one would not be

lipase naturally present in the microorganism or the coding for it

Nucleic acid sequence was introduced into the microorganism in a targeted manner using genetic engineering methods, so that the microorganism would have been enriched with the lipase or the nucleic acid sequence coding for it. However, a lipase that is naturally present in a microorganism of the species Thermomyces lanuginosus or Rhizopus oryzae or Mucor javanicus may have been produced recombinantly by another organism.

The fungus Thermomyces lanuginosus (also known as Humicola lanuginosa) belongs to the class of Eurotiomycetes (subclass Eurotiomycetidae), here to the order of the Eurotiales and here to the family Trichocomaceae and the genus Thermomyces. The fungus Rhizopus oryzae belongs to the class of the Zygomycetes (subclass Incertae sedis), here to the order Mucorales and here again to the family Mucoraceae and the genus Rhizopus. The fungus Mucor javanicus also belongs to the class of the Zygomycetes (subclass Incertae sedis), here to the order Mucorales and again to the Mucoraceae family, and then to the genus Mucor. The names Thermomyces lanuginosus, Rhizopus oryzae and Mucor javanicus are the biological ones

Species designations within the respective genus.

Lipases preferred according to the invention are those from Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE® and Lipase F® (also Lipase JV®) available lipase enzymes. For example, Lipase F® is naturally present in Rhizopus oryzae. Lipase M-AP10®, for example, is naturally present in Mucor javanicus.

Compositions of a very particularly preferred embodiment of the invention contain at least one lipase which is selected from at least one or more polypeptides with an amino acid sequence which is at least 90% (and increasingly preferred at least 81%, 82%, 83%, 84%, 85 %, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94 , 5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99, 1%, 99.2% , 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%) is identical to the wild-type lipase from the strain DSM 4109 Thermomyces lanuginosus. It is again preferred if, based on said wild-type lipase from strain DSM 4109, there is at least the amino acid change N233R.

Within the scope of a further embodiment, in particular those lipases derived from the wild-type lipase from strain DSM 4109 which are selected from at least one lipase enzyme according to at least one of the

Claims 1 to 13 of document WO 00/60063 A1. Reference is expressly made in full to the disclosure in publication WO 00/60063 A1.

Particular preference is given to using at least one lipase in the compositions of the invention which is derived from the wild-type lipase from strain DSM 4109 and in which, based on said wild-type lipase, at least one substitution of an electrically neutral or negatively charged amino acid by a positively charged amino acid was carried out. The charge is determined in water at pH 10. Negative amino acids in the sense of the invention are E, D, Y and C. Positively charged amino acids in the sense of the invention are R, K and H, in particular R and K. Neutral amino acids in the sense of the invention are G, A, V, L, I , P, F, W, S, T, M, N, Q and C if C forms a disulfide bridge.

In the context of this embodiment of the invention, it is also preferred if, starting from the wild-type lipase from strain DSM 4109, at least one of the following

Amino acid exchanges in positions D96L, T213R and / or N233R, particularly preferably T213R and N233R, are present.

A highly preferred lipase is commercially available from Novozymes (Denmark) under the trade name Lipex® and can advantageously be used in the cleaning compositions according to the invention. Lipase Lipex® is particularly preferred

100 L (ex Novozymes A / S, Denmark). Preferred compositions are characterized in that, based on the total weight of the composition, said lipase Enzyme from Lipex® 100 L is contained in a total amount of 0.01 to 1.0% by weight, in particular 0.02 to 0.1% by weight.

The compositions according to the invention can additionally contain at least one mannanase as enzyme. A mannanase contained in the composition according to the invention (in particular in a washing and cleaning agent for textiles preferred according to the invention) catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans and galactoglucomannans as part of its mannanase activity.

Said mannanase enzymes according to the invention are, according to the enzyme nomenclature, as E.C. 3.2.1.78 classified.

The mannanase activity of a polypeptide or enzyme can be according to the literature

Test methods can be determined. For example, a test solution is placed in 4 mm diameter holes of an agar plate containing 0.2% by weight of AZGL galactomannan (carob), i.e. Substrate for the endo-1,4-beta-D-mannanase essay, available under catalog number 1-AZGMA from Megazyme (http://www.megazyme.com), introduced.

Suitable compositions according to the invention contain, for example, mannanase, which is marketed under the name Mannaway® by Novozymes.

Mannanase enzymes have been identified in numerous Bacillus organisms:

WO 99/64619 discloses examples of liquid, protease-containing detergent compositions with a high total surfactant content of at least 20% by weight, which additionally comprise mannanase enzyme.

The compositions according to the invention preferably contain mannanase in a total amount of 0.01 to, based on the total weight of the composition

1.0% by weight, in particular from 0.02 to 0.1% by weight.

Mannanase polypeptides from strains of the Thermoanaerobacter group, such as caldicellulose ruptor, are preferably suitable according to the invention. Mannanase polypeptides of the fungi Humicola or Scytalidium, in particular of the species Humicola insolens or Scytalidium thermophilum, can also be used in the context of the invention.

It is particularly preferred according to the invention if the compositions according to the invention as mannanase enzyme have at least one mannanase polypeptide from gram-positive alkalophilic strains of Bacillus, in particular selected from at least one member of the group from Bacillus subtilis, Bacillus ientus, Bacillus clausii, Bacillus agaradhaerens, Bacillus brevis, Bacillus stearothermophilus, Bacillus alkalophilus, Bacillus amyloliquefaciens, Bacillus coagulans, Bacillus circulans, Bacillus lautus, Bacillus thuringiensis, Bacillus cheniformis, and Bacillus sp., particularly preferably selected from at least one member of the group from Bacillus sp. 1633, Bacillus sp. AAI12, Bacillus clausii, Bacillus agaradhaerens and Bacillus licheniformis.

A preferred mannanase according to the invention is selected from at least one representative from the group that is formed from

i) polypeptides comprising an amino acid sequence which is at least 90% (more preferably at least 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94 , 5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99, 1%, 99.2% , 99.3%, 99.4%, 99.5%, 99.6%, 99.7% or 99.8%) sequence identity to the polypeptide according to SEQ ID No.1 (cf.

Sequence listing from WO 99/64619), and

ii) polypeptides that are a fragment of (i).

It is again preferred if said preferred mannanase in a total amount of 0.01 to 1.0% by weight, in particular 0.02 to 0.1% by weight, in each case based on the total weight of the composition, in the composition according to the invention is included.

Particularly preferably, the composition according to the invention contains, in addition to the preferred protease of the type of the alkaline protease from Bacillus lentus DSM 5483 or in addition to the protease sufficiently similar to this (based on the sequence identity), several of these

Has changes in combination, in addition at least one a-amylase. a-Amylases (E.C. 3.2.1.1) hydrolyze as internal enzyme a-1, 4-glycosidic bonds of starch and starch-like polymers. This a-amylase activity is measured, for example, according to the applications WO 97/03160 A1 and GB 1296839 in KNU (Kilo Novo Units). 1 KNU stands for the amount of enzyme, the 5.25 g of starch (available from Merck, Darmstadt, Germany) per hour at 37 ° C., pH 5.6 and in the presence of 0.0043 M.

Calcium ions hydrolyzed. An alternative activity determination method is the so-called DNS method, which is described for example in the application WO 02/10356 A2. Then the oligosaccharides, disaccharides and glucose units released by the enzyme during the hydrolysis of starch are oxidized by oxidation of the reducing ends

Detected dinitrosalicylic acid (DNA). The activity is obtained in pmol of reducing sugars (based on maltose) per min and ml; this results in activity values in TAU. The same enzyme can be determined by different methods, the respective

Conversion factors may vary depending on the enzyme and must therefore be determined using a standard. You can roughly calculate that 1 KNU corresponds to approx. 50 TAU. Another activity determination method is measurement using the Quick-Start ^® test kit from Abbott, Abott Park, Illinois, USA. A preferred area of use of the compositions according to the invention is the cleaning of textiles. Because laundry detergents and cleaning agents for textiles mainly have alkaline pH values, a-amylases, which are active in the alkaline medium, are used in particular. These are produced and secreted by microorganisms, ie fungi or bacteria, especially those of the genera Aspergillus and Bacillus. Starting from these natural enzymes, there is still an almost unmanageable abundance of variants which have been derived via mutagenesis and which have specific advantages depending on the area of use.

Examples of this are the a-amylases from Bacillus licheniformis, from B. amyloliquefaciens and from B. stearothermophilus as well as their further developments for use in detergents or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST.

Further development products of this a-amylase are from Novozymes among the

Trade names Duramyl ^® and Termamyl ^® ultra, available from Genencor under the name Purastar ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^® . The a-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the alpha-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Examples of a-amylases from other organisms are further developments of a-amylase sold under the trade names Fungamyl.RTM ^® from Novozymes from Aspergillus niger and A. oryzae. Another commercial product is the Amylase-LT ^® .

The prior art includes the three patent applications WO 96/23873 A1,

WO 00/60060 A2 and WO 01/66712 A2, which have been registered by Novozymes.

WO 96/23873 A1 describes several different point mutations in a total of more than 30 different positions in four different wild-type amylases and claims them for all amylases with at least 80% identity to one of these four; they should have changed enzymatic properties with regard to thermal stability, oxidation stability and calcium dependence. The application WO 00/60060 A2 also names a large number of possible amino acid exchanges in 10 different positions on the a-amylases from two different microorganisms and claims those for all amylases with a homology of at least 96% identity to them. Finally, WO 01/66712 A2 denotes 31 different amino acid positions, some of which are identical with the abovementioned, which have been mutated in one of the two a-amylases mentioned in the application WO 00/60060 A2. For example, WO 96/23873 A1 concretely shows the possibility of replacing an M in position 9 in the a-amylases mentioned according to the AA560 count with an L, in position 202 M for L and that in positions 182 and 183 ( or 183 and 184) lying amino acids. WO 00/60060 A2 specifically discloses the

Amino acid variation N195X (basically against any other amino acid).

WO 01/66712 A2 discloses, inter alia, the amino acid variations R1 18K, G186X (including in particular the G186R exchange not relevant here), N299X (including in particular the N299A exchange not relevant here), R320K, E345R and R458K.

The composition according to the invention very particularly preferably contains, in addition to the preferred protease of the alkaline protease type from Bacillus lentus DSM 5483 or a protease which is sufficiently similar to this (based on the sequence identity) and which has several of these changes in combination, additionally at least one a-amylase, the at

Temperatures between 10 and 20 ° C has a higher activity than the amylase with the trade name "Stainzyme 12 L" from Novozymes.

Compositions preferred according to the invention contain α-amylase in a total amount of 0.01 to 1.0% by weight, in particular 0.02 to 0.1% by weight.

It is preferred that at least one optical brightener tyrylbiphenyle from the substance classes of the diskette, the stilbenes, the ^{^{4,4-diamino-2,2-stilbenedisulfonic}} acids, coumarins, the dihydroquinolinones, the 1, 3-diaryl pyrazolines, naphthalimides of , the benzoxazole systems, the benzisoxazole systems, the benzimidazole systems, the heterocycle-substituted pyrene derivatives and mixtures thereof. These substance classes of optical brighteners have a high stability, a high light and oxygen resistance and a high affinity for fibers.

The following optical brighteners, which are selected from the group consisting of disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulfonate, disodium 2,2, are particularly good and stable 'bis (phenyl-styryl) disulfonate, 4,4'-bis [(4-anilino-6- [bis (2-hydroxyethyl) amino] -1,3,5-triazin-2-yl) amino] stilbene -2,2'-disulfonic acid, hexasodium-2,2 '- [vinylenebis [(3-sulphonato-4,1-phenylene) imino [6- (diethylamino) -1,3,5-triazine-4,2-diyl ] imino]] bis- (benzene-1,4-disulfonate), 2,2 '- (2,5-thiophenediyl) bis [5-1, 1-dimethylethyl) benzoxazole (available, for example, as Tinopal® SFP from BASF SE ) and / or 2,5-bis (benzoxazol-2-yl) thiophene are selected, incorporate.

According to the invention, the composition can further comprise builders. Polymeric polycarboxylates, for example, are suitable as builders. These are, for example

Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g / mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn be preferred from this group.

Copolymers of polycarboxylates are furthermore suitable, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve water solubility, the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

As builders, which can be contained in the composition according to the invention, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are to be mentioned in particular. Organic builders are particularly suitable as additional builders, for example the polycarboxylic acids which can be used in the form of their sodium salts or also as acids

Polycarboxylic acids are understood to mean those carboxylic acids which carry more than one acid function. For example, these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, in particular glutamic acid-N, N-diacetic acid (GLDA) and methylglycine-N, N-diacetic acid (MGDA), and mixtures of these. Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g / mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn be preferred from this group. Copolymers of polycarboxylates are also suitable, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with

Maleic acid. The polymers can also be used to improve water solubility

Allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer. Soluble builders, such as acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol, are preferably used in liquid components.

However, soluble builders, such as citric acid, or acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol are particularly preferably used.

The composition preferably further contains one or more non-aqueous solvents. Suitable non-aqueous solvents include monohydric or polyhydric alcohols or glycol ethers, such as ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methyl propanediol, glycerol, glycols, such as diglycol, propyl diglycol, butyl diglycol, Hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether,

Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether,

Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol,

Ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, 2,2-dimethyl-4-hydroxymethyl-1, 3-dioxolane, propylene glycol t-butyl ether, di-n-octyl ether and low molecular weight polyalkylene glycols, such as PEG 400, and mixtures of these solvents.

The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether,

Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether,

Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether,

Propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these

Solvent.

In addition, the compositions according to the invention can additionally contain components which have a positive influence on the oil and fat washability from textiles, so-called soil release active substances. This effect becomes particularly clear when a textile is soiled that has already been washed several times with an agent that contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives with monomeric and / or polymeric diols, in particular polymers

Ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Such are for example under the

Trade names Texcare ^® commercially available.

Antiredeposition agents which can be used are in particular based on (co) polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol, preferably in mixtures with

Anti-redeposition agents.

The composition can preferably also contain color transfer inhibitors, preferably in amounts of 0.1% by weight to 2% by weight, in particular 0.1% by weight to 1% by weight, which are contained in a preferred embodiment of the invention are polymers of vinyl pyrrolidone, vinyl imidazole, vinyl pyridine N-oxide or copolymers of these.

Graying inhibitors have the task of keeping the dirt detached from the textile fibers suspended in the liquor. Water-soluble colloids of mostly organic nature are suitable for this, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch derivatives other than those mentioned above can also be used, for example aldehyde starches. Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition, can preferably be used become.

It is preferred that the color transfer inhibitor is a polymer or copolymer of cyclic amines such as vinyl pyrrolidone and / or vinyl imidazole. As

Color transfer inhibitor-suitable polymers include polyvinyl pyrrolidone (PVP),

Polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI),

Polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole and mixtures thereof.

Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) are particularly preferably used as color transfer inhibitors. The polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53 available. The copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000 g / mol. A PVP / PVI copolymer is commercially available, for example, from BASF under the name Sokalan® HP 56. Another extremely preferred color transfer inhibitor is polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, from BASF under the name Sokalan® HP 66 are.

The composition is used in particular in the context of a washing process for textiles. The compositions described herein are suitable on the one hand as

Washing aids that are used as textile pretreatment and aftertreatment agents in textile washing, that is to say as agents with which the item of laundry is brought into contact before the actual washing, for example to dissolve stubborn soiling. The composition can be present in a portion prepared for a wash cycle (eg as a water-soluble multi-chamber pouch) or in a multi-chamber storage container with a possible mixing chamber.

For the purposes of the invention, a surfactant-containing liquor is a liquid preparation for the treatment of a substrate which can be obtained by using the multi-component detergent of the present invention with dilution with at least one solvent (preferably water). Fabrics or textiles (such as clothing) can be used as substrates. The compositions according to the invention are preferably used to provide a surfactant-containing liquor in the context of machine cleaning processes, such as those e.g. run by a washing machine for textiles.

If it is a multi-component detergent, the further components of the multi-component detergent can be in any dosage form established according to the prior art and / or in any expedient form. These include, for example, liquid, gel-like or pasty dosage forms. The container is preferably a pouch with two, three, four, five, six, seven or eight chambers, both in large containers and packaged in portions.

However, it is very particularly preferred according to the invention if the multicomponent detergent comprises only liquid components, the liquid components preferably being packaged separately from one another.

In a further particularly preferred embodiment, the multicomponent detergent is a multicomponent color detergent, in particular a liquid detergent, that is to say a textile detergent for colored textiles.

The detergents according to the invention preferably contain at least one alkalizing agent or its salt in a total amount of 1 to 20% by weight, preferably 2 to 15% by weight.

The total amount of the alkalizing agent and its salt, or the total amount of all of the following preferred representatives, is calculated on the basis of the base form, i.e. if that

Alkalizing agent in the detergent according to the invention (partially) in its salt form, the counter ion is neglected in the quantity calculation and only the base form without the proton taken up is assumed for the salt fraction.

The alkalizing agents are preferably selected from (C2 to C6) alkanolamine,

Sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate or mixtures thereof. According to the invention, the term (C2 to C6) alkanolamine is to be understood as meaning organic amine compounds which have a carbon skeleton of two to six carbon atoms to which at least one amino group (preferably exactly one amino group) and at least one hydroxyl group (again preferably precisely one hydroxyl group) binds .

Preferred (C2 to C6) alkanolamines according to the invention are primary amines.

In the context of the invention it is preferred to use at least one (C2 to C6) alkanolamine with exactly one amino group. Again, this is preferably a primary amine.

The composition according to the invention preferably contains at least one (C2 to Ob) alkanolamine selected from 2-aminoethan-1-ol (monoethanolamine), tris (2-hydroxyethyl) amine (triethanolamine), 3-aminopropan-1-ol, 4-aminobutane 1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4- ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1, 2-diol, 2-amino-2-methylpropan-1, 3-diol ( especially under 2-aminoethan-1-ol, 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propan-1, 3-diol), or mixtures thereof. Monoethanolamine has proven to be a very particularly suitable (C2 to C6) alkanolamine as an alkalizing agent.

(C2 to C6) alkanolamine or its salt is particularly preferably present in a total amount of 1 to 20% by weight, preferably 2 to 15% by weight, in the detergents according to the invention, in each case based on the basic form.

According to the invention, the liquid composition is preferably in a container (pouch) made of water-soluble material. The container for said multi-component detergent comprises at least two spatially separate chambers

(Multi-chamber pouch), for example 2, 3, 4, 5, 6, 7 or 8 chambers. These chambers are separated from one another in such a way that the liquid or liquid and solid components of the detergent contained do not come into contact with one another. This separation can be done, for example, by a wall made of the same material as the container itself.

It is therefore particularly preferred according to the invention to package the multi-component detergent in a container made of water-soluble material with at least two separate chambers.

A material is water-soluble in the sense of the present invention if at 20 ° C. 0.1 g of the material with stirring (stirring speed magnetic stirrer 300 rpm, stirring rod: 6.8 cm long, diameter 10 mm, beaker 1000 ml low form from Schott , Mainz) within 600 Dissolves in 800 mL water for seconds so that no single solid particles of the material are visible to the naked eye.

The water solubility of the material used for the production of pouches for wrapping in the form of a film can be determined with the aid of a square film of said material (film: 22 x 22 mm with a thickness of) fixed in a square frame (edge length on the inside: 20 mm) 76 gm) can be determined according to the following measurement protocol. Said framed film is immersed in 800 ml of distilled water at a temperature of 20 ° C. in a 1 liter beaker with a circular base (Schott, Mainz, beaker 1000 ml, low form), so that the surface of the clamped film is at a right angle to the Bottom surface of the beaker is arranged, the upper edge of the frame is 1 cm below the water surface and the

Bottom edge of the frame is aligned parallel to the bottom surface of the beaker in such a way that the bottom edge of the frame runs along the radius of the bottom surface of the beaker and the center of the bottom edge of the frame is arranged above the center of the radius of the beaker bottom. The material should dissolve within 600 seconds while stirring (stirring speed magnetic stirrer 300 rpm, stirring rod: 6.8 cm long, diameter 10 mm) in such a way that no individual solid film particles are visible to the naked eye.

The water-soluble or water-dispersible material can comprise a polymer, a copolymer or mixtures thereof. Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.

Preferred water-soluble materials preferably comprise at least partly at least one substance from the group consisting of (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, polyvinyl alcohols substituted with sulphate, carbonate and / or citrate, polyalkylene oxides, acrylamides, cellulose esters, cellulose ethers, cellulose amides, cellulose, polyvinyl acetates , Polycarboxylic acids and their salts, polyamino acids or peptides, polyamides, polyacrylamides, copolymers of maleic acid and acrylic acid, copolymers of acrylamides and (meth) acrylic acid, polysaccharides, such as, for example, starch or guar derivatives, gelatin and under the INCI names Polyquaternium 2, Polyquaternium 17 , Polyquaternium 18 and Polyquaternium 27. The water-soluble material is particularly preferred

Polyvinyl alcohol.

In one embodiment of the invention, the water-soluble material comprises mixtures of different substances. Such mixtures enable the mechanical properties of the container to be adjusted and can influence the degree of water solubility. The water-soluble material preferably contains at least one polyvinyl alcohol and / or at least one polyvinyl alcohol copolymer. "Polyvinyl alcohol" (abbreviation PVAL or PVA occasionally also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

- CH ₂ - CH— CH— CH ₂ -

OH OH included.

Commercially available polyvinyl alcohols with white-yellowish powder or granules

Degrees of polymerization in the range of approximately 100 to 2500 (molar masses of approximately 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 98 to 99 mol% or 87 to 89 mol%, and therefore still contain a residual content of acetyl groups . The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the

Starting polymers, the degree of hydrolysis, the saponification number or

Solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The coatings made of polyvinyl alcohol are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but leave

Pass water vapor through.

In the context of the present invention, it is preferred that the water-soluble material at least partially comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -%. In a preferred embodiment, the water-soluble material consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight from a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 Mol%.

The polyvinyl alcohols described above are widely available commercially, for example under the trademark Mowiol® (Clariant). Polyvinyl alcohols which are particularly suitable in the context of the present invention are, for example, Mowiole 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 and L648, L734, Mowiflex LPTC 221 ex KSE and the compounds from Texas Polymers such as for example Vinex 2034.

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and

Mixtures thereof, itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof.

The water solubility of polyvinyl alcohol polymer can be increased by post-treatment with

Aldehydes (acetalization) or ketones (ketalization) can be changed. Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have turned out to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water.

Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to the desired values. These are preferably not included. Films made of PVAL are largely

impenetrable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

In addition to polyvinyl alcohol, the film material suitable as a water-soluble material can additionally have polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid and / or mixtures of the above polymers.

Suitable water-soluble films for use as the water-soluble material of the water-soluble portion according to the invention are films sold under the name Monosol M8630 or M8720 distributed by MonoSol LLC. Other suitable films include films with the

Description Solublon® PT, Solublon® KA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.

Preferred water-soluble materials are characterized in that they

Hydroxypropylmethyl cellulose (HPMC), which have a degree of substitution (average number of methoxy groups per anhydroglucose unit of cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of

Hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

Polyvinylpyrrolidones, referred to as PVP for short, are produced by radical polymerization of 1-vinylpyrrolidone. Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [0-CH ₂ -CH ₂ ] n-0H which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems with ethylene glycol as the starting molecule. They usually have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxyl end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies in

Dependence on its provenance. The use of gelatin as a water soluble

Envelope material is particularly widespread in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

In the context of the present invention, preference is given to water-soluble materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof. Starch is a homoglycan, with the glucose units linked a-glycosidically. Starch is made up of two components of different molecular weights (MW): approx. 20 to 30% straight-chain amylose (MW approx. 50,000 to 150,000 g / mol) and 70 to 80% branched-chain amylopectin (MW approx. 300,000 to 2,000,000 g / mol). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6 binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which can be obtained from polymer-analogous reactions from starch are also suitable for the production of water-soluble containers in the context of the present invention. Such chemically modified starches include, for example, products

Esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.

Pure cellulose has the formal gross composition (C6H10O5) and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molar masses of 50,000 to 500,000 g / mol. As

Cellulose-based disintegrants can also be used in the context of the present invention, cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The water-soluble material can have other additives. This is it

for example plasticizers, such as dipropylene glycol, ethylene glycol or diethylene glycol, water or disintegrating agents.

Polyvinyl alcohol is particularly preferably used as the water-soluble material. On the one hand, this is easy to process and inexpensive to maintain. In addition, it is particularly soluble in water and thus enables the container to be used in a variety of ways. It is preferred according to the invention if at least one bittering agent is contained in the water-soluble material to increase product safety.

Preferred bittering agents have a bitter value of at least 1,000, preferably at least 10,000, particularly preferably at least 200,000. The standardized procedure described in the European Pharmacopoeia (5th edition Grundwerk, Stuttgart 2005, Volume 1 General Part Monograph Groups, 2.8.15 Bitter Value p. 278) is used to determine the bitter value. An aqueous solution of quinine hydrochloride, whose bitter value is fixed at 200,000, serves as a comparison. This means that 1 gram of quinine hydrochloride makes 200 liters of water bitter. The inter-individual taste differences in the organoleptic examination of bitterness are compensated by a correction factor.

Very particularly preferred bittering agents are selected from denatonium benzoate, glycosides, isoprenoids, alkaloids, amino acids and mixtures thereof, particularly preferred

Denatonium benzoate.

Glycosides are organic compounds of the general structure R-O-Z, in which an alcohol (R-OH) is linked to a sugar part (Z) via a glycosidic bond.

Suitable glycosides are, for example, flavonoids such as quercetin or naringin or iridoid, such as aucubin and in particular secoiridoid, such as amarogentin, dihydrofoliamentin, gentiopicroside, gentiopikrin, swertiamarin, sweroside, gentioflavoside, centauroside, methiafolin, harpaguranginin and centapurosinin and cent.

Isoprenoids are compounds that are formally derived from isoprene. Examples are in particular terpenes and terpenoids.

Suitable isoprenoids include, for example, sequiterpene lactones such as absinthin, artabsin, cnicin, lactucin, lactucopikrin or salonitenolide, monoterpene ketones (thujones) such as

for example a-thujone or ß-thujone, tetranortriterpenes (limonoids) such as desoxylimones, deoxylimonic acid, limonin, ichangin, iso-obacunonic acid, obacunon, obacunonic acid, nomilin or nomilic acid, terpenes such as marrubin, premarrubin, carnosol or quinosol, carnosol.

Alkaloids refer to naturally occurring, chemically heterogeneous, mostly alkaline, nitrogen-containing organic compounds of secondary metabolism that act on the animal or human organism.

Suitable alkaloids are, for example, quinine hydrochloride, quinine hydrogen sulfate,

Quinine dihydrochloride, quinine sulfate, columbine and caffeine. Suitable amino acids include, for example, threonine, methionine, phenylalanine, tryptophan, arginine, histidine, valine and aspartic acid.

Particularly preferred bitter substances are quinine sulfate (bitter value = 10,000), naringin (bitter value = 10,000), sucrose octaacetate (bitter value = 100,000), quinine hydrochloride, denatonium benzoate (bitter value> 100,000,000) and mixtures thereof, very particularly preferred

Denatonium benzoate (eg available as Bitrex ^® ).

Based on its total weight, the water-soluble material preferably contains bittering agents (particularly preferably denatonium benzoate) in a total amount of at most 1 part by weight of bitter substance to 250 parts by weight of viscoelastic, solid composition (1: 250), particularly preferably at most 1: 500, very particularly preferably at most 1: 1000.

It is preferred to use the composition for washing textiles, in particular for removing stains based on constituents and residues of deodorants, rust, berries, tea and red wine.

As already mentioned, the soiling with the composition according to the invention can be pretreated for the actual washing process and / or initially a surfactant-containing liquor is provided as a washing solution which contains the multicomponent detergent according to the invention and which is then brought into contact with the textile to be cleaned.

Processes for cleaning textiles are generally distinguished by the fact that, in several process steps, various cleaning-active substances are applied to the items to be cleaned and washed off after the exposure time, or that the items to be cleaned are treated in some other way with a detergent or a solution of the composition.

In the washing processes described, temperatures of 60 ° C. or less, for example 40 ° C. or less, are used in various embodiments of the invention. These temperature specifications relate to the temperatures used in the washing steps.

It is further preferred to carry out the method according to the invention in a washing machine. It has been found to be particularly effective and therefore preferred if the said composition is metered into the drum of a washing machine.

All described herein in connection with the detergents of the invention

Embodiments, in particular with regard to the specification of the ingredients, are equally applicable to the methods and uses described and vice versa. Examples

The following liquid detergents were produced:

¹ catechol compound of the formula (I) according to the invention with R ¹ and R ² equal to n-propyl, prepared using n-propylamine analogously to the specification of Example 2 of WO 2016/074936 A1.

When the formulation E1 according to the invention was stored at 25 ° C., no discoloration of the composition occurred over a period of 4 weeks.

Claims

Patent claims

1. Detergent, in particular a multi-component detergent, preferably with 2 to 6

Chambers, particularly preferably 2 to 4 chambers, which

at least one catechol compound of the formula (I)

wherein

X represents a sulfone group -SO2R ¹ or an amide group -C-NH-R ² ,

II

O

Y ¹ and Y ² stand for a hydrogen atom, for a sulfone group -SO2R ³ or

for an amide group -

R ¹ and R ³ independently of one another represent a group -NR ^a ,

R ² and R ⁴ each independently represent a hydrocarbon radical having 1 to 20 carbon atoms, which is optionally substituted by at least one radical selected from hydroxy, carboxyl, (Ci-C4) alkoxy, (Ci-C4) alkoxy (CH2CH20 ) _n -, -NR ^' R ^“ or -N ⁺ RR ^" R ^" A-, and n = 1 to 10, R ^' , R ^" and R ^" independently of one another represent H or a straight-chain or branched-chain aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2 carbon atoms and A for stand an anion;

at least one tinting dye that is substantially free of transition metal ions;

at least one surfactant, preferably in a total amount of 2 to 70% by weight,

in particular from 10 to 65% by weight, particularly preferably from 15 to 60% by weight;

optionally other active substances; and

Water from 1 to 50% by weight, preferably 2 to 30% by weight, particularly preferably 3 to 25% by weight, very particularly preferably 5 to 25% by weight, in particular 5 to 35% by weight, preferably 5 to 30% by weight. %, particularly preferably 5 to 25% by weight, very particularly preferably 8 to 15% by weight, based on the total weight of the detergent, or consists of, wherein

the detergent is preferably essentially free of transition metal ions.

2. Detergent according to claim 1, characterized in that when X is selected from said sulfone group according to formula (I), Y ^{1 is selected} from said sulfone group and Y ^{2 represents} a hydrogen atom.

3. Detergent according to one of the preceding claims, characterized in that when X is selected according to formula (I) from said amide group, Y ^{1 represents} a hydrogen atom and Y ^{2 is selected} from said amide group.

4. Liquid multi-component detergent according to claim 3, characterized in that the catechol compound of the formula (I) is selected from at least one catechol compound of the formula (Ia)

wherein

Are carbon atoms, which is optionally substituted with at least one radical selected from (Ci-C4) alkoxy, (Ci-C4) alkoxy (CH2CH20) _n -, -NR R ^" , -N ⁺ R ^' R ^" R ^"' A, and n = 1 to 10, R ^' , R ^" and R ^" independently of one another represent H or a straight-chain or branched-chain aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2 carbon atoms and A- are an anion.

5. Detergent according to one of the preceding claims, characterized in that according to formula (I) or according to formula (la) the radicals R ² and R ⁴ independently of one another for an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a

Hydroxyalkyloxyalkyl group, (N-hydroxyethyl) aminoethyl, (N-methoxyethyl) aminoethyl or (N-ethoxyethyl) aminoethyl, or an aromatic group.

6. Detergent according to one of the preceding claims, characterized in that the radicals R ² and R ^{4 are the} same according to formula (I) or according to formula (la).

7. Detergent according to one of the preceding claims, characterized in that the at least one catechol compound of the formula (I) in 0.2 to 90% by weight, preferably 1 to 85% by weight, in particular 2.5 to 75% by weight , is included.

8. Detergent according to one of the preceding claims, wherein

the detergent has a pH at 20 ° C. of 3 to 11.5, preferably 5 to 9, more preferably 7.

9. Detergent according to one of the preceding claims, characterized in that at least one anionic surfactant and / or at least one nonionic surfactant is contained.

10. Detergent according to one of the preceding claims, characterized in that based on the total weight of the detergent, the at least one tinting dye in a total amount of 0.001 to 10 wt .-%, in particular from 0.01 to 0.1 wt .-%, contain is.

1 1. Detergent according to one of the preceding claims, characterized in that the tinting dyes methine blue and violet dyes, azo dyes, azine dyes, oxazine dyes, and xanthene dyes or dyes based on anthraquinone,

Acridine, benzodifuran, benzodifuranone, carotenoids, coumarin, cyanines, diazahemicyanines, diphenylmethane, formazan, hemicyanides, indigoids, methine, naphthalimides,

Naphthoquinones, nitro and nitroso compounds, oxazines, phthalocyanines, pyrazoles, polyethyleneimines, stilbenes, styrene, triarylmethanes, triphenylmethanes, xanthenes, triphenooxazines, and thiophenes or mixtures thereof.

12. Multi-component detergent according to one of the preceding claims,

characterized in that it is a multi-component detergent, preferably with 2 to 6 compartments, the other components being independent of one another are a liquid composition or a powdery composition or granules.

13. Multi-component detergent according to claim 12, characterized in that the multi-component detergent is in the form of a multi-chamber pouch, in particular with a water-soluble film, particularly preferably based on polyvinyl alcohol.

14. Multi-component detergent according to one of claims 12 or 13, characterized

characterized in that the multi-component detergent contains a bitter substance, preferably the bitter substance is contained in the detergent and / or in the container of the multi-component detergent, in particular in the film.

15. A method of washing textiles, comprising the steps of

Add a detergent according to any one of claims 1 to 11 or one

Multi-component detergent according to one of claims 12 to 14 to a fabric or textile; and

Carrying out a washing procedure, preferably in a washing machine.