WO2020074144A1

WO2020074144A1 - Liquid composition with dihydroxyterephthalic acid diamide compound with a high surfactant quantity

Info

Publication number: WO2020074144A1
Application number: PCT/EP2019/065991
Authority: WO
Inventors: Ulrich Pegelow; Sabine Schuemann; Mareile Job; 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: DE102018217399A1; EP3864119A1; EP3864119B1; PL3864119T3

Abstract

The invention relates to a liquid composition, in particular for washing textiles, containing the following, in each case based on the total weight of the composition: - a total quantity of 20 to 70 wt.% of surfactant and - at least one catechol compound of the formula (I), in which R¹ and R² independently of each other represent a hydrocarbon group with at least three carbon atoms. The invention also relates to a method for treating a substrate, having the steps of (a) providing an aqueous liquor by mixing 0.5 L to 40.0 L of water with 0.5 to 100 g of said composition and (b) bringing a substrate, in particular a textile, into contact with the aqueous liquor produced according to step (a), and to the use of an aqueous liquor which can be obtained by mixing 0.5 L to 40.0 L of water with 0.5 to 100 g of said composition in order to treat textiles, in particular in order to clean textiles.

Description

“Liquid composition with dihydroxy terephthalic acid diamide compound and high

Amount of surfactant "

The invention relates to liquid surfactant compositions with a high surfactant content, which are particularly suitable as laundry detergents.

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, this is made more difficult by the fact that instead of removing the so-called bleachable stains, which are normally at least partially removed by the use of peroxygen-based bleach, on the contrary, often one

Intensification and / or deterioration of the removability of the soiling is brought about, which should not least be due 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 which contain polymerizable substances. The polymerizable substances are mainly polyphenolic dyes, preferably flavonoids, in particular from the class of anthocyanidins or anthocyanins. The soiling can have been caused in particular by food products or beverages containing appropriate dyes. 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.

The German patent application DE 102016214660 A1 and the publication WO 2016/074936 A1 relate to the use of dihydroxy terephthalic acid derivatives in detergents and cleaning agents to improve the washing or cleaning performance.

It has been shown that dihydroxyterephthalic acid diamides are difficult to convert into liquid,

Allow surfactant compositions to be incorporated since the dihydroxy terephthalic acid diamides sediment under storage conditions. This problem exists particularly in compositions with a high surfactant content. Surprisingly, it was found that the use of

Dihydroxy terephthalic acid diamides with special substitution on the amide nitrogen atom can improve the stability of liquid surfactant compositions. The used according to the invention

Dihydroxy terephthalic acid diamides are easily incorporated into liquid surfactant compositions. In addition, the washing performance, especially with regard to bleachable soiling, is significantly increased.

A first object of the present invention is therefore a liquid (and preferred

water-containing) composition, in particular for textile washing, each based on their total weight

- a total of 20 to 70 wt .-% surfactant, and

- at least one catechol compound of the formula (I)

wherein

R ¹ and R ² independently of one another for a hydrocarbon radical having at least 3

Carbon atoms.

"Liquid" as used herein in relation to compositions of the invention includes all compositions flowable under standard conditions (20 ° C, 1013 mbar) in the form of

Liquids and particularly records liquids, flowable gels and pasty

Compositions. In particular, the term also includes non-Newtonian liquids which have a yield point. Granular batches (flowable solids such as powder or

Mixture of granules) are known not to be liquids and are therefore not included.

A chemical compound or its structural unit is organic if its molecular structure contains at least one covalent bond between carbon and hydrogen.

Conversely to the definition “organic”, a chemical compound or its structural unit is inorganic if its molecular structure does not contain a covalent bond between carbon and hydrogen.

Unless explicitly stated otherwise, the average molar masses given for polymeric ingredients in the context of this application are always weight-average molar masses M _w , which can in principle be determined by means of gel permeation chromatography with the aid of an R1 detector, the measurement expediently against an external standard he follows. For the purposes of the invention, a “surfactant-containing liquor” is a liquid that can be obtained by using a surfactant-containing agent diluted with at least one solvent (preferably water)

Preparation for the treatment of a substrate. Fabrics or textiles (such as clothing) can be used as substrates. The preparations according to the invention are preferably used to provide a surfactant-containing liquor in the course of machine cleaning processes, such as those e.g. run by a washing machine for textiles.

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 quantities which relate to at least one constituent always relate to the total amount of this type of constituent which is 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 constituents of the compositions described herein, this information does not refer to the absolute amount of molecules but to the type of constituent. "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.

If number ranges are defined from one number to another number within the scope of the application, the limit values are also included in the range.

If ranges of numbers between a number and another number are defined within the scope of the application, the limit values are not included in the range.

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).

The composition according to the invention contains, based on the weight of the liquid composition according to the invention, surfactant in a total amount of 20 to 70% by weight. It is preferred if surfactant is contained in a total amount of 25 to 65% by weight, preferably 30 to 50% by weight, particularly preferably 35 to 45% by weight.

The group of surfactants includes the nonionic, anionic, cationic and amphoteric surfactants. According to the invention, the liquid

Composition of one or more of the surfactants mentioned. The liquid composition according to the invention particularly preferably comprises at least one anionic surfactant. Anionic surfactant is particularly preferred in a total amount of 15 to 50% by weight, in particular from 20 to 40% by weight, from 15 to 35% by weight, in particular from 20 to 30% by weight, in each case based on the weight of the liquid composition.

The at least one anionic surfactant is preferably selected from the group comprising Cs -is alkylbenzenesulfonates, olefin sulfonates, Ci2-i8 alkanesulfonates, Ci2-i8 ester sulfonates, C 12-18 alkyl sulfates, Ci2-18 alkenyl sulfates, Ci2-i8- Fatty alcohol ether sulfates and mixtures thereof. It has been shown that these sulfonate and sulfate surfactants are particularly suitable for producing stable liquid compositions with a flow limit. Liquid compositions which comprise C9-Ci3-alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant have particularly good, dispersing properties. The surfactants of the sulfonate type are preferably C9-Ci3-alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from Ci2-Ci8 monoolefins having an end or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.

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 in particular the sodium salts of the sulfuric acid semi-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, are secondary Alcohols of these chain lengths 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 C9-11 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 for a linear, unsubstituted alkyl radical, particularly preferably for 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 are preferred. Particularly preferred radicals R ^{1 of} the formula (A-1) are derived from Fatty alcohols with 12 to 18 carbon atoms, for example coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or 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 nth 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 liquid composition contain a mixture of sulfonate and sulfate surfactants. In a particularly preferred embodiment, the composition contains at least one C9-13-alkylbenzenesulfonate and optionally additionally at least one C 12-18-fatty alcohol ether sulfate as the anionic surfactant.

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

+

Y

(A-3),

in the

R ^' and R ^" independently of one another are 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.

The composition can also contain soaps as an anionic surfactant. 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 from natural

Fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, derived

Soap mixtures.

The anionic surfactants 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 before, wherein said ammonium ion is 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 liquid composition can (preferably together with at least one anionic surfactant) also have at least one nonionic surfactant.

If at least one anionic surfactant and at least one nonionic surfactant are present in the composition according to the invention, it is preferred if the weight ratio of anionic to nonionic surfactant is in the weight ratio range from 1 to 1 to 3 to 1, in particular from 1.5 to 1 to 2.5 to 1 , lies.

The nonionic surfactant comprises 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 liquid composition according to the invention, nonionic surfactant in a total amount of 5 to 40% by weight, in particular 7 to 35% by weight, more preferably 5 to 20% by weight, particularly preferably from 10 to 15% 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 linearly 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. The 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 5 EO or 7 EO and mixtures of these. The specified

Degrees of ethoxylation are statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a restricted one

Homolog distribution on (narrow ranks 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 C16-C18 Fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. The washing, cleaning, aftertreatment or auxiliary washing agent 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 liquid 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. Das

Agents according to the invention can contain mixtures of nonionic surfactants which have 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)

(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 particularly preferably contain water. It is very particularly preferred if, in the composition, based on its total weight, water in a total amount of 1 to 50% by weight, more preferably 2 to 30% by weight, particularly preferably 3 to 25% by weight, very particularly preferably 5 up to 25% by weight, in particular from 5 and 45% by weight, more preferably from 10 and 40% by weight, more preferably from 5 to 30% by weight, very particularly preferably from 8 to 25% by weight.

The liquid composition preferably additionally contains at least one organic solvent. Suitable organic 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 methyl ether, propylene glycol methyl methyl ether, propylene glycol methyl methyl ether, propylene glycol methyl methyl ether, propylene glycol methyl methyl ether, propylene glycol methyl methyl ether, propylene glycol methyl methyl propylene glycol,

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, methyl propanediol, 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 solvents.

Organic solvents are advantageously present in a total amount of 5% by weight to 20% by weight, particularly preferably 10% by weight to 15% by weight, based in each case on the total weight of the composition.

The composition according to the invention additionally contains at least one catechol compound of the formula (I) in addition to the said amount of surfactant. The catechol compounds according to formula (I) can be provided analogously to the synthesis instructions according to example 2 of WO 2016/074936 A1.

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 0.05 to 10.0% by weight, more preferably 0.1 to 4% by weight, more preferably of 0.2 to 2.0 wt .-%, very particularly preferably from 0.3 to 3.0 wt .-%, is contained.

The effect according to the invention is particularly evident when the at least one catechol compound of the formula (I) of the liquid composition is selected one or more Catechol compounds of formula (I) in which R ¹ and R ² independently of one another represent a carbon radical having 3 to 20 carbon atoms, preferably having 3 to 10 carbon atoms, particularly preferably having 3 to 6 carbon atoms. Particularly preferred radicals R ¹ and R ^{2 of} the formula (I) independently of one another stand for a linear or branched C3-C ₂ o-alkyl group, a linear or branched C3-Cio-alkyl group, a linear or branched C3-C6-alkyl group, a linear or branched _{C3-C2o-alkenyl} group, a linear or branched C3-Cio-alkenyl group, a linear or branched C3-C6-alkenyl, a cyclic C3-Cio-alkyl group, a propyl group, a phenyl group or a benzyl group.

R ¹ and R ^{2 of} the formula (I) very particularly preferably independently of one another stand for n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl , tert-pentyl, 2,2-dimethylpropyl, 1, 2-dimethylpropyl, cyclopentyl, n-hexyl, iso-hexyl, neo-hexyl, cyclohexyl, allyl, but-2-enyl or benzyl. Again, n-propyl and iso-propyl are the most preferred groups of the radicals R ¹ and R ² .

The radicals R ¹ and R ² can be different or the same. A symmetrical substitution has proven to be particularly advantageous for the synthesis of the catechol compounds of the formula (I). The radicals R ¹ and R ² according to formula (I) are therefore very particularly preferably the same.

The liquid 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, bleaching agents, 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 ingredients.

It is preferred if the liquid 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 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 to be understood as substitutions of one amino acid for another amino acid. According to the invention, such substitutions are specified in the internationally customary single-letter code, indicating the positions in which the exchange takes place, optionally combined with the relevant amino acids. "Exchange in position 320" means, for example, that a variant in the position that is in the sequence of a reference protein Position 320 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.

Basically, are those according to the invention designated by the present application

Amino acid exchanges are not limited to being 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. According to the invention, each of the enzymes from class EC 3.4 is included (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) are characterized in that they have two further amino acid residues in the active center in addition to said serine with histidine and aspartame. 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 carried out 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 alkaline protease type from Bacillus lentus DSM 5483 or a protease sufficiently similar to this (based on the

Sequence identity), which has several of these changes in combination, particularly suitable for use in and in the liquid surfactant composition according to the invention

is advantageously improved stabilized. Advantages of using this protease thus arise in particular 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 (cf. for example Altschul, SF, Gish, W., Miller, W., Myers, EW & Lipman, DJ (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 by the fact that similar sequences of nucleotides or amino acids in the nucleic acid or

Amino acid sequences can be assigned to each other. A tabular assignment of the relevant positions is called alignment. Another algorithm available in the prior art is the FASTA algorithm. Sequence comparisons (alignments), especially multiple

Sequence comparisons are made with 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 patent application, all sequence comparisons (alignments) were created with the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the specified standard parameters, whose AlignX module for the 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 expressed in percent identity, that is, the proportion of identical

Nucleotides or amino acid residues are indicated at the same or in an alignment corresponding positions. The broader concept of homology also includes conserved amino acid exchanges in amino acid sequences, that is, amino acids with similar chemical activity, since these usually 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.

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

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

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

Protect inactivation.

Compositions according to the invention can be added to the enzymes obtained in any form established according to the prior art. These include in particular the solid preparations obtained by granulation, extrusion or lyophilization, advantageously as concentrated as possible, low in water and / or mixed with stabilizers. In an alternative administration 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 Core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. In layered layers can additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, are additionally applied. 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 liquid 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 offered by Novozymes under the Celluzyme® trade name. 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®. Cellulases which are available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch® and which are based at least in part on the 20 kD EG from melanocarpus can also be used, for example. 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 from that

Danisco / Genencor is available 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 the international patent application WO 98/12307, cellulases from Melanocarpus, in particular Melanocarpus albomyces, which are disclosed in the international patent application WO 97/14804, cellulases of the EGIII type from Trichoderma reesei, which in the European

Patent application EP 1 305 432 are disclosed or variants obtainable therefrom, in particular those which are disclosed in European patent applications EP 1240525 and EP 1305432, and cellulases which are disclosed in 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 patent application.

Liquid 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 that have a homology of over 80% (increasingly preferred from 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 known from international patent application WO 97/14804. 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 genetically produced

Trichoderma reseei transformants are produced. Cellulases which have a homology of more than 80% (increasingly preferred more than 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90) are also usable in the context of the present invention %, 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%) for 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 which produces reducing sugar in an amount corresponding to 1 nmol glucose per second), in particular from 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 liquid 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%) for this purpose has to use at least one further second cellulase different from the first cellulase.

It is preferred according to the invention if the liquid 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 liquid 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 type Thermomyces lanuginosus or is derived by mutagenesis from the aforementioned lipases which are naturally present in Thermomyces lanuginosus.

In this context, naturally present means that the lipase is a separate enzyme of the microorganism. The lipase can therefore be found in the microorganism of one

Nucleic acid sequence are expressed, which 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 to this, a lipase that is not naturally present in the microorganism or the nucleic acid sequence coding for it would have been 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 species names within the respective genus.

Preferred lipases according to the invention are the lipase enzymes available from Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE® and Lipase F® (also Lipase JV®). 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%) for the wild-type lipase from the strain DSM 4109 Thermomyces lanuginosus is identical. 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 are preferably used according to the invention, which are selected from at least one lipase enzyme according to at least one of claims 1 to 13 of publication 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 again preferred if, starting from the wild-type lipase from strain DSM 4109, at least one of the following amino acid exchanges is present in positions D96L, T213R and / or N233R, particularly preferably T213R and N233R.

A most preferred lipase is commercially available under the trade name Lipex®

Company Novozymes (Denmark) and can advantageously be used in the cleaning compositions according to the invention. The Lipase Lipex® 100 L (ex Novozymes A / S, Denmark) is particularly preferred. Preferred compositions are characterized in that, based on the total weight of the composition, said lipase enzyme from Lipex®

100 L in a total amount of 0.01 to 1.0% by weight, in particular 0.02 to 0.1% by weight, is contained.

The liquid compositions according to the invention can additionally contain at least one mannanase as enzyme. One contained in the composition according to the invention (in particular in a washing and cleaning agent for textiles preferred according to the invention)

As part of its mannanase activity, mannanase catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans and

Galactoglucomannans. 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 from the company under catalog number I-AZGMA

Megazyme (http://www.megazyme.com). 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, based on the

Total weight of the mannanase composition in a total amount of 0.01 to 1.0% by weight, in particular 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. Can also be used within the scope of the invention

Mannanase polypeptides of the fungi Humicola or Scytalidium, in particular the species Humicola insolens or Scytalidium thermophilum.

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 that 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 which composition according to the invention is included.

Particularly preferably, the liquid surfactant composition according to the invention contains, in addition to the preferred protease of the alkaline protease type from Bacillus Ientus DSM 5483 or in addition to the 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 . a-Amylases (EC 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 which hydrolyzes 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. An alternative activity determination method is the so-called DNS method, for example in the

Application WO 02/10356 A2 is described. Then the oligosaccharides, disaccharides and glucose units released by the enzyme during the hydrolysis of starch are detected by oxidation of the reducing ends with 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 using different methods, whereby the respective conversion factors can vary depending on the enzyme and thus using one

Standards need to be set. Approximately one can calculate that 1 KNU approx.

Corresponds to 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 according to the invention of the liquid according to the invention

Surfactant compositions 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. Based on these natural enzymes, there is still an almost unmanageable abundance of variants that have been derived via mutagenesis and depending on

Have specific advantages.

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, 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 ones

Amino acid exchange in 10 different positions on the a-amylases from two different microorganisms and claims them for all amylases with a homology of at least 96% identity to them. WO 01/66712 A2, finally, designates 31 different amino acid positions, some of which are identical to those mentioned above, in one of the two in the application

WO 00/60060 A2 called a-amylases have been mutated.

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 liquid surfactant 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 , which has a higher activity at temperatures between 10 and 20 ° C than the amylase with the trade name "Stainzyme 12 L" from Novozymes.

Preferred liquid compositions according to the invention contain a-amylase in one

Total amount from 0.01 to 1.0% by weight, in particular from 0.02 to 0.1% by weight.

It is preferred if the liquid composition contains at least one optical brightener. The optical brighteners are preferred from the substance classes of distyrylbiphenyls, the stilbenes, the ^{^{diamino-2,2-stilbenedisulfonic}} acids 4.4, the 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- Thiophendiyl) bis [5-1, 1-dimethylethyl) benzoxazole (for example available as Tinopal® SFP from BASF SE) and / or 2, 5-bis (benzoxazol-2-yl) thiophene. are selected, incorporate.

According to the invention, the liquid composition can further comprise builders. Polymeric polycarboxylates, for example, are 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 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 being 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, especially glutamic acid-N, N-diacetic acid (GLDA) and methylglycine-N, N-diacetic acid (MGDA), as well as 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 are preferably a

Have molecular weights 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. Soluble builders, such as

Acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol are used.

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. In addition, the liquid compositions according to the invention can additionally

Contain components that positively influence the oil and fat washability from textiles, so-called soil release agents. For this purpose, the liquid composition preferably additionally contains at least one dirt-repellent polymer (also known as SRP). The effect of SRP becomes particularly clear if 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 from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the non-ionic

Cellulose ethers, as well as 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 of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. These are commercially available, for example, under the trade name Texcare ^® .

Anti-redeposition agents are particularly selected from copolymers based on

Polyethyleneimine, based on polyvinyl acetate and based on polyethylene glycol.

The liquid composition can preferably also contain at least one polymer that inhibits color transfer. Such color transfer inhibitors are preferably present in amounts of 0.1% by weight to 2% by weight, in particular 0.1% by weight to 1% by weight, which in a preferred embodiment of the invention comprise polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N - Oxide or copolymers of these are.

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 according to the invention.

It is preferred that the color transfer inhibitor is a polymer or copolymer of cyclic amines such as vinyl pyrrolidone and / or vinyl imidazole. Polymers useful as a color transfer inhibitor include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol-modified copolymers of vinylpyridone and vinylpyridone as well as mixtures thereof. Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) are particularly preferred as color transfer inhibitors used. 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 available from BASF as Sokalan® HP 50 or Sokalan® HP 53.

The copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000. 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 vinyl pyrrolidone and vinyl imidazole, which are available, for example, from BASF under the name Sokalan® HP 66.

Preferred liquid compositions of the invention additionally contain at least one

Bluing agent. A “bluing agent” is a blue to violet dye that dyes blue to violet to increase the whiteness of white textiles. A method of determining the presence of a bluing agent is the colorimetric measurement of the Lab values, as described in the

Document WO 2014/089386 A1 on page 7, line 20 to page 9, line 6 is described, to which express reference is made. A bluing agent is present, for example, if the blue to violet dye produces a DE ^* value on the textile according to the aforementioned test method of at least 2.0 DE ^* units, preferably at least 3.0 DE ^* units, particularly preferably at least 4.0 DE ^* units .

It is preferred according to the invention if the blueing agent in solution or dispersion (ethanol, at 20 ° C.) has an absorption maximum in a wavelength range from 510 and 640 nm, particularly preferably from 530 to 620 nm.

The bluing agent is preferably a dye whose maximum extinction coefficient in a wavelength range from 400 to 750 nm is preferably greater than 1,000 L / mol / cm.

In an aqueous solution which has a pH range from 7 to 11, the bluing agent is preferably not charged or has an anionic charge, and the dye is particularly preferably nonionic.

The bluing agent is preferably a compound of the following general formula BL-1:

F - L - CO2M (BL-1) in which F stands for the monoazo dye. The extinction coefficient mentioned above relates to this dye F in the compound F-H in an ethanolic solution.

L according to formula BL-1 is an organic group which connects the monoazo dye F with the carboxyl group CO2M. This connecting group L preferably has a molecular weight in the range from 14 to 1000 g / mol, in particular from 14 to 600 g / mol particularly preferably from 28 to 300 g / mol. The group L preferably comprises essentially exclusively carbon and hydrogen and optionally also oxygen and / or nitrogen.

L particularly preferably represents a C-i-20-alkyl group which may have ether and / or ester and / or amide groups as branching sites. The alkyl chain can be substituted according to the invention. Possible substituents are -OH, -CN, -NO2, -SO2CH3, -CL, -BR.

In the aforementioned general formula BL-1, M stands for any counter ion, usually hydrogen, sodium or potassium.

In a preferred embodiment, the bluing agent comprises the following general formula BL-2:

in which each independently

R is a C _2-12 alkyl radical _{1- 20,} or C, which optionally contains ether and / or ester and / or amide groups as the branching points and the further Aklylkette

optionally substituted, for example, with -OH, -CN, NO ₂ , -SO ₂ CH3, -CL, -BR;

R ¹ and R ^{2 are} each independently selected and represent, for example, hydrogen; they are preferably each independently selected from electron-withdrawing groups such as, for example, -CN, -NO ₂ , -SO ₂ CH3, -CL, -BR;

Z is selected from an electron-withdrawing group and is preferably selected from cyano-, sulfamoyl, N: N-diethylsulfamoyl, N-ethylsulfamoyl, trifluoromethyl, ethylsulfonyl, nitrosylfonyl, N-methylsulfamoyl, chloro and bromo; in particular Z is a nitro group;

Y is hydrogen, a short (C-) alkyl radical, halogen, -NHCOR, preferably hydrogen, -CH3 or -CI;

X is hydrogen, a short (C _1-4 ) alkoxy chain or halogen, especially hydrogen, methoxy, ethoxy or chloride.

Examples of short-chain alkyl and / or alkoxy radicals are methyl, ethyl, n-propyl, n-butyl, ethoxy and methoxy. Examples of the optionally substituted, short-chain alkyl radicals, which are represented by R in the general formula 2, are β-hydroxyethyl, β-cyanoethyl, β- (methoxy or ethoxy) ethyl, g-methoxypropyl, benzyl or β-phenylethyl, ß-methoxycarbonyl-ethyl or ß-acetoxyethyl. The bluing agent according to the invention can have, for example, the following general formula BL-3:

in which Z, R, X, Y and L represent the same radicals as others already explained above for formula 1 and formula 2.

Particularly preferred bluing agents are Basic Violet 10, Liquitint® Violet 200, Liquitint Violet CT or compounds of the following formula:

wherein each R ¹ and R ^{2 is} independently selected from R, - [(CH2CR'HO) x (CH2CR "HO) _y H] and mixtures thereof, wherein each R is independently selected from H, linear or branched Ci-C ₄ -alkyl groups, benzyl and mixtures thereof; each R 'is independently selected from H, CH ₂ 0 (CH ₂ CH ₂ 0) zH and mixtures thereof and each R "is independently selected from H, CFb, CH ₂ 0 ( CH ₂ CH ₂ 0) zH and mixtures thereof; where x + y <5;y> 1 and z = 0 to 5.

In particular low-water, liquid compositions according to the invention of the first

Subject of the invention can be in pre-portioned form (portion). In this

As an embodiment, the composition according to the invention is present in a container made of water-soluble or water-dispersible material.

If the composition according to the invention is packaged in a water-soluble or water-dispersible material, it is preferred that the water content is between 5 and 20% by weight, based on the total agent.

The container made of water-soluble material comprises at least one chamber, preferably at least two spatially separated chambers (multi-chamber pouch). The water-soluble material forms walls of the chamber and thereby envelops at least one according to the invention

Composition.

The water solubility of the material can be measured using a square frame

(Edge length on the inside: 20 mm) fixed square film of the said material (film: 22 x 22 mm with a thickness of 76 pm) can be determined according to the following measurement protocol. Said Framed film is in 800 mL of distilled water at 20 ° C in a 1 liter

Beaker with a circular bottom surface (Schott, Mainz, beaker 1000 mL, low form) immersed so that the surface of the clamped film is at right angles to the bottom surface of the beaker, the top 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 lower edge of the frame runs along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is arranged above the center of the radius of the beaker base. 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 walls are preferably made of a water-soluble film. According to the invention, this film can preferably have a thickness of at most 150 pm (particularly preferably of at most 120 pm). Preferred walls are accordingly made of a water-soluble film and have a thickness of at most 150 pm (particularly preferably of at most 120 pm, very particularly preferably of at most 90 pm).

Such portions can be made by either vertical form fill sealing (VFFS) or thermoforming. Walls of at least one chamber are particularly preferably created by sealing at least one film of water-soluble material, in particular by sealing in the context of a form-fill-seal process.

The thermoforming process generally includes forming a first layer of a water-soluble sheet material to form at least one bulge for receiving at least one composition of the invention therein, filling the

Composition in the respective bulge, covering the bulges filled with the composition with a second layer of a water-soluble film material and sealing the first and second layers together at least around the bulges.

The water-soluble material preferably contains at least one water-soluble polymer. In addition, the water-soluble material preferably contains a water-soluble film material selected from polymers or polymer mixtures. The sheath can be formed from one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, can be the same or different.

It is preferred that the water soluble material is a polyvinyl alcohol or a

Contains polyvinyl alcohol copolymer.

Suitable water-soluble films as water-soluble material are preferably based on a

Polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in each case in the range from 10,000 to 1,000,000 gmol ¹ , preferably from 20,000 to 500,000 gmol ^-1 , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 . Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct route of synthesis is not possible. The same applies to polyvinyl alcohol copolymers which are produced from polyvinyl acetate copolymers accordingly.

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

- CH ₂ - CH— CH ₂ - CH—

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

contain.

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 polymer, the degree of hydrolysis, the saponification number and the 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. Water solubility can be achieved by post-treatment with aldehydes (acetalization)

Reduce complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but leave water vapor

step 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, of a polyvinyl alcohol, the 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 changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). 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. PVAL films are largely impenetrable for 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.

The film material suitable as a water-soluble material can additionally contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, Polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.

Foil material used as the water-soluble material of the walls has a preferred thickness in a range from 65 to 180 gm, in particular from 70 to 150 gm, more preferably 75 to 120 gm.

In the said water-soluble material the walls of the portion is used to increase the

Product safety preferably incorporates a bittering agent. Corresponding embodiments of the water-soluble material with bittering agent are described in the publications EP-B1-2 885 220 and EP-B1-2 885 221. A preferred bittering agent is denatonium benzoate.

Suitable water-soluble films for use as the water-soluble material of the wall of the water-soluble portion according to the invention are films which are sold under the name Monosol M8630 by MonoSol LLC. Other suitable films include films with the designation Solublon® PT, Solublon® KA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray, or HiSelon SH2312 from Nippon Gohsei.

A second subject of the invention is a method for substrate treatment, in particular textile treatment, comprising the process steps

(a) providing an aqueous liquor by mixing 0.5 L to 40.0 L water with 0.5 to 100 g of a composition of the first subject matter, and

(b) bringing a substrate, in particular a textile, into contact with the substrate according to (a)

manufactured aqueous liquor.

As already mentioned, it can be soiled in the context of a textile wash

the inventive composition of the first subject of the invention are pretreated before step (a).

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

It is preferred in step (a) to provide an aqueous liquor by mixing 5.0 to 20.0 L of water with 5 to 75 g (in particular 10 to 55 g) of a composition of the first subject of the invention.

In the washing processes described, in various embodiments of the invention in step (b) the aqueous liquor is set to temperatures of 60 ° C. or less, for example 40 ° C. or less.

It is further preferred to carry out the method according to the invention in a washing machine. It has proven particularly effective and therefore preferred if the said liquid composition of the first subject of the invention is metered into the metering device of a washing machine or the drum of a washing machine. In the embodiment as a portion, it is preferred to dose the portion into the drum of a washing machine.

A third subject of the invention is the use of an aqueous liquor, obtainable by mixing 0.5 L to 40.0 L of water with 0.5 to 100 g of a liquid composition of the first subject of the invention (in particular according to one of items 1 to 22 (vide infra)), for

Textile treatment, in particular for cleaning textiles.

It is preferred to use an aqueous liquor obtainable by mixing 5.0 to 20.0 L of water with 5 to 75 g (in particular 10 to 55 g) of a composition of the first subject of the invention.

All of the embodiments described herein in connection with the liquid compositions of the invention, particularly with regard to the specification of the ingredients, are

equally applicable to the methods and uses described and vice versa.

The following points 1 to 24 can be summarized as (preferred) embodiments of the invention, without restricting the invention thereto:

1. Liquid composition, in particular for textile washing, each based on their total weight

- a total of 20 to 70 wt .-% surfactant, and

- at least one catechol compound of the formula (I)

wherein

Carbon atoms.

2. Liquid composition according to item 1, characterized in that surfactant in one

Total amount of 25 to 65 wt .-%, preferably from 30 to 50 wt .-%, particularly preferably from 35 to 45 wt .-%, is contained.

3. Liquid composition according to one of the preceding points, characterized in that it contains at least one anionic surfactant.

4. Liquid composition according to item 3, characterized in that, based on the weight of the composition, a total amount of anionic surfactant from 15 to 35% by weight, in particular from 20 to 30% by weight, is contained. Liquid composition according to one of items 3 or 4, characterized in that at least one anionic surfactant selected from the group consisting of Cs -is-alkylbenzenesulfonates, olefin sulfonates, Ci2-i8-alkanesulfonates, Ci2-i8-ester sulfonates, C12-18-alkylsulfates , Ci2-18 alkenyl sulfates, Ci2-i8 fatty alcohol ether sulfates and mixtures thereof.

Liquid composition according to one of items 3 to 5, characterized in that it contains at least one anionic surfactant of the formula (A-3),

+

Y

(A-3),

in the

Liquid composition according to one of the preceding points, characterized in that it contains at least one nonionic surfactant.

Liquid composition according to item 7, characterized in that, based on the weight of the composition, a total amount of nonionic surfactant of 5 to 20% by weight, in particular 10 to 15% by weight, is contained.

Liquid composition according to one of items 7 or 8, characterized in that at least one nonionic surfactant according to formula (N-1) is contained

R ³ -0- (XO) mH, (N-1) in the

Liquid composition according to one of items 1 to 9, characterized in that the weight ratio of anionic to nonionic surfactant is in the weight ratio range from 1 to 1 to 3 to 1, in particular from 1.5 to 1 to 2.5 to 1.

Liquid composition according to one of the preceding points, characterized in that water (preferably in a total amount of 5 and 45% by weight, more preferably 10 and 40% by weight, more preferably 5 to 30% by weight, very particularly preferably of 8 to 25% by weight) is contained.

Liquid composition according to one of the preceding points, characterized in that at least one organic solvent (in particular in a total amount from 5% by weight to 20% by weight, particularly preferably from 10% by weight to 15% by weight) in each case based on the total weight of the composition) is included. Liquid composition according to one of the preceding points, characterized in that, according to formula (I), R ¹ and R ² independently of one another represent a carbon radical having 3 to 20 carbon atoms, preferably having 3 to 10 carbon atoms, particularly preferably having 3 to 6 carbon atoms.

Liquid composition according to one of the preceding points, characterized in that according to formula (I) R ¹ and R ² independently of one another for a linear or branched C3-C2o-alkyl group, a linear or branched C3-Cio-alkyl group, a linear or branched C3 -C6-alkyl group, a linear or branched C3-C ₂ o-alkenyl group, a linear or branched C3-Cio-alkenyl group, a linear or branched C3-C6-alkenyl group, a cyclic C3-Cio-alkyl group, a propyl group, a phenyl group or a benzyl group. Liquid composition according to one of the preceding points, characterized in that, according to formula (I), R ¹ and R ² independently of one another for n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n -Pentyl, iso-pentyl, neopentyl, tert-pentyl, 2,2-dimethylpropyl, 1, 2-dimethylpropyl, cyclopentyl, n-hexyl, iso-hexyl, neo-hexyl, cyclohexyl, allyl, but-2-enyl or benzyl .

Liquid composition according to one of the preceding points, characterized in that according to formula (I) R ¹ and R ^{2 are the} same.

Liquid composition according to one of the preceding points, characterized in that, based on the total weight of the composition, the at least one

Catechol compound according to formula (I) in a total amount of 0.05 to 10.0% by weight, more preferably 0.1 to 4% by weight, more preferably 0.2 to 2.0% by weight, very particularly preferably from 0.3 to 3.0% by weight.

Liquid composition according to one of the preceding points, characterized in that at least one enzyme, in particular at least one lipase, is additionally present. Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one polymer which inhibits color transfer.

Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one dirt-repellent polymer (SRP).

Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one optical brightener.

Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one bluing agent.

Process for substrate treatment comprising the process steps

(a) providing an aqueous liquor by mixing 0.5 L to 40.0 L water with 0.5 to 100 g of a liquid composition according to any one of items 1 to 22, and

manufactured aqueous liquor.

Use of an aqueous liquor, obtainable by mixing 0.5 L to 40.0 L water with 0.5 to 100 g of a liquid composition according to one of items 1 to 22, for

Textile treatment, in particular for cleaning textiles. Examples

The following compositions in Table 1 were prepared by mixing the components in a conventional manner.

Table 1: Liquid detergent

¹ 2,3-dihydroxy-N, N'-di (n-propyl) terephthalamide as the catechol compound of the formula (I) according to the invention with R ¹ and R ² being n-propyl, prepared using n-propylamine analogously to the procedure of the example 2 of WO 2016/074936 A1.

² catechol compound 2,3-dihydroxy-N, N'-diethylterephthalamide according to Example 2 of WO 2016/074936 A1 not according to the invention.

The compositions were then stored at 0 ° C for 8 weeks and then assessed visually. Formula V1 not according to the invention showed a clear one

Sedimentation, whereas the formula E1 according to the invention was stable.

Claims

Patent claims

- a total of 20 to 70 wt .-% surfactant, and

- at least one catechol compound of the formula (I)

wherein

Carbon atoms.

2. Liquid composition according to claim 1, characterized in that surfactant is contained in a total amount of 25 to 65 wt .-%, preferably from 30 to 50 wt .-%, particularly preferably from 35 to 45 wt .-%.

3. Liquid composition according to one of the preceding claims, characterized

characterized in that at least one anionic surfactant is contained.

4. Liquid composition according to claim 3, characterized in that, based on the weight of the composition, a total amount of anionic surfactant from 15 to 35 wt .-%, in particular from 20 to 30 wt .-%, is included.

5. Liquid composition according to one of claims 3 or 4, characterized in that at least one anionic surfactant selected from the group consisting of Cs -is alkylbenzenesulfonates, olefin sulfonates, Ci2-i8 alkanesulfonates, Ci2-i8 ester sulfonates, C12-18 - Alkyl sulfates, Ci2-18-alkenyl sulfates, Ci2-i8 fatty alcohol ether sulfates and mixtures thereof is contained.

6. Liquid composition according to one of the preceding claims, characterized

characterized in that it contains at least one nonionic surfactant.

7. Liquid composition according to claim 6, characterized in that based on the weight of the composition, a total amount of nonionic surfactant from 5 to 20 wt .-%, in particular from 10 to 15 wt .-%, is included.

8. Liquid composition according to one of claims 1 to 7, characterized in that the weight ratio of anionic to nonionic surfactant is in the weight ratio range from 1 to 1 to 3 to 1, in particular from 1.5 to 1 to 2.5 to 1.

9. Liquid composition according to one of the preceding claims, characterized in that water (preferably in a total amount of 5 and 45 wt .-%, more preferably from 10 and 40 wt .-%, more preferably from 5 to 30 wt .-%, very particularly preferably from 8 to 25% by weight) and optionally additionally at least one organic solvent (in particular in a total amount from 5% by weight to 20% by weight, particularly preferably from 10% by weight to 15% by weight) , each based on the total weight of the

Composition) is included.

10. Liquid composition according to one of the preceding claims, characterized

characterized in that according to formula (I) R ¹ and R ² independently of one another for a

Carbon residue with 3 to 20 carbon atoms, preferably with 3 to 10 carbon atoms, particularly preferably with 3 to 6 carbon atoms.

1 1. Liquid composition according to one of the preceding claims, characterized

characterized in that according to formula (I) R ¹ and R ² independently of one another for a linear or branched C3-C ₂ o-alkyl group, a linear or branched C3-Cio-alkyl group, a linear or branched C3-C6-alkyl group, a linear or branched _{C3-C2o-alkenyl} group, a linear or branched C3-Cio-alkenyl group, a linear or branched C3-C6-alkenyl, a cyclic C3-Cio-alkyl group, a propyl group, a phenyl group or a

Benzyl group.

12. Liquid composition according to one of the preceding claims, characterized

characterized in that, according to formula (I), R ¹ and R ² independently of one another are n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, tert-pentyl, 2,2-dimethylpropyl, 1, 2-dimethylpropyl, cyclopentyl, n-hexyl, iso-hexyl, neo-hexyl, cyclohexyl, allyl, but-2-enyl or benzyl.

13. Liquid composition according to one of the preceding claims, characterized

characterized in that according to formula (I) R ¹ and R ^{2 are the} same.

14. Liquid composition according to one of the preceding claims, characterized

characterized in that, based on the total weight of the composition, the at least one catechol compound of the formula (I) in a total amount of 0.05 to 10.0% by weight, more preferably 0.1 to 4% by weight, more preferably 0.2 up to 2.0% by weight, very particularly preferably from 0.3 to 3.0% by weight, is contained.

15. Process for substrate treatment comprising the process steps

(a) providing an aqueous liquor by mixing 0.5 L to 40.0 L water with 0.5 to 100 g of a liquid composition according to any one of claims 1 to 14, and

manufactured aqueous liquor.

16. Use of an aqueous liquor, obtainable by mixing 0.5 L to 40.0 L water with 0.5 to 100 g of a liquid composition according to one of claims 1 to 14, for

Textile treatment, in particular for cleaning textiles.