DE102018217399A1 - Liquid composition with dihydroxy terephthalic acid diamide compound and high amount of surfactant - Google Patents

Abstract

Catechol compounds of the formula (I) in which R a, independently of one another, stand for a hydrocarbon radical having at least 3 carbon atoms, can be easily and stably incorporated into liquid compositions with a surfactant content of 20 to 70% by weight. Concentrated liquid surfactant compositions are obtained which are stable in storage and have excellent detergency.

Description

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, it is aggravated that instead of removing the so-called bleachable stains, which are normally at least partially removed by the use of bleaching agents based on peroxygen, on the contrary, the washing process often leads to an intensification and / or deterioration in the removability of the stain, This should not least be attributed to initiated chemical reactions, which may consist, for example, in the polymerisation 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 in particular have been caused by food products or beverages that contain the corresponding colorants. The soiling can be, in particular, stains from fruits or vegetables or also red wine stains, which in particular contain polyphenolic dyes, especially those from the class of anthocyanidins or anthocyanins.

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 dihydroxy terephthalic acid diamides are difficult to incorporate into liquid surfactant compositions, 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 stability of liquid surfactant compositions can be improved by using dihydroxy terephthalic acid diamides with special substitution on the amide nitrogen atom. The dihydroxy terephthalic acid diamides used according to the invention can easily be incorporated into liquid surfactant compositions. In addition, the washing performance, especially with regard to bleachable soiling, is significantly increased.

• - eine Gesamtmenge von 20 bis 70 Gew.-% Tensid, und
• - mindestens eine Catecholverbindung der Formel (I)
  
  worin R¹ und R² unabhängig voneinander für einen Kohlenwasserstoffrest mit mindestens 3 Kohlenstoffatomen steht.

A first subject of the present invention is therefore a liquid (and preferably water-containing) composition, in particular for textile washing, each based on its 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 represent a hydrocarbon radical having at least 3 carbon atoms.

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

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 molecular weights specified for polymeric ingredients in the context of this application are always weight-average molecular weights M _w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement expediently against an external standard he follows.

For the purposes of the invention, a “surfactant-containing liquor” is a liquid preparation which can be obtained by using a surfactant-containing agent and diluted with at least one solvent (preferably water) 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 components of the compositions described herein, this information does not refer to the absolute amount of molecules but to the nature of the component. "At least one nonionic surfactant" therefore means, for example, one or more different nonionic surfactants, i.e. one or more different types of nonionic surfactants. Together with quantity information, the quantity information relates to the total quantity of the correspondingly designated type of constituent, as already defined above.

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 according to the invention can comprise 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 20 to 40% by weight, 15 to 35% by weight, in particular 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 C _8-18 alkylbenzenesulfonates, olefin sulfonates, C _12-18 alkanesulfonates, C _12-18 estersulfonates, C _12-18 alkyl sulfates, C _12-18 alkenyl sulfates, C. _12-18 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 C ₉ -C ₁₃ alkylbenzenesulfonates and fatty alcohol ether sulfates as the anionic surfactant have particularly good dispersing properties. Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are C ₁₂ -C ₁₈ alkanesulfonates and the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ 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 C ₇ -C ₂₁ 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 -O- (AO) _n ^- SO ₃ ^- X ⁺ (A-1)

In this formula (A-1), R ^{1 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ^{1 of} the formula (A-1) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the Representatives with an even number of carbon atoms 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 from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 20 carbon atoms .

AO in formula (A-1) represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n of the formula (A-1) is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n 2, 3, 4, 5, 6, 7 or 8 is very particularly preferred. X is a monovalent cation or the 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 NH4 ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na Fettalkoholethersulfate mit 12 bis 18 C-Atomen und 2 EO (k = 11 bis 13, n = 2 in Formel A-1). Der angegebenen Ethoxylierungsgrad stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann. Die angegebenen Alkoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoxylate/Ethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE).Particularly preferred detergents contain an alkyl ether sulfate selected from fatty alcohol ether sulfates of the formula A-2

with k = 11 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 C atoms and 2 EO (k = 11 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.

in der
R' und R" unabhängig voneinander H oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 C-Atome enthalten, und Y⁺ ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations (insbesondere Na⁺) bedeuten.It is very particularly preferred if the liquid composition contains at least one anionic surfactant of the formula (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 soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants can be in the form of their sodium, potassium or magnesium or ammonium salts. The anionic surfactants are preferably in the form of their ammonium salts, said ammonium ion being derived from at least one (C ₂ -C ₆ ) -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 includes alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof. It is again particularly preferred if, based on the weight of the 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 surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as is 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, C9-11 alcohol with 7 EO, C13-15 alcohols with 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO (propylene oxide) groups together in the molecule can also be used according to the invention. Also suitable are a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C ₁₆ -C ₁₈ fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. The washing, cleaning, post-treatment or auxiliary washing agent particularly preferably contains a C ₁₂ -C ₁₈ fatty alcohol with 7 EO or a C ₁₃ -C ₁₅ oxo alcohol with 7 EO as a nonionic surfactant.

R³

für einen linearen oder verzweigten C₈-C₁₈-Alkylrest, einen Arylrest oder Alkylarylrest,

XO

unabhängig voneinander für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

m

für ganze Zahlen von 1 bis 50 stehen.

The liquid composition particularly preferably contains at least one nonionic surfactant of the formula (N-1) R ³ -O- (XO) _m -H, (N-1) in the

R ³

for a linear or branched C ₈ -C ₁₈ alkyl radical, an aryl radical or alkylaryl radical,

XO

independently of one another for an ethylene oxide (EO) or propylene oxide (PO) group,

m

stand for integers from 1 to 50.

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

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

mit k = 9 bis 17, m = 3, 4, 5, 6 oder 7. Ganz besonders bevorzugte Vertreter sind Fettalkohole mit 10 bis 18 C-Atomen und mit 7 EO (k = 11-17, m = 7 in Formel N-2).In summary, particularly preferred fatty alcohol alkoxylates are those of the formula (N-2)

with k = 9 to 17, m = 3, 4, 5, 6 or 7. Very particularly preferred representatives are fatty alcohols with 10 to 18 carbon atoms and with 7 EO (k = 11-17, m = 7 in formula N- 2).

Such fatty alcohol or oxo alcohol ethoxylates are available under the trade names Dehydol LT7 ^® (BASF) Lutensol AO7 ^® (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 one Total amount from 1 to 50% by weight, more preferably 2 to 30% by weight, particularly preferably 3 to 25% by weight, very particularly preferably from 5 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, for example, ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methyl propanediol, glycerol, glycols, such as diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether , Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, 3-ethoxytrigoxyethyl, 2-oxytrigoxyethyl, 3-methoxybutyloxy, 3-methoxybutyloxy-2, -4-hydroxymethyl-1,3-dioxolane, propylene glycol t-butyl ether, di-n-octyl ether and low molecular weight polyalkylene glycols, such as PEG 400, and mixtures of these solvents.

The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol monoethyl n-butylene glycol 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-methoxybutyl ether, and methyl-3-methoxybutyl ether 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 analogous to the synthesis instructions according to Example 2 of the WO 2016/074936 A1 provide.

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 the formula (I), in which R ¹ and R ² independently of one another are preferred for a carbon radical having 3 to 20 carbon atoms with 3 to 10 carbon atoms, particularly preferably with 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 C ₃ -C ₂₀ alkyl group, a linear or branched C ₃ -C ₁₀ alkyl group, a linear or branched C ₃ -C ₆ -Alkyl group, a linear or branched C ₃ -C ₂₀ alkenyl group, a linear or branched C ₃ -C ₁₀ alkenyl group, a linear or branched C ₃ -C ₆ alkenyl group, a cyclic C ₃ -C ₁₀ 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 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. 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.

• - Textilpflegemittel wie Weichmacher, Phobier- und Imprägniermittel gegen Wasser und Wiederanschmutzungen, Bleichmittel, Bleichaktivatoren, Enzyme, Silikonöle, Antiredepositionsmittel, optische Aufheller, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, Germizide, Fungizide, Antioxidantien, Antistatika, Bügelhilfsmittel, Quell- und Schiebefestmittel, UV-Absorber, kationische Polymere,
• - Hautpflegemittel oder
• - Parfüm(öl) oder Riechstoffe.

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:

• - Fabric care agents such as emollients, waterproofing and impregnation against water and Wiederanschmutzungen, bleaches, bleach activators, enzymes, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, shrink preventatives, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, 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 ingredient is preferably selected from enzymes, optical brighteners, builders, solvents, anti-deposition 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 which are variants in themselves, that is to say which have already been modified compared to the wild-type molecules. 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 used one-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 has position 320 in the sequence of a reference protein has a different amino acid. Such exchanges are usually carried out at the DNA level via mutations of individual base pairs (see above). “R320K” means, for example, that the reference enzyme at position 320 has the amino acid arginine, while the variant under consideration has the amino acid lysine at the position that can be homologated with it. “320K” means that any, that is to say usually a naturally prescribed, amino acid at a position which corresponds to position 320 has been replaced by a lysine which is located precisely at this point in the present molecule. "R320K, L" means that the amino acid arginine at position 320 is replaced by lysine or leucine. And "R320X" means that the amino acid arginine in position 320 is replaced by any other amino acid.

In principle, the amino acid exchanges according to the invention designated by the present application are not limited to the fact that they are the only exchanges in which the variant in question differs from the wild-type molecule. It is known in the prior art that the advantageous properties of individual point mutations can complement one another. Thus, embodiments of the present invention include all variants which, in addition to other exchanges with the wild-type molecule, also have the exchanges according to the invention.

Furthermore, in principle it does not matter in what order the amino acid exchanges in question have been carried out, that is to say whether a corresponding point mutant is further developed according to the invention or, for example, a variant according to the invention is first generated from a wild-type molecule which is further developed in accordance with other teachings to be found in the prior art . Several exchanges can also be carried out simultaneously in a mutagenesis approach, for example the invention and others together.

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

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

• Trypsin-artig, wobei eine Spaltung des Amidesubstrates nach den Aminosäuren Arg oder Lys bei P1 erfolgt; Chymotrypsin-artig, wobei eine Spaltung nach einer der hydrophoben Aminosäuren bei P1 erfolgt; und Elastase-artig, wobei eine Spaltung des Amidsubstrates nach Ala bei P1 erfolgt.

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

• Trypsin-like, with cleavage of the amide substrate according to the amino acids Arg or Lys at P1; Chymotrypsin-like, with cleavage after one of the hydrophobic amino acids at P1; and elastase-like, with cleavage of the amide substrate according to Ala at P1.

The protease activity can be determined by the method described in Tenside, Volume 7 (1970), pp. 125-132. Accordingly, it is given in PE (protease units). The protease activity of an enzyme can be determined according to standard methods, such as in particular using BSA as substrate (bovine albumin) and / or using the AAPF method.

Surprisingly, it was found that a protease of the type of the alkaline protease from Bacillus lentus DSM 5483 or a protease sufficiently similar to this (based on the sequence identity), which exhibits several of these changes in combination, is particularly suitable 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, pp.3389-3402 ) and happens principally in that similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences are assigned to 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), in particular multiple sequence comparisons, are created using computer programs. The Clustal series (cf. for example Chenna et al. (2003): Multiple sequence alignment with the Clustal series of programs. Nucleic Acid Research 31, 3497-3500), T-Coffee (cf. for example Notredame et al . (2000): T-Coffee: A novel method for multiple sequence alignments. J. Mol. Biol. 302, 205-217) or programs based on these programs or algorithms. In the present 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 sequence comparisons is based on ClustalW .

Such a comparison also allows a statement about the similarity of the compared sequences to one another. It is usually given in percent identity, that is to say the proportion of identical nucleotides or amino acid residues in the same positions or in an alignment corresponding to one another. The broader concept of homology also includes conserved amino acid exchanges 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. So far not otherwise stated, identity or homology information in the present application relate to the total length of the nucleic acid or amino acid sequence specified in each case.

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 as enzyme at least one enzyme selected from α-amylase, cellulase, mannanase, lipase, pectate lyase.

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

Compositions according to the invention can be added to the enzymes obtained in any form established according to the prior art. 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. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in layers. Capsules of this type are applied by methods known per se, for example by shaking 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 in determining 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.

Cellulases (endoglucanases, EG) which can be made up according to the invention include, for example, the fungal cellulase preparation rich in endoglucanase (EG) or its further developments, which is offered by the Novozymes company under the trade name Celluzyme®. 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 is available from Danisco / Genencor under the trade name Puradax®. Other usable commercial products from Danisco / Genencor are “Genencor detergent cellulase L” and IndiAge®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 described in the international patent application WO 98/12307 are disclosed cellulases from Melanocarpus, in particular Melanocarpus albomyces, which are disclosed in the international patent application WO 97/14804 are disclosed, cellulases of the EGIII type from Trichoderma reesei, which are disclosed in the European patent application EP 1 305 432 are disclosed or variants obtainable therefrom, in particular those which are disclosed in the European patent applications EP 1240525 and EP 1305432 , as well as cellulases, which are disclosed in the international publications 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 which have a homology of over 80% (increasingly preferred of over 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90 , 5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5 %, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99, 6%, 99.7%, 99.8%, 99.9%).

The from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase is from the international patent application WO 97/14804 known. As described there, it has a molecular weight of about 20 kDa and has at least 80% of its maximum activity at 50 ° C. in the pH range from 4 to 9, with almost 50% of the maximum activity remaining at pH 10. As also described there, it can be isolated from Melanocarpus albomyces and produced in genetically engineered Trichoderma reseei transformants. Cellulases which have a homology of 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, such as from MJ Bailey et al. in Enzyme Microb. Technol. 3: 153 (1981) described; 1 NCU defines the amount of enzyme that 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 entire 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 ) can be determined.

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 (E.C. 3.1.1.3) and lipoprotein lipase (E.C. 3.1.1.34) and monoglyceride lipase (E.C. 3.1.1.23).

Furthermore, the lipase preferably contained in a liquid composition according to the invention is naturally in a microorganism of the Thermomyces type lanuginosus or Rhizopus oryzae or Mucor javanicus present or 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 thus be expressed in the microorganism by a nucleic acid sequence that is part of the chromosomal DNA of the microorganism in its wild-type form. It or the nucleic acid sequence coding for it is consequently present in the wild-type form of the microorganism and / or can be isolated from the wild-type form of the microorganism. In contrast, 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%) is identical to the wild-type lipase from the strain DSM 4109 Thermomyces lanuginosus. It is again preferred if, based on said wild-type lipase from strain DSM 4109, there is at least the amino acid change N233R.

In a further embodiment, in particular those lipases derived from the wild-type lipase from strain DSM 4109 are preferably usable according to the invention, which are selected from at least one lipase enzyme according to at least one of claims 1 to 13 of the document WO 00/60063 A1 . Printed on the revelation WO 00/60063 A1 explicit reference is made in full.

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

The liquid compositions according to the invention can additionally contain at least one mannanase as enzyme. A mannanase contained in the composition according to the invention (in particular in a washing and cleaning agent for textiles preferred according to the invention) catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans and galactoglucomannans as part of its mannanase activity. Said mannanase enzymes according to the invention are, according to the enzyme nomenclature, as E.C. 3.2.1.78 classified.

The mannanase activity of a polypeptide or enzyme can be determined according to test methods known from the literature. For example, a test solution is made into holes with a diameter of 4 mm Agar plate containing 0.2% by weight of AZGL galactomannan (carob), ie the substrate for the endo-1,4-beta-D-mannanase essay, available under catalog number I-AZGMA from Megazyme (https://www.megazyme.com ), brought in.

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

• WO 99/64619 offenbart Beispiele für flüssige, proteasehaltige Waschmittelzusammensetzungen mit hohem Gesamttensidgehalt von mindestens 20 Gew.-%, die zusätzlich Mannanase-Enzym umfassen.

Mannanase enzymes have been identified in numerous Bacillus organisms:

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

The compositions according to the invention preferably contain mannanase in a total amount of 0.01 to 1.0% by weight, in particular 0.02 to 0.1% by weight, based on the total weight of the composition.

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

It is particularly preferred according to the invention if the compositions according to the invention as mannanase enzyme have at least one mannanase polypeptide from gram-positive alkalophilic strains of Bacillus, in particular selected from at least one member of the group from Bacillus subtilis, Bacillus lentus, 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.

• i) Polypeptiden, die eine Aminosäuresequenz umfassen, die mindestens 90% (zunehmend bevorzugt mindestens 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% oder 99,8%) Sequenzidentität zu dem Polypeptid gemäß SEQ ID No.1 (vgl. Sequenzprotokoll aus WO 99/64619 ), und
• ii) Polypeptiden, die ein Fragment von (i) sind.

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 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 wt .-%, in particular 0.02 to 0.1 wt .-%, each based on the total weight of the composition in the 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 lentus DSM 5483 or in addition to the protease sufficiently similar to this (based on the sequence identity), which has several of these changes in combination, at least one α-amylase .

As an enzyme, α-amylases (EC 3.2.1.1) hydrolyze internal α-1,4-glycosidic bonds of starch and starch-like polymers. This α-amylase activity is, for example, the applications WO 97/03160 A1 and GB 1296839 measured 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 µmol 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 must therefore be determined using a standard. You can roughly calculate that 1 KNU corresponds to approx. 50 TAU. Another activity determination method is measurement using the Quick-Start ^® test kit from Abbott, Abott Park, Illinois, USA.

A preferred area of application of the liquid surfactant compositions according to the invention is the cleaning of textiles. Because laundry detergents and cleaning agents for textiles mainly have alkaline pH values, α-amylases, which are active in the alkaline medium, are used in particular. These are produced and secreted by microorganisms, ie fungi or bacteria, especially those of the genera Aspergillus and Bacillus. Starting from these natural enzymes, there is still an almost unmanageable abundance of variants which have been derived via mutagenesis and which have specific advantages depending on the area of use.

Examples of this are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens and from B. stearothermophilus and their further developments improved 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. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

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

The state of the art includes the three patent applications WO 96/23873 A1 , WO 00/60060 A2 and WO 01/66712 A2 registered by Novozymes. WO 96/23873 A1 describes in part 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 registration WO 00/60060 A2 also names a large number of possible amino acid exchanges in 10 different positions on the α-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, denotes 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 mentioned α-amylases have been mutated.

Out WO 96/23873 A1 For example, the possibility of replacing an M in position 9 according to the AA560 count with an L in the α-amylases mentioned, specifically in position 202 M for L and in positions 182 and 183 (or 183 and 184) To delete amino acids. WO 00/60060 A2 among other things, specifically discloses the amino acid variation N195X (that is, in principle against any other amino acid). WO 01/66712 A2 discloses, inter alia, the amino acid variations R118K, 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 α-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.

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

It is preferred if the liquid composition contains at least one optical brightener. The optical brighteners are preferred from the substance classes of distyrylbiphenyls, the stilbenes, the 4,4'-diamino-2,2'-stilbene disulfonic acids, the coumarins, the dihydroquinolinones, the 1,3-diarylpyrazolines, the naphthalic imides, 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-thiophene diyl) bis [5-1,1-dimethylethyl) benzoxazole (available, for example, as Tinopal® SFP from BASF SE ) and / or 2,5-bis (benzoxazol-2-yl) thiophene. are selected, incorporate.

According to the invention, the 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.

Also suitable are copolymeric polycarboxylates, 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 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. Also suitable are copolymeric polycarboxylates, 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 preferably used in liquid detergents.

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 also contain components which have a positive influence on the oil and fat washability from textiles, so-called soil release active substances. 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 of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives with monomeric and / or polymeric diols known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of this. These are commercially available, for example, under the trade name Texcare ^® .

Anti-redeposition agents are selected in particular 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, can preferably be used.

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

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 publication WO 2014/089386 A1 on page 7, line 20 to page 9, line 6, 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— CO ₂ M (BL-1) in which F stands for the monoazo dye. The extinction coefficient mentioned above relates to this dye F in the compound FH in an ethanolic solution.

L according to formula BL-1 is an organic group which connects the monoazo dye F with the carboxyl group CO ₂ M. 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 _1-20 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, -NO ₂ , -SO ₂ CH ₃ , -CL, -BR.

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

in welcher jeweils unabhängig voneinander

• R für einen C_1-20, oder C_2-12 Alkylrest steht, welcher gegebenenfalls Ether- und/oder Ester- und/oder Amidgruppen als Verzweigungsstellen aufweist und die Aklylkette weiterhin gegebenenfalls beispielsweise mit -OH, -CN, NO₂, -SO₂CH₃, -CL, -BR substituiert ist;
• R¹ und R² jeweils unabhängig voneinander ausgewählt sind und beispielsweise Wasserstoff darstellen; vorzugsweise sind sie jeweils unabhängig voneinander ausgewählt aus Elektronenziehenden Gruppen wie beispielsweise -CN, -NO₂, -SO₂CH₃, -CL, -BR;
• Z ausgewählt ist aus einer elektronenziehenden Gruppe und ist vorzugsweise ausgewählt aus Cyano-, Sulfamoyl, N:N-Diethylsulfamoyl, N-Ethylsulfamoyl, Trifluoromethyl, Ethylsulfonyl, Nitrosylfonyl, N-Methylsulfamoyl, Chloro und Bromo; insbesondere ist Z eine Nitrogruppe;
• Y Wasserstoff, ein kurzer (C_1-4) Alkylrest, Halogen, -NHCOR, vorzugsweise Wasserstoff, -CH₃ oder -CI ist;
• X Wasserstoff, eine kurze (C_1-4) Alkoxykette oder Halogen, insbesondere Wasserstoff, Methoxy, Ethoxy oder Chlorid ist.

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

in which each independently

• R stands for a C _1-20 or C _2-12 alkyl radical, which may have ether and / or ester and / or amide groups as branching sites and the alkyl chain furthermore optionally with, for example, -OH, -CN, NO ₂ , -SO ₂ CH ₃ , -CL, -BR is substituted;
• 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 CH ₃ , -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 _1-4 ) alkyl radical, halogen, -NHCOR, preferably hydrogen, -CH ₃ 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 represented by R in general formula 2 are β-hydroxyethyl, β-cyanoethyl, β- (methoxy or ethoxy) ethyl, γ-methoxypropyl, benzyl or β-phenylethyl, β-methoxycarbonyl-ethyl or ß-acetoxyethyl.

in welcher Z, R, X, Y und L die gleichen Reste darstellen, wie weitere oben zu Formel 1 und Formel 2 bereits erläutert.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.

worin jedes R¹ und R² unabhängig voneinander ausgewählt ist aus R, -[(CH₂CR'HO)_x(CH₂CR"HO)_yH] und Mischungen daraus, worin jedes R unabhängig voneinander ausgewählt ist aus H, linearen oder verzweigten C₁-C₄-Alkylgruppen, Benzyl und Mischungen daraus; jedes R' unabhängig voneinander ausgewählt ist aus H, CH₂OCH₂CH₂O)_ZH und Mischungen daraus und jedes R" unabhängig voneinander ausgewählt ist aus H, CH₃, CH₂O(CH₂CH₂O)_ZH und Mischungen daraus; worin x + y < 5; y ≥ 1 und z = 0 bis 5 ist. 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, - [(CH ₂ CR'HO) _x (CH ₂ CR "HO) _y H] and mixtures thereof, wherein each R is independently selected from H, linear or branched C ₁ -C ₄ alkyl groups, benzyl and mixtures thereof; each R 'is independently selected from H, CH ₂ OCH ₂ CH ₂ O) _Z H and mixtures thereof and each R "is independently selected from H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _Z H 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 present in pre-portioned form (portion). In this embodiment, as a portion, the composition according to the invention is 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 composition according to the invention.

The water solubility of the material can be determined with the aid of a square film of said material (film: 22 x 22 mm with a thickness of 76 µm) fixed in a square frame (edge length on the inside: 20 mm) according to the following measurement protocol. Said framed film is immersed in 800 ml of distilled water at a temperature of 20 ° C. in a 1 liter beaker with a circular base (Schott, Mainz, beaker 1000 mL, low form), so that the surface of the clamped film is at a right angle to Bottom surface of the beaker is arranged, 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 so that the bottom edge of the frame runs along the radius of the bottom surface of the beaker and the center of the bottom edge of the frame is arranged above the center of the radius of the beaker bottom. The material should dissolve within 600 seconds while stirring (stirring speed magnetic stirrer 300 rpm, stirring rod: 6.8 cm long, diameter 10 mm) in such a way that no individual solid film particles are visible to the naked eye. The walls are preferably made of a water-soluble film. According to the invention, this film can preferably have a thickness of at most 150 μm (particularly preferably of at most 120 μm). Preferred walls are accordingly made of a water-soluble film and have a thickness of at most 150 μm (particularly preferably of at most 120 μm, very particularly preferably of at most 90 μm).

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 film material to form at least one bulge for receiving at least one composition according to the invention therein, filling the composition into the respective bulge, covering the bulges filled with the composition with a second layer of one 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 contain polyvinyl alcohol or a polyvinyl alcohol copolymer.

Suitable water-soluble films as water-soluble material are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which 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.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.The water-soluble material preferably contains at least one polyvinyl alcohol and / or at least one polyvinyl alcohol copolymer. "Polyvinyl alcohol" (abbreviation PVAL or PVA occasionally also PVOH) is the name for polymers of the general structure

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

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98 to 99 mol% or 87 to 89 mol -%, so 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. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass 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.

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 can additionally be added to the film material suitable as a water-soluble material.

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

A bittering agent is preferably incorporated into said water-soluble material of the portion walls to increase product safety. Corresponding embodiments of the water-soluble material with bittering agent are in the publications EP-B1-2 885 220 and EP-B1-2 885 221 described. 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) Bereitstellen einer wässrigen Flotte durch Mischen von 0,5 L bis 40,0 L Wasser mit 0,5 bis 100 g einer Zusammensetzung des ersten Erfindungsgegenstandes, und
• (b) In Kontakt bringen eines Substrats, insbesondere eines Textils, mit der gemäß (a) hergestellten wässrigen Flotte.

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 aqueous liquor prepared according to (a).

As already mentioned, the soiling can be pretreated with the composition according to the invention of the first subject of the invention before step (a) as part of a textile wash.

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

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

1. 1. Flüssige Zusammensetzung, insbesondere für die Textilwäsche, enthaltend jeweils bezogen auf deren Gesamtgewicht
   • - eine Gesamtmenge von 20 bis 70 Gew.-% Tensid, und
   • - mindestens eine Catecholverbindung der Formel (I)
     
     worin R¹ und R² unabhängig voneinander für einen Kohlenwasserstoffrest mit mindestens 3 Kohlenstoffatomen steht.
2. 2. Flüssige Zusammensetzung nach Punkt 1, dadurch gekennzeichnet, dass Tensid in einer Gesamtmenge von 25 bis 65 Gew.-%, bevorzugt von 30 bis 50 Gew.-%, besonders bevorzugt von 35 bis 45 Gew.-%, enthalten ist.
3. 3. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass mindestens ein anionisches Tensid enthalten ist.
4. 4. Flüssige Zusammensetzung nach Punkt 3, dadurch gekennzeichnet, dass bezogen auf das Gewicht der Zusammensetzung eine Gesamtmenge an anionischem Tensid von 15 bis 35 Gew.- %, insbesondere von 20 bis 30 Gew.-%, enthalten ist.
5. 5. Flüssige Zusammensetzung nach einem der Punkte 3 oder 4, dadurch gekennzeichnet, dass mindestens ein anionisches Tensid, ausgewählt aus der Gruppe bestehend aus C_8-18-Alkylbenzolsulfonaten, Olefinsulfonaten, C_12-18-Alkansulfonaten, C_12-18-Estersulfonaten, C_12-18-Alkylsulfaten, C_12-18-Alkenylsulfaten, C_12-18-Fettalkoholethersulfaten und Mischungen daraus, enthalten ist.
6. 6. Flüssige Zusammensetzung nach einem der Punkte 3 bis 5, dadurch gekennzeichnet, dass mindestens ein anionisches Tensid der Formel (A-3) enthalten ist,
   
   in der R' und R" unabhängig voneinander H oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 C-Atome enthalten, und Y⁺ ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations (insbesondere Na⁺) bedeuten.
7. 7. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass mindestens ein nichtionisches Tensid enthalten ist.
8. 8. Flüssige Zusammensetzung nach Punkt 7, dadurch gekennzeichnet, dass bezogen auf das Gewicht der Zusammensetzung eine Gesamtmenge an nichtionischem Tensid von 5 bis 20 Gew.-%, insbesondere von 10 bis 15 Gew.-%, enthalten ist.
9. 9. Flüssige Zusammensetzung nach einem der Punkte 7 oder 8, dadurch gekennzeichnet, dass mindestens ein nichtionisches Tensid gemäß Formel (N-1) enthalten ist R³-O-(XO)_m-H, (N-1) in der

   R³

   für einen linearen oder verzweigten C₈-C₁₈-Alkylrest, einen Arylrest oder Alkylarylrest,

   XO

   unabhängig voneinander für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

   m

   für ganze Zahlen von 1 bis 50 stehen.

10. 10. Flüssige Zusammensetzung nach einem der Punkte 1 bis 9, dadurch gekennzeichnet, dass das Gewichtsverhältnis von anionischem zu nichtionischem Tensid im Gewichtsverhältnisbereich von 1 zu 1 bis 3 zu 1, insbesondere von 1,5 zu 1 bis 2.5 zu 1, liegt.
11. 11. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass Wasser (bevorzugt in einer Gesamtmenge von 5 und 45 Gew.-%, bevorzugter von 10 und 40 Gew.-%, bevorzugter von 5 bis 30 Gew.%, ganz besonders bevorzugt von 8 bis 25 Gew.%) enthalten ist.
12. 12. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass mindestens ein organisches Lösemittel (insbesondere in einer Gesamtmenge von 5 Gew.-% bis 20 Gew.-%, besonders bevorzugt von 10 Gew.-% bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung) enthalten ist.
13. 13. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass gemäß Formel (I) R¹ und R² unabhängig voneinander für einen Kohlenstoffrest mit 3 bis 20 Kohlenstoffatomen, bevorzugt mit 3 bis 10 Kohlenstoffatomen, besonders bevorzugt mit 3 bis 6 Kohlenstoffatomen, steht.
14. 14. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass gemäß Formel (I) R¹ und R² unabhängig voneinander für eine lineare oder verzweigte C₃-C₂₀-Alkylgruppe, eine lineare oder verzweigte C₃-C₁₀-Alkylgruppe, eine lineare oder verzweigte C₃-C₆-Alkylgruppe, eine lineare oder verzweigte C₃-C₂₀-Alkenylgruppe, eine lineare oder verzweigte C₃-C₁₀-Alkenylgruppe, eine lineare oder verzweigte C₃-C₆-Alkenylgruppe, eine zyklische C₃-C₁₀-Alkylgruppe, eine Propylgruppe, eine Phenylgruppe oder eine Benzylgruppe.
15. 15. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass gemäß Formel (I) R¹ und R² unabhängig voneinander für 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 oder Benzyl.
16. 16. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass gemäß Formel (I) R¹ und R² gleich sind.
17. 17. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass bezogen auf das Gesamtgewicht der Zusammensetzung die mindestens eine Catecholverbindung gemäß Formel (I) in einer Gesamtmenge von 0,05 bis 10,0 Gew.-%, bevorzugter 0,1 bis 4 Gew.-%, bevorzugter von 0,2 bis 2,0 Gew.-%, ganz besonders bevorzugt von 0,3 bis 3,0 Gew.-%, enthalten ist.
18. 18. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass zusätzlich mindestens ein Enzym, insbesondere mindestens eine Lipase, enthalten ist.
19. 19. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass zusätzlich mindestens ein die Farbübertragung inhibierendes Polymer enthalten ist.
20. 20. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass zusätzlich mindestens ein schmutzabweisendes Polymer (SRP) enthalten ist.
21. 21. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass zusätzlich mindestens ein optischer Aufheller enthalten ist.
22. 22. Flüssige Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass zusätzlich mindestens ein Bläuungsmittel enthalten ist.
23. 23. Verfahren zur Substratbehandlung umfassend die Verfahrensschritte
    • (a) Bereitstellen einer wässrigen Flotte durch Mischen von 0,5 L bis 40,0 L Wasser mit 0,5 bis 100 g einer flüssigen Zusammensetzung gemäß einem der Punkte 1 bis 22, und
    • (b) In Kontakt bringen eines Substrats, insbesondere eines Textils, mit der gemäß (a) hergestellten wässrigen Flotte.
24. 24. Verwendung einer wässrigen Flotte, erhältlich durch Mischen von 0,5 L bis 40,0 L Wasser mit 0,5 bis 100 g einer flüssigen Zusammensetzung nach einem der Punkte 1 bis 22, zur Textilbehandlung, insbesondere zur Textilreinigung.

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

1. 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 R ¹ and R ² independently of one another represent a hydrocarbon radical having at least 3 carbon atoms.
2. 2. Liquid composition according to item 1, characterized in that 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.
3. 3. Liquid composition according to one of the preceding points, characterized in that it contains at least one anionic surfactant.
4. 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.
5. 5. Liquid composition according to one of items 3 or 4, characterized in that at least one anionic surfactant selected from the group consisting of C _8-18 alkylbenzenesulfonates, olefin sulfonates, C _12-18 alkanesulfonates, C _12-18 ester sulfonates, C _12-18 alkyl sulfates, C _12-18 alkenyl sulfates, C _12-18 fatty alcohol ether sulfates and mixtures thereof.
6. 6. Liquid composition according to one of items 3 to 5, characterized in that at least one anionic surfactant of the formula (A-3) is present,
   
   in which R 'and R "are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms, and Y ^{+ is} a monovalent cation or the nth part of an n-valent cation (in particular Na ⁺ ) mean.
7. 7. Liquid composition according to one of the preceding points, characterized in that it contains at least one nonionic surfactant.
8. 8. Liquid composition according to item 7, 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.
9. 9. 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 -O- (XO) _m -H, (N-1) in the

   R ³

   for a linear or branched C ₈ -C ₁₈ 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.

10. 10. 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.
11. 11. 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 from 8 to 25% by weight) is contained.
12. 12. 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 , each based on the total weight of the composition) is included.
13. 13. 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 carbon radical having 3 to 20 carbon atoms, preferably having 3 to 10 carbon atoms, particularly preferably having 3 to 6 carbon atoms, stands.
14. 14. 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 C ₃ -C ₂₀ alkyl group, a linear or branched C ₃ -C ₁₀ alkyl group, a linear or branched C ₃ -C ₆ alkyl group, a linear or branched C ₃ -C ₂₀ alkenyl group, a linear or branched C ₃ -C ₁₀ alkenyl group, a linear or branched C ₃ -C ₆ alkenyl group, a cyclic C ₃ -C ₁₀ alkyl group, a propyl group, a phenyl group or a benzyl group.
15. 15. 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, isopentyl, neopentyl, tert-pentyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, cyclopentyl, n-hexyl, iso-hexyl, neo-hexyl, cyclohexyl, allyl, but-2-enyl or benzyl.
16. 16. Liquid composition according to one of the preceding points, characterized in that according to formula (I) R ¹ and R ^{2 are the} same.
17. 17. 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 from 0.2 to 2.0% by weight, very particularly preferably from 0.3 to 3.0% by weight, is contained.
18. 18. 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.
19. 19. Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one polymer which inhibits color transfer.
20. 20. Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one dirt-repellent polymer (SRP).
21. 21. Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one optical brightener.
22. 22. Liquid composition according to one of the preceding points, characterized in that it additionally contains at least one bluing agent.
23. 23. 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
    • (b) bringing a substrate, in particular a textile, into contact with the aqueous liquor prepared according to (a).
24. 24. 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 textile cleaning.

Examples

The following compositions in Table 1 were prepared by mixing the components in a conventional manner. Table 1: Liquid detergent E1 [% by weight] V1 [% by weight] C _11-13 alkylbenzenesulfonic acid 20.0 20.0 (C _12-14 ) fatty alcohol ether sulfate with 2 units of ethylene oxide 5.0 5.0 Fatty alcohol ether ethoxylated with 7 moles of ethylene oxide 10.0 10.0 2-aminoethanol 8.0 8.0 Sodium hydroxide 1.0 1.0 DTA-1 ¹ 0.5 - DTA-2 ² - 0.5 C _12-18 fatty acid 3.0 3.0 Etidronic acid (HEDP) 0.6 0.6 citric acid 3.0 3.0 Boric acid 2.0 2.0 1,2-propylene glycol 12.0 12.0 Denatonium benzoate 0.001 0.001 Dye, protease, amylase, lipase, cellulase, optical brightener of the stilbene type 1.7 1.7 Perfume 1.0 1.0 distilled water ad 100 ad 100 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 the invention WO 2016/074936 A1 . The compositions were then stored at 0 ° C for 8 weeks and then assessed visually. Formula V1 not according to the invention showed significant sedimentation, whereas formula E1 according to the invention was stable.

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• DE 102016214660 A1 [0004]
• WO 2016/074936 A1 [0004, 0044, 0160]
• WO 98/12307 [0069]
• WO 97/14804 [0069, 0071]
• EP 1305432 [0069]
• EP 1240525 [0069]
• WO 1992006165 [0069]
• WO 9629397 [0069]
• WO 02/099091 [0069]
• WO 0060063 A1 [0081]
• WO 9964619 [0088, 0092]
• WO 9703160 A1 [0095]
• GB 1296839 [0095]
• WO 02/10356 A2 [0095]
• WO 96/23873 A1 [0099]
• WO 0060060 A2 [0099, 0100]
• WO 0166712 A2 [0099, 0100]
• WO 9623873 A1 [0099, 0100]
• WO 00/60060 A2 [0099]
• WO 2014/089386 A1 [0115]
• EP 2885220 B1 [0148]
• EP 2885221 B1 [0148]

Non-patent literature cited

• Altschul, S.F., Gish, W., Miller, W., Myers, E.W. & Lipman, D.J. (1990) "Basic local alignment search tool." J. Mol. Biol. 215: 403-410 [0061]
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Claims (11)

Liquid composition, in particular for textile washing, each containing, based on their total weight, a total amount of 20 to 70% by weight of surfactant, and at least one catechol compound of the formula (I)

wherein R ¹ and R ² independently of one another represent a hydrocarbon radical having at least 3 carbon atoms. Liquid composition after 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 .-%. Liquid composition according to one of the preceding claims, characterized in that at least one anionic surfactant, in particular in a total amount of 15 to 35% by weight, in particular 20 to 30% by weight, is contained. Liquid composition according to one of the preceding claims, characterized in that at least one nonionic surfactant, in particular in a total amount of 5 to 20 wt .-%, in particular from 10 to 15 wt .-%, is contained. Liquid composition according to one of the Claims 1 to 4th , 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 claims, 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 claims, 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 claims, characterized in that according to formula (I) R ¹ and R ² independently of one another for a linear or branched C ₃ -C ₂₀ alkyl group, a linear or branched C ₃ -C ₁₀ alkyl group linear or branched C ₃ -C ₆ alkyl group, a linear or branched C ₃ -C ₂₀ alkenyl group, a linear or branched C ₃ -C ₁₀ alkenyl group, a linear or branched C ₃ -C ₆ alkenyl group, a cyclic C ₃ -C ₁₀ alkyl group, a propyl group, a phenyl group or a benzyl group. Liquid composition according to one of the preceding claims, characterized in that according to formula (I) R ¹ and R ² independently of one another stand 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 claims, characterized in that according to formula (I) R ¹ and R ^{2 are the} same. Liquid composition according to one of the preceding claims, 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 from 0.2 to 2.0 wt .-%, very particularly preferably from 0.3 to 3.0 wt .-%, is contained.