DE102015215591A1 - Low-water, two-phase liquid detergent with acidic pH - Google Patents

Abstract

The present application is directed to liquid detergent compositions having acidic pH and two continuous phases containing hydroxycarboxylic acid, alkalizing agent, enzyme and at least one nonionic surfactant, the use of such liquid detergents to remove stains, especially those on deodorant ingredients and debris , but also rust, berries, tea and red wine, as well as a washing process in which such an agent is used.

Description

The present application is directed to low acid liquid pH liquid detergent compositions having two continuous phases containing hydroxycarboxylic acid, alkalizing agent, enzyme and at least one nonionic surfactant, the use of such liquid detergents to remove stains, especially those on ingredients and residues of deodorants, but also fat, starch, rust, berries, tea and red wine, as well as to a washing process in which such an agent is used.

Consumer deodorants, with human skin secretions, form sparingly soluble, yellowish residues on worn textiles, consisting essentially of aluminum hydroxychloride, perfume oil ingredients, waxes, e.g. Myristyl myristate and human skin components and sweat low molecular weight fatty acids. Other poorly soluble stains on textiles can come from rust and food residues, especially berries, tea and red wine.

Conventional liquid detergents are based on surfactant mixtures which comprise, for example, soaps, fatty alcohol ether sulfates and ethoxylates, the total quantities of surfactants in liquid detergents being about 20% by weight and in concentrated media about 50% by weight. However, such known liquid detergents do not remove such sparingly soluble residues or insufficiently. It is therefore a general endeavor to provide liquid detergents with improved cleaning performance, in particular on stains which are based on constituents and residues of deodorants, but also on rust, berries, tea and red wine.

It has been found that homogeneous liquid detergents which are low in water or anhydrous, 5 to 30 wt.%, Preferably 10 to 30 wt.%, In particular 15 to 25 wt.% Hydroxycarboxylic acid and 5 to 55 wt.%, Preferably 20 to 55 wt .%, In particular 35 to 50 wt.% Of at least one nonionic surfactant, and a pH <5, preferably in the range 2 to 4, particularly preferably have a pH of 2.2, an increased cleaning performance, in particular stains, the On ingredients and residues of deodorants are also based on rust, berries, tea and red wine residues show. However, these detergents have weaknesses when incorporating enzymes. Conventional enzymes can not be incorporated sufficiently stable in storage in the aforementioned compositions. The use of known enzyme stabilizers such as boric acid and its derivatives in conventional amounts is not sufficient. The liquid detergent according to the invention may preferably make do with small amounts of boric acid compound, and yet the storage stability of the enzymes incorporated therein must be ensured. The detergent should continue to perform well against stains that are based on ingredients and residues of deodorants but also against rust, berries, tea and red wine residues act.

• a) Wasser von 5 bis 35 Gew.%, bevorzugt 8 bis 30 Gew.%, besonders bevorzugt 10 bis 30 Gew.%, ganz besonders bevorzugt 15 bis 25 Gew.%
• b) mindestens eine Hydroxycarbonsäure mit 2 bis 8 Kohlenstoffatomen oder deren Salz von 5 bis 30 Gew.%, vorzugsweise 10 bis 30 Gew.%, insbesondere 15 bis 25 Gew.%, jeweils bezogen auf die Säureform,
• c) mindestens ein nichtionisches Tensid von 5 bis 55 Gew.%, vorzugsweise 20 bis 55 Gew.%, insbesondere 35 bis 50 Gew.%,
• d) mindestens ein Enzym,
• e) mindestens ein Alkalisierungsmittel oder dessen Salz von 5 bis 20 Gew.-%, bevorzugt von 7 bis 15 Gew.-%, jeweils bezogen auf die basische Form,

wobei das flüssige Waschmittel

• i) in Form eines Zweiphasensystems mit zwei separaten kontinuierlichen Phasen mit gemeinsamer Phasengrenze vorliegt und
• ii) einen pH-Wert zwischen 2 und 6,5, insbesondere von 3 bis 5,5, besonders bevorzugt von 4,0 bis 6,0, aufweist.

With the help of the first subject of the invention, this object is achieved. The first subject of the invention is a liquid detergent containing, based on the weight of the total detergent in each case in a total amount

• a) water of 5 to 35 wt.%, preferably 8 to 30 wt.%, particularly preferably 10 to 30 wt.%, very particularly preferably 15 to 25 wt.%
• b) at least one hydroxycarboxylic acid having 2 to 8 carbon atoms or its salt of 5 to 30% by weight, preferably 10 to 30% by weight, in particular 15 to 25% by weight, in each case based on the acid form,
• c) at least one nonionic surfactant of from 5 to 55% by weight, preferably from 20 to 55% by weight, in particular from 35 to 50% by weight,
• d) at least one enzyme,
• e) at least one alkalizing agent or its salt of from 5 to 20% by weight, preferably from 7 to 15% by weight, based in each case on the basic form,

the liquid detergent

• i) is in the form of a two-phase system with two separate continuous phases with common phase boundary, and
• ii) has a pH between 2 and 6.5, in particular from 3 to 5.5, particularly preferably from 4.0 to 6.0.

• • eine wässrige Phase und eine davon separiert vorliegende nichtwässrige Phase, die als separate, kontinuierliche Phasen mit gemeinsamer Phasengrenze vorliegen
• • eine Öl-in-Wasser-Emulsion und eine davon separiert vorliegende nichtwässrige Phase, die als separate, kontinuierliche Phasen mit gemeinsamer Phasengrenze vorliegen
• • eine Wasser-in-Öl-Emulsion und eine davon separiert vorliegende wässrige Phase, die als separate, kontinuierliche Phasen mit gemeinsamer Phasengrenze vorliegen.

The detergent according to the invention is formulated in the form of a two-phase system. Two-phase systems used according to the invention are systems in which two separate, continuous, liquid Phases are present which have a common phase boundary. Examples of such systems have the following phases:

• An aqueous phase and a non-aqueous phase separated therefrom, which are present as separate, continuous phases with common phase boundary
• An oil-in-water emulsion and a non-aqueous phase separated therefrom, which are present as separate, continuous phases with common phase boundary
• A water-in-oil emulsion and an aqueous phase separate therefrom, which are present as separate, continuous phases with common phase boundary.

No two-phase systems in the context of the present invention are systems in which only a continuous phase is present, such. As pure oil-in-water or water-in-oil emulsions.

In the context of the invention, cleaning performance (detergency) is understood to mean the removal of one or more soiling, in particular laundry soils, which are bleach-sensitive, enzyme-sensitive or surfactant-sensitive, in particular surfactant-sensitive. The distance can be measured by a brightening of the soiling measured as well as assessed visually.

The detergents described herein may be detergents for textiles or natural fibers. Detergents in the context of the invention also include washing aids which are metered into the actual detergent during manual or automatic textile washing in order to achieve a further effect or to enhance an effect. Furthermore, detergents within the scope of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the item of laundry is brought into contact before the actual washing, for example for dissolving stubborn soiling, and also agents which are in a downstream of the actual textile laundry step give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge. Among the latter, i.a. calculated the fabric softener.

The use of the liquid detergent described herein removes stains based on deodorant ingredients and debris, as well as soiling with rust, berries, tea and red wine. Pretreatment of the affected fabric at the dirty spot significantly improves stain removal. A certain moisture of the textile enhances the effect of citric acid.

The term "low in water" as used herein means that the composition thus characterized contains 20% by weight of water or less. In particular, this term covers compositions which contain 1 to 20% by weight of water, 1 to 15% by weight of water, 5 to 15% by weight of water or 10 to less than 20% by weight of water.

"Anhydrous" as used herein means that a composition contains less than 5% by weight, more preferably less than 3% by weight, preferably less than 1% by weight of water.

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

"Liquid" as used herein with respect to the detergent of the present invention includes all of the flowable compositions at standard conditions (20 ° C, 1013 mbar) and more particularly includes gels and pasty compositions. In particular, the term also includes non-Newtonian fluids having a yield point.

All amounts stated in connection with the constituents of the detergent described herein, unless stated otherwise, are based on% by weight, in each case based on the total weight of the detergent. Further, such amounts referring to at least one ingredient always refer to the total amount of that type of ingredient contained in the detergent, unless explicitly stated otherwise. That is, such amounts, 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 the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the nature of the ingredient. "At least one Nonionic surfactant "therefore means, for example, one or more different nonionic surfactants, ie one or more different types of nonionic surfactants. Together with quantities, the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.

When referring herein to the pH of the composition / detergent, the indicated values always refer to the pH of a 1% (wt%) solution of the homogenized detergent in distilled water at 25 ° C.

The low-water to anhydrous liquid detergent comprises 5 to 30% by weight, preferably 10 to 30% by weight, in particular 15 to 25% by weight of at least one hydroxycarboxylic acid having 2 to 8 carbon atoms, aliphatic hydroxycarboxylic acids having 2 to 8 carbon atoms being preferred.

The total amount of the hydroxycarboxylic acid having 2 to 8 carbon atoms, or the total amount of all the following preferred representatives, is calculated on the basis of the acid form, ie if the acid is partially present in its salt form as a carboxylate in the detergent according to the invention, is assumed in the quantitative calculation as a counterion as H ⁺ ,

The liquid detergent according to the invention particularly preferably contains at least one hydroxycarboxylic acid selected from at least one member of the group which is formed from citric acid, lactic acid, tartaric acid, malic acid, salicylic acid.

Most preferably, the liquid detergent according to the invention contains 5 to 30 wt.%, Preferably 10 to 30 wt.%, In particular 15 to 25 wt.% Of at least one aliphatic hydroxycarboxylic acid having 3 to 6 carbon atoms, wherein said hydroxycarboxylic acid is linear or branched.

The liquid detergent according to the invention very particularly preferably contains 5 to 30% by weight, preferably 10 to 30% by weight, in particular 15 to 25% by weight of at least one aliphatic hydroxycarboxylic acid having 3 to 6 carbon atoms selected from citric acid, lactic acid or a mixture thereof.

As citric acid, both anhydrous citric acid and citric acid monohydrate or mixtures thereof can be used. Preferably, citric acid monohydrate is used.

Lactic acid is understood as meaning both the racemate and the optically active D / L variants.

In addition, mixtures of citric acid and lactic acid are well suited, and while keeping said total amount of said hydroxycarboxylic acids, the amount of lactic acid is from 1 to 10% by weight and the amount of citric acid is from 4 to 29% by weight.

If a combination of lactic acid and citric acid is used, it is preferred according to the invention the weight ratio of lactic acid to citric acid in a weight ratio range of 1 to 2 to 1 to 10, more preferably from 1 to 3 to 1 to 7, most preferably from 1 to 4 to 1 to 6, adjust.

Again, it is most preferable to select the amount of lactic acid from 1 to 10% by weight and the amount of citric acid from 4 to 29% by weight while maintaining the said total amount of said hydroxycarboxylic acids and the weight ratio of lactic acid to citric acid in a weight ratio range of from 1 to 2 to 1 to 10, more preferably from 1 to 3 to 1 to 7, most preferably from 1 to 4 to 1 to 6.

Furthermore, the liquid detergent according to the present invention contains 5 to 55 wt.%, Preferably 20 to 55 wt.%, In particular 35 to 50 wt.% Of at least one nonionic surfactant based on the total amount of the detergent. Suitable nonionic surfactants include all known surfactants commonly used in detergents, especially those selected from the group consisting of alkyl glycol ethers, alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl ( poly) glucosides and mixtures thereof.

In various embodiments of the invention, the detergents described herein contain at least one fatty alcohol alkoxylate having the following formula (I)

R ^{1 is} -O- (AO) _m -H (I), in which
R ^{1 is} a linear or branched alkyl radical,
AO is an ethylene oxide (EO) and / or propylene oxide (PO) grouping,
m is an integer from 1 to 50.

In the above formula, R ^{1 is} a linear or branched, substituted or unsubstituted alkyl radical. 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 and mixtures thereof, with the even number of C atoms being preferred , Particularly preferred radicals R ¹ are derived from fatty alcohols having 12 to 19 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxo alcohols having 10 to 19 carbon atoms.

AO is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index m is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7. The composition according to the invention can comprise mixtures of nonionic surfactants which have different degrees of ethoxylation. Surfactants having alkoxylation / ethoxylation degrees 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 C-1). In summary, particularly preferred fatty alcohol alkoxylates are those of the formula

with k = 9 to 17, m = 3, 4, 5, 6 or 7. Very particularly preferred representatives are fatty alcohols with 10 to 18 C atoms and with 7 EO (k = 11-17, m = 7 in formula C). 1).

Such fatty alcohol or oxo alcohol ethoxylates are available under the brand names 45-7 Dehydol LT7 ^® (Cognis), Lutensol AO7 ^® (BASF) Lutensol ^® M7 (BASF), and Neodol ^® (Shell Chemicals).

The fatty alcohol ethoxylates mentioned above preferably have degrees of ethoxylation of at least 3, more preferably at least 5, again preferably from 7. Such fatty alcohol ethoxylates can be used alone, (BASF), used as mixtures of such fatty alcohol ethoxylates or as mixtures with low-ethoxylated fatty alcohol ethoxylates such as Lutensol ^® AO3 , In such mixtures, it is preferred that the fatty alcohol ethoxylates have degrees of ethoxylation of at least 5, preferably 7, at least 50 weight percent, preferably at least 75 weight percent of the total amount of fatty alcohol ethoxylates.

Likewise, adducts of ethylene oxide and propylene oxide C according to the invention can be employed with fatty alcohols, such as Dehydol ^® 980, _10-16 fatty alcohol with an average of 1.2 units and 6.4 propylene oxide units of ethylene oxide.

• – Polyolfettsäureester, wie beispielsweise das Handelsprodukt Hydagen^® HSP (Cognis) oder Sovermol-Typen (Cognis),
• – alkoxylierte Triglyceride,
• – alkoxylierte Fettsäurealkylester der Formel R³CO-(OCH₂CHR⁴)_wOR⁵, in der R³CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 C-Atomen, R⁴ für Wasserstoff oder Methyl und R⁵ für lineare oder verzweigte Alkylreste mit 1 bis 4 C-Atomen steht und w 1 bis 20 ist,
• – Aminoxide,
• – Hydroxymischether,
• – Sorbitanfettsäureester und Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate,
• – Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester,
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• – Fettsäure-N-alkylglucamide, und
• – Alkyl(poly)glycoside der Formel R²O-[G]_p, in der R² ein lineares oder verzweigtes Alkyl mit 12 bis 16 C-Atomen, G ein Zuckerrest mit 5 oder 6 C-Atomen, insbesondere Glucose, und der Index p 1 bis 10 ist.

Other usable nonionic surfactants may be, for example

• - polyol, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol types (Cognis),
• - alkoxylated triglycerides,
• - alkoxylated fatty acid alkyl esters of the formula R ³ CO- (OCH ₂ CHR ⁴ ) _w OR ⁵ , in the R ³ CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{4 is} hydrogen or methyl and R ^{5 is} linear or branched alkyl radicals having 1 to 4 C atoms and w is 1 to 20,
• - amine oxides,
• - hydroxymix ether,
• Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,
• Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,
• Adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Fatty acid N-alkylglucamides, and
• - Alkyl (poly) glycosides of the formula R ² O- [G] _p , in which R ^{2 is} a linear or branched alkyl having 12 to 16 carbon atoms, G is a sugar residue with 5 or 6 C-atoms, in particular glucose, and the Index p is 1 to 10.

The at least one nonionic surfactant which is used according to the invention preferably has an HLB value of at least 5 but at most 18, preferably from 8 to 17 and particularly preferably from 9 to 16.

The term "HLB" (hydrophilic-lipophilic balance) defines the hydrophilic and lipophilic portion of corresponding classes of substances (here surfactants) in a value range of 1 to 20 according to the following formula ( Griffin, Classification of surface active agents by HLB, J. Soc. Cosmet. Chem. 1, 1949 ): HLB = 20 × (1 - (M ₁ / M)) with M = molecular weight of the entire molecule
and M1 = molecular weight of the lipophilic portion of the molecule

Low HLB values (≥ 1) describe lipophilic substances, high HLB values (≤ 20) describe hydrophilic substances. For example, defoamers typically have HLB values in the range of 1.5 to 3 and are insoluble in water. Emulsifiers for W / O emulsions typically have HLB values in the range of 3 to 8, whereas emulsifiers for O / W emulsions typically have HLB values in the range of 8 to 18. Detergent-active substances typically have HLB values in the range of 13 to 15 and solubilizer values in the range of 12 to 18.

In various embodiments of the invention, the nonionic surfactants used according to the invention have critical micelle concentrations of 10 ^-3 mol / L or more, in particular 10 ^-2 mol / L or more. In accordance with common understanding in the art, the critical micelle formation concentration (CMC) indicates the surfactant concentration at which micelles form and all the additional surfactant added migrates into the micelles.

Furthermore, the detergent may contain at least one anionic surfactant, in particular an alkylbenzenesulfonate and / or an alkyl ether sulfate and / or a fatty acid soap. Such anionic surfactants can also be used in the form of their salts as the corresponding acids.

Preferred surfactants of the sulfonate type are alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins having 12 to 18 carbon atoms with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkane sulfonates having 12 to 18 carbon atoms and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable. Particularly preferably suitable are secondary alkane sulfonates having 12 to 18 carbon atoms, such as are sold for example under the trade name Hostapur SAS ^® by the company WeylChem.

in der R´ und R´´ unabhängig Wasserstoff oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 C-Atome enthalten. Ein ganz besonders bevorzugter Vertreter ist Natriumdodecylbenzylsulfonat. In verschiedenen bevorzugten Ausführungsformen kommen die korrespondierenden Säuren der oben genannten Alkylbenzolsulfonate zum Einsatz. Alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula

in which R'and R'' are independently hydrogen or alkyl and together contain 9 to 19, preferably 9 to 15 and especially 9 to 13 C-atoms. A most preferred representative is sodium dodecylbenzylsulfonate. In various preferred embodiments, the corresponding acids of the above-mentioned alkylbenzenesulfonates are used.

Preferred alk (en) ylsulfates are the salts of the sulfuric acid half-esters of fatty alcohols containing 12 to 18 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the oxo alcohols having 10 to 20 carbon atoms and those half-esters of secondary alcohols of these chain lengths are preferred. From the point of view of washing technology, preference is given to alkyl sulfates having 12 to 16 carbon atoms and alkyl sulfates having 12 to 15 carbon atoms and alkyl sulfates having 14 and 15 carbon atoms. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also alkyl ether sulfates having the formula R ^{1 is} -O- (AO) _n -SO ₃ ^- X ⁺ are suitable. In this formula, R ^{1 is} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ¹ are derived from fatty alcohols having 12 to 18 C atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxo alcohols having 10 to 20 C atoms.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n is an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n is 2, 3, 4, 5, 6, 7 or 8. X is a monovalent cation or the n-th part of an n-valent cation, preferred are the alkali metal ions and including Na ⁺ or K ⁺ , with Na ^{+ being} extremely preferred. Other cations X + may be selected from NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn 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-1

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na fatty alcohol ether sulfates having 12 to 18 C atoms and 2 EO (k = 11 to 13, n = 2 in formula A-1). The stated degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product. The indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

Furthermore, alkyl and / or alkenyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates derived from alkyl and / or alkenyl oligoglycosides of the general formula (A-2) R ⁶ -O- (G) (A-2) derive, be used, where
R ^{6 is} alkyl having 6 to 22 C atoms or alkenyl having 6 to 22 C atoms,
G glycoside unit, which is derived from a sugar with 5 or 6 carbon atoms,
p number from 1 to 10.

The use of alkyl and / or alkenyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates in textile treatment agents such as, for example, detergents or softeners, among other things, leads to improved color stability of dyed textiles and to improved cleaning performance of the detergent. When used in liquid detergents, in particular liquid detergents, the storage stability of the composition is increased compared with conventional dye transfer inhibitors. It is possible to use alkyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates, preferably alkyl oligoglycoside carboxylates or phosphates, in particular alkyl glycoside carboxylates.

In the alkyl and / or alkenyl oligoglycosides at least one hydroxyl group is preferably in at least one of the radicals G by -OC _1-12 -alkenyl-COOM, -OSO ₃ M, -OP (O) (OM) ₂ or -O- CH ₂ -CH ₂ - SO ₃ M, O-CH ₂ -CH ₂ -O-SO ₃ M, each with M = H, alkali metal or NH ₄ replaced. It is particularly preferred to use an alkyl oligoglycoside carboxylate in which -OC _1-12 -alkylene-COOM or -O (CH ₂ -) _n COOM with M = H, Na or K and n = 1 to 3, respectively. Particularly preferably, at least one OH group of the radical G according to the above formula is replaced by a group -O-CH ₂ -COONa.

Particular preference is given to using an alkyl oligoglycoside carboxylate in which the alkyl radical is a lauryl radical. Especially preferred is a Laurylglucosidcarboxylat as a Plantapon ^® LGC and Plantapon ^® LGC Sorb by BASF SE is available.

In the alkyl glycosides of the above formula (A-2), the glycoside units G are preferably derived from aldoses or ketoses.

Preferably, because of the better reactivity, the reducing saccharides, the aldoses, are used. Among the aldoses, glucose is particularly suitable for their easy accessibility and technical availability. The alkyl glycosides used as starting materials are therefore the alkylglucosides.

The index number p indicates the degree of oligomerization, i. The distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in a given compound always has to be an integer and can take here especially the values p = 1 to 6, the value p for a particular alkyl glycoside an analytic calculated arithmetical variable, which usually represents a fractional number. Preferably, alkyl glycosides having an average degree of oligomerization p of from 1.1 to 3.0 are used. Particularly preferred are those alkyl glycosides whose degree of oligomerization is less than 1.5 and in particular between 1.1, and 1.4.

The alkyl radical R is derived from primary alcohols having 6 to 22, preferably 12 to 18 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol and technical fractions which, in addition to the saturated alcohols mentioned, may also contain portions of unsaturated alcohols and which are based on natural fats and oils, for example palm oil, palm kernel oil, Coconut oil or beef tallow are obtained. The use of technical coconut oil is particularly preferred here.

In addition to the fatty alcohols mentioned, the alkyl glycosides can also be derived from synthetic primary alcohols having 6 to 22 carbon atoms, in particular the so-called oxo alcohols, which have a proportion of 5 to 40% by weight of branched isomers.

Particularly preferred alkyl radicals are those having 8/10, 12/14, 8 to 16, 12 to 16 or 16 to 18 carbon atoms. Mixtures of the alkyl radicals result in a production starting from natural fats and oils or mineral oils.

Processes for the preparation of these alkyl glycosides are described, for example, in the American patents US 3,547,828 and US 3,839,318 as well as the German patent application DE-A-37 23 826 described. For alkyl polyglycosides per se, for example, on the DE-A-100 27 975 . DE-A-101 38 094 and DE-A-100 31 014 to get expelled.

For a further discussion of the alkyl oligo / polyglycosides (APG), see the International Patent Publication WO 03/013450 directed.

The alkyl or alkenyl oligoglycoside carboxylates, phosphates, sulfates or isethionates used according to the invention can be prepared by known processes. The carboxylates are prepared, for example, by reacting the alkyloligoglycosides with salts of chlorocarboxylic acids in the presence of bases. For example, it can be reacted with 2-chloroacetic acid sodium salt in the presence of NaOH. In the reaction, both the hydroxyl groups in the ring and the -CH ₂ -OH group can be reacted. The degree of conversion depends inter alia on the stoichiometry of the feedstock. Preferably, the alkyl oligoglycosides are reacted at least on the -CH ₂ -OH group, optionally with an agent capable of reacting one or more of the hydroxyl groups on the ring.

Other hydroxyl groups may also be etherified, for example. The preparation of the isethionates is for example in the WO 94/26857 described. The preparation of the sulfates is for example in the WO 93/10208 and WO 91/15192 described. In the latter document are also mixtures of APG sulfates with, inter alia Alkyl sulfates or alkyl ether sulfates and other ingredients described. The preparation of the sulfates can also as in EP-A-0 186 242 described described. For example, the corresponding alkyl glycoside can be reacted with gaseous sulfur trioxide or with sulfuric acid followed by neutralization.

The anionic surfactants including the fatty acid soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts and / or ammonium salts. Amines which can be used for the neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being preferred. As already described above, however, the anionic surfactants can also be used as acid.

The liquid detergent according to the invention necessarily contains at least one enzyme.

"Variant" is at the level of proteins the term corresponding to "mutant" at the level of the nucleic acids. The precursor or parent molecules may be wild-type enzymes, that is, those obtainable from natural sources. They may also be enzymes which in themselves already represent variants, that is to say have already been changed with respect to the wild-type molecules. These include, for example, point mutants, those with changes in the amino acid sequence, multiple positions or longer contiguous regions, or else hybrid molecules composed of complementary sections of various wild-type enzymes.

By amino acid substitutions are meant substitutions of one amino acid against another amino acid. According to the invention, such substitutions are indicated by designation of the positions in which the exchange takes place, if appropriate combined with the relevant amino acids in the internationally used single-letter code. For example, "position 320 replacement" means that a variant in position having position 320 in the sequence of a reference protein has a different amino acid. Usually, such exchanges are carried out at the DNA level via mutations of single base pairs (see above). For example, "R320K" means that the reference enzyme at position 320 has the amino acid arginine, while the variant under consideration has the amino acid lysine at the homologizable position. "320K" means that any, that is usually a naturally given, amino acid at a position corresponding to position 320 is replaced with a lysine, which is located in that molecule in the same place. "R320K, L" means that the amino acid arginine at position 320 is replaced with lysine or leucine. And "R320X" means that the amino acid arginine at position 320 is replaced with an essentially any other amino acid.

In principle, the amino acid substitutions according to the invention designated by the present application are not limited to being the only substitutions in which the variant in question differs from the wild-type molecule. It is known in the art that the beneficial properties of single point mutations can complement each other. Thus, embodiments of the present invention include all variants which, in addition to other exchanges with the wild-type molecule, also comprise the exchanges according to the invention.

Furthermore, in principle, it does not matter in which order the relevant amino acid substitutions have been made, that is to say whether a corresponding point mutant is further developed according to the invention or if, for example, a variant of the invention is produced from a wild-type molecule which is further developed according to other teachings found in the prior art , It is also possible to carry out several exchanges simultaneously in a mutagenesis approach, for example according to the invention and others together.

It is preferred according to the invention if the enzyme contains at least one protease. A protease is an enzyme that cleaves peptide bonds by hydrolysis. Each of the enzymes from class EC 3.4 is included according to the invention (comprising each of the thirteen subclasses below). The EC number corresponds to Enzyme Nomenclature 1992 of NC-IUBMB, Academic Press, San Diego, Calif., 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 subgroup of serine proteases. The serine proteases or serine peptidases are a subset of the proteases that have serine in the active site of the enzyme that forms a covalent adduct with the substrate. Furthermore, the subtilases (and serine proteases) are thereby characterized by having two more amino acid residues in the active site 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 pyrolysin family. The proteases preferably excluded from the compositions according to the invention or preferably contained in reduced amounts are endopeptidases (EC 3.4.21).

"Protease activity" is present according to the invention if the enzyme has proteolytic activity (EC 3.4). Various types of protease activity are known: the three main types are: trypsin-like, with cleavage of the amide substrate following the amino acids Arg or Lys at P1; Chymotrypsin-like, with cleavage after one of the hydrophobic amino acids at P1; and elastase-like, wherein cleavage of the amide substrate after Ala occurs at P1.

The protease activity can after the in Surfactants, Vol. 7 (1970), pp. 125-132 method described. It is accordingly stated in PE (protease units). The protease activity of an enzyme can be determined according to customary standard methods, in particular using BSA as substrate (bovine albumin) and / or with the AAPF method.

It has surprisingly been found that a protease of the alkaline protease type from Bacillus lentus DSM 5483, or a sufficiently similar protease (in terms of sequence identity), which has several of these changes in combination, is particularly suitable and useful in the liquid surfactant composition of the invention advantageously improved stabilized. Advantages of the use of this protease thus arise in particular with regard to the washing performance and / or the 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 in the prior art and commonly used (cf., for example, US Pat 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 in principle occurs 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 respective positions is referred to as alignment. Another algorithm available in the prior art is the FASTA algorithm. Sequence comparisons (alignments), in particular multiple sequence comparisons, are created with computer programs. Frequently used, for example, the Clustal series (see, 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 application, all sequence comparisons (alignments) with the computer program Vector NTI ^® Suite 10.3 were (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, United States) created with the preset default parameters whose AlignX module for sequence comparisons ClustalW based ,

Such a comparison also allows a statement about the similarity of the compared sequences to each other. It is usually given in percent identity, that is, the proportion of identical nucleotides or amino acid residues at the same or in an alignment corresponding positions. The broader concept of homology involves conserved amino acid substitutions in the consideration of amino acid sequences, that is, amino acids with similar chemical activity, as these usually perform similar chemical activities within the protein. Therefore, the similarity of the sequences compared may also be stated as percent homology or percent similarity. Identity and / or homology information can be made about whole polypeptides or genes or only over individual regions. 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 comprise only a few nucleotides or amino acids. Often, such small regions exert essential functions for the overall activity of the protein. It may therefore be useful to relate sequence matches only to individual, possibly small areas. Unless otherwise indicated, identity or homology information in the present application, however, refers to the total length of the particular nucleic acid or amino acid sequence indicated.

The concentration of the protease in the detergent intended for this washing system is from 0.001 to 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 (preferably in addition to the protease) contain as enzyme at least one enzyme selected from α-amylase, cellulase, mannanase, lipase, pectate lyase.

In general, the enzymes contained in a composition of the invention may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation.

Compositions according to the invention may be added to the resulting enzymes in any form known in the art. These include in particular the solid preparations obtained by granulation, extrusion or lyophilization, advantageously as concentrated as possible, low in water and / or added with stabilizers. In an alternative dosage form, the enzymes may 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 entrapped as in a solidified gel, or in such Core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

The liquid surfactant compositions preferably additionally contain at least one cellulase. A cellulase is an enzyme. For cellulases, synonymous terms may be used, especially endoglucanase, endo-1,4-beta-glucanase, carboxymethylcellulase, endo-1,4-beta-D-glucanase, beta-1,4-glucanase, beta-1,4-endoglucan hydrolase , Celludextrinase or Avicelase. Crucial for determining whether an enzyme is a cellulase according to the invention is its ability to hydrolyze 1,4-.beta.-D-glucosidic bonds in cellulose.

According to the invention attachable cellulases (endoglucanases, EC) include, for example, fungal endoglucanase (EG) -rich cellulase preparation and developments thereof, which is offered by the company Novozymes under the trade name Celluzyme ^®. The products Endolase ^® and Carezyme ^® , also available from Novozymes, are based on the 50 kD EG or the 43 kD EG from Humicola insolens DSM 1800. Further commercial products of this company are Cellusoft ^® , Renozyme ^® and Celluclean ^® . Also usable are, for example cellulases, which are available from the company AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^®, and the at least partly based on the 20 kD EG Melanocarpus. Other cellulases from the company AB Enzymes are Econase® ^® and ECOPULP ^®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp. CBS 670.93 by the company Danisco / Genencor under the trade name Puradax® ^® available. Further usable commercial products of the company Danisco / Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants described in International Publication WO 98/12307 Cellulases from Melanocarpus, in particular Melanocarpus albomyces, disclosed in the international publication WO 97/14804 Cellulases of the EGIII type from Trichoderma reesei disclosed in the European patent application EP 1 305 432 and variations obtainable therefrom, in particular those disclosed in the European patent applications EP 1240525 and EP 1305432 , as well as cellulases, which are disclosed in international publications WO 1992006165 . WO 96/29397 and WO 02/099091. A The respective disclosure is therefore expressly referred to, or the disclosure content of which in this regard is expressly included in the present patent application.

Particularly preferred compositions according to the invention are characterized in that as additional cellulase at least one cellulase from Melanocarpus sp. or Myriococcum sp. 20K cellulase or those having homology in excess of 80% (more preferably greater than 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. 20K cellulase available is from the international patent application WO 97/14804 known. It has as described there a molecular weight of about 20 kDa and has at 50 ° C in the pH range of 4 to 9 at least 80% of their maximum activity, while still maintaining almost 50% of the maximum activity at pH 10. It can, as also described there, be isolated from Melanocarpus albomyces and produced in genetically engineered Trichoderma reseei transformants. Also useful in the present invention are cellulases having a homology of greater than 80% (more preferably greater than 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%) %, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5% , 99.6%, 99.7%, 99.8%, 99.9%) to 20K cellulase.

K20 cellulase is preferably used in amounts such that a composition of the present invention has a cellulolytic activity of from 1 NCU / g to 500 NCU / g (determinable by the hydrolysis of 1 wt% carboxymethylcellulose at 50 ° C and neutral pH and determination of the reducing Sugar by dinitrosalicylic acid, as from MJ Bailey et al. in Enzyme Microb. Technol. 3: 153 (1981) described; 1 NCU defines the amount of enzyme which produces reducing sugars in an amount corresponding to 1 nmol of glucose per second), in particular from 2 NCU / g to 400 NCU / g and more preferably from 6 NCU / g to 200 NCU / g. In addition, the composition according to the invention may optionally contain further cellulases.

A composition according to the invention preferably contains from 0.001 mg to 0.5 mg, in particular from 0.02 mg to 0.3 mg, of cellulolytic protein per gram of the total composition. The protein concentration can be determined by known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem. 177, 751-766, 1948 ).

It is again particularly preferred according to the invention, in addition to at least one first cellulase from Melanocarpus sp. or Myriococcum sp. 20K cellulase or those having homology in excess of 80% (more preferably greater than 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90%) , 5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5 %, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99, 6%, 99.7%, 99.8%, 99.9%) to employ at least one other second cellulase other than the first cellulase.

It is preferred according to the invention if the liquid surfactant compositions according to the invention additionally contain at least one lipase. Lipase enzymes which are preferred according to the invention are selected from at least one enzyme of 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).

The preferred field of use of the compositions according to the invention is the cleaning of textiles. Because washing and cleaning agents for textiles predominantly have alkaline pH values, lipases which are active in the alkaline medium are used in particular for this purpose.

Furthermore, the lipase preferably contained in a composition according to the invention is naturally present in a microorganism of the species Thermomyces lanuginosus or Rhizopus oryzae or Mucor javanicus or derived from the aforementioned naturally occurring lipases by mutagenesis. More preferably, the compositions according to the invention comprise at least one lipase naturally present in a microorganism of the species Thermomyces lanuginosus or derived from the aforementioned naturally occurring lipases in Thermomyces lanuginosus by mutagenesis. Naturally present in this context means that the lipase is a separate enzyme of the microorganism. The lipase can thus be expressed in the microorganism from a nucleic acid sequence which is part of the chromosomal DNA of the microorganism in its wild-type form. It or the coding for them nucleic acid sequence is therefore present in the wild-type form of the microorganism and / or can be isolated from the wild-type form of the microorganism from this. In contrast to this, a lipase not present in the microorganism or the nucleic acid sequence coding for it would have been deliberately introduced into the microorganism with the aid of genetic engineering, so that the microorganism would have been enriched by the lipase or the nucleic acid sequence coding for it. However, a lipase naturally present in a microorganism of the species Thermomyces lanuginosus or Rhizopus oryzae or Mucor javanicus may well have been produced recombinantly from another organism.

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

According to preferred lipases are those of the company Amano Pharmaceuticals under the names Lipase M-AP10 ^®, Lipase LE ^® and Lipase F ^® lipase enzymes (including lipase JV ^®) available. For example, the ^{Lipase F®} is naturally present in Rhizopus oryzae. The lipase M-AP10 ^®, for example, naturally present in Mucor javanicus.

Compositions of a most preferred embodiment of the invention contain at least one lipase selected from at least one or more polypeptides having an amino acid sequence that is at least 90% (and more preferably 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 strain DSM 4109 Thermomyces lanuginosus. It is again preferred if, starting from said wild-type lipase from strain DSM 4109, at least the amino acid change N233R is present.

In the context of 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 , On the revelation pamphlet WO 00/60063 A1 is expressly referred to in its entirety.

It is particularly preferred to employ in the compositions of the invention at least one lipase derived from the wild-type lipase of strain DSM 4109, in which at least one substitution of an electrically neutral or negatively charged amino acid by a positively charged amino acid was carried out from said wild-type lipase. 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 acid in the sense of the invention are G, A, V, L, I. , P, F, W, S, T, M, N, Q and C when C forms a disulfide bond. 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 substitutions is present in positions D96L, T213R and / or N233R, particularly preferably T213R and N233R.

A highly preferred lipase is commercially available under the tradename Lipex ^® from the company Novozymes (Denmark) to relate and advantageously used in the inventive cleaning compositions. Particularly preferred here are the lipase Lipex ^® 100 L (ex Novozymes A / S, Denmark) is. Preferred compositions are characterized in that, based on the total weight of the composition of said lipase enzyme from Lipex ^® 100 L in a total amount of 0.01 to 1.0 wt .-%, in particular from 0.02 to 0.1 by weight %, is included.

The compositions of the invention may additionally contain at least one mannanase as enzyme. Mannanase present in the composition according to the invention (in particular in a textile washing and cleaning agent preferred according to the invention) catalyzes, as part of its mannanase activity, the hydrolysis of 1,4-β-D-mannosidic bonds in mannans, galactomannans, glucomannans and galactoglucomannans. Said mannanase enzymes according to the invention are named according to enzyme nomenclature as E.C. Classified 3.2.1.78.

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

Suitable compositions of the invention contain, for example, mannanase, which is marketed under the name Mannaway ^® from Novozymes.

Mannanase enzymes have been identified in numerous Bacillus organisms:
WO 99/64619 discloses examples of high total surfactant liquid protease-containing detergent compositions of at least 20% by weight which additionally comprise mannanase enzyme.

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

Mannanase polypeptides from strains of the Thermoanaerobacter group, such as Caldicellulosiruptor, are preferably suitable according to the invention. Also useful in the invention are mannanase polypeptides of the fungi Humicola or Scytalidium, in particular the species Humicola insolens or Scytalidium thermophilum.

It is particularly preferred according to the invention when the mannanase enzyme compositions according to the invention comprise 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., more preferably selected from at least one member of the group from Bacillus sp. I633, 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 of the invention is selected from at least one member of the group that is formed

• i) polypeptides comprising an amino acid sequence which is at least 90% (more preferably at least 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94%) , 5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2% , 99.3%, 99.4%, 99.5%, 99.6%, 99.7% or 99.8%) Sequence identity to the polypeptide according to SEQ ID No.1 (see Sequence Listing WO 99/64619 ), and
• ii) polypeptides which 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 from 0.02 to 0.1 wt .-%, each based on the total weight of the composition in the The composition of the invention is included.

More preferably, in addition to the preferred protease of the alkaline protease type from Bacillus lentus DSM 5483 or in addition to the sufficiently similar protease (in terms of sequence identity), which has several of these changes in combination, the liquid surfactant composition of the invention additionally contains at least one α-amylase ,

α-Amylases (EC 3.2.1.1) hydrolyze internal α-1,4-glycosidic bonds of starch and starch-like polymers as an enzyme. This α-amylase activity, for example, the applications WO 97/03160 A1 and GB 1296839 measured in KNU (Kilo Novo Units). Here, 1 KNU stands for the amount of enzyme which hydrolyses 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, which is described, for example, in the application WO 02/10356 A2 is described. Thereafter, the oligosaccharides, disaccharides and glucose units released by the enzyme in the hydrolysis of starch are detected by oxidation of the reducing ends with dinitrosalic acid (DNS). The activity is obtained in μmol reducing sugars (in terms of maltose) per min and ml; This results in activity values in TAU. The same enzyme can be determined by various methods, whereby the respective conversion factors can vary depending on the enzyme and must therefore be determined by means of a standard. As an approximation one can calculate that 1 KNU corresponds to approx. 50 TAU. Another activity determination method is the measurement using the Quick-Start ^® test kit from Abbott, Abott Park, Illinois, USA.

An inventively preferred field of application of the liquid surfactant compositions according to the invention is the cleaning of textiles. Because detergents and cleaners for textiles predominantly have alkaline pH values, in particular α-amylases which are active in the alkaline medium are used for this purpose. Such are produced and secreted by microorganisms, ie fungi or bacteria, especially those of the genera Aspergillus and Bacillus. Based on these natural enzymes, there remains an almost unmanageable wealth of variants that have been derived by mutagenesis and have specific advantages depending on the field of application.

Examples of these are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens and from B. stearothermophilus, as well as their further developments improved for use in detergents or cleaners. 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, for example, the amylase ^LT® .

The prior art includes, inter alia, the three patent applications WO 96/23873 A1 . WO 00/60060 A2 and WO 01/66712 A2 , which have been registered by the company 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 those for all amylases with at least 80% identity to one of these four; they are said to have altered enzymatic properties in terms of thermal stability, oxidation stability and calcium dependence. The registration WO 00/60060 A2 also names a variety of possible amino acid changes in 10 different positions on the α-amylases from two different microorganisms and claims those for all amylases with a homology of at least 96% identity to them. WO 01/66712 A2 , finally, denotes 31 different, in part, with the aforementioned identical amino acid positions, in either of the two in the application WO 00/60060 A2 α-amylases have been mutated.

Out WO 96/23873 A1 For example, there is a concrete possibility to substitute an M in position 9 according to the count of AA560 for an L in the mentioned α-amylases, in position 202 M versus L and those in positions 182 and 183 (or 183 and 184) To delete amino acids. WO 00/60060 A2 among other things, specifically reveals 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 not relevant here G186R exchange), N299X (including in particular the not relevant here replacement N299A), R320K, E345R and R458K.

Most preferably, in addition to the preferred protease of the alkaline protease type from Bacillus lentus DSM 5483 or a sufficiently similar protease (in terms of sequence identity) comprising several of these changes in combination, the liquid surfactant composition of the invention additionally contains at least one α-amylase , which has a higher activity at temperatures between 10 and 20 ° C, as the amylase with the trade name "Stainzyme 12 L" from Novozymes.

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

wobei R¹ und R² jeweils unabhängig voneinander ausgewählt sind aus -OH, -Cl, -F, -Br, substituierten oder unsubstituierten C_1-8 Alkyl- oder Alkenylgruppen, substituierten oder unsubstituierten C_1-8 Heteroalkyl- oder Heteroalkenylgruppen, substituierten oder unsubstituierten Arylgruppen und substituierten oder unsubstituierten Heteroarylgruppen. Usually boron compounds such as boric acid are used to stabilize enzymes. In the context of the present invention, it is preferred if the detergent according to the invention based on its total weight less than 0.5 wt .-%, in particular less than 0.1 wt .-%, more preferably less than 0.05 wt .-% compounds of the formula (II)

wherein R ¹ and R ^{2 are} each independently selected from -OH, -Cl, -F, -Br, substituted or unsubstituted C _1-8 alkyl or alkenyl groups, substituted or unsubstituted C _1-8 heteroalkyl or heteroalkenyl groups, substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups.

The liquid detergents according to the invention necessarily contain at least one alkalizing agent or its salt in a total amount of from 5 to 20% by weight, preferably from 7 to 15% by weight.

The alkalizing agent or its salt is different from the components a), b) c) and d) of the detergent according to the invention and acts as a Brönsted base at least for the acid form of hydroxycarboxylic acid having 2 to 8 carbon atoms.

The total amount of the alkalizing agent and its salt, or the total of all the following preferred representatives, is calculated on the basis of the base form, i. if the alkalizing agent in the detergent according to the invention (partially) in its salt form, the counterion is neglected in the calculation of quantities and assumed for the salt content only the base form without the absorbed proton.

The alkalizing agents are preferably selected from (C ₂ to C ₆ ) alkanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or mixtures thereof.

According to the invention, the term (C ₂ to C ₆ ) -alkanolamine means organic amine compounds which have a carbon skeleton of two to six carbon atoms, to which at least one amino group (preferably exactly one amino group) and at least one hydroxyl group (again preferably exactly one hydroxy group ) binds.

Preferred (C ₂ to C ₆ ) alkanolamines according to the invention are preferably primary amines.

In the context of the invention, it is preferable to use at least one (C ₂ to C ₆ ) alkanolamine having exactly one amino group. Again, this is preferably a primary amine.

The composition according to the invention preferably contains at least one (C ₂ to C ₆ ) alkanolamine selected from 2-aminoethane-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentane-1 -ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropane -1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol (especially under 2-aminoethane-1-ol , 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropane-1,3-diol). Monoethanolamine has proven to be a particularly suitable (C ₂ to C ₆ ) alkanolamine as an alkalizing agent.

(C ₂ to C ₆ ) alkanolamine or its salt is particularly preferably contained in a total amount of 5 to 20 wt .-%, preferably from 7 to 15 wt .-%, in the detergents according to the invention.

In addition, inorganic salts (such as sodium, potassium, NH4 ⁺ , calcium or magnesium salts) may additionally be present in particular in a total amount of from 0.01 to 5% by weight, preferably in an amount of from 2 to 4% by weight.

The continuous phases of the detergents described herein are preferably homogeneous, low viscosity liquids in their own right. "Homogeneous" as used in this context refers to molecular disperse solutions and colloidal solutions which are stable under standard conditions, i. after 24 h at room temperature (25 ° C) and 1013 mbar have no optically perceptible phase separation, including precipitation.

"Low Viscosity" as used herein means that the low to no water anhydrous liquid detergent as described herein has a viscosity of less than 15,000 mPas, preferably from 1,000 to 5,000 mPas, more preferably from 2,000 to 3,000 mPas (Brookfield Viscometer, spindle # 3 at 20 ° C).

The said phases can be converted into a homogeneous, metastable phase by mechanical action, such as stirring or shaking, which converts back into the two-phase system within a service life of about 2 to 10 minutes. Before the dosage of the detergent according to the invention this must be converted by mechanical action in a homogeneous system.

In a preferred embodiment, in each case based on the weight of the respective phase contains a first continuous phase 1 wt .-% to 20 wt .-%, in particular 5 wt .-% to 15 wt .-% of component a) of the detergent according to the invention and a second continuous phase 20 to 50 wt .-%, in particular 30 to 45 wt .-% of component a) of the detergent according to the invention.

In a preferred embodiment, in each case based on the weight of the respective phase contains a first continuous phase 65 wt .-% to 95 wt .-%, in particular 70 wt .-% to 80 wt .-% component c) of the detergent according to the invention and a second continuous phase 5 to 35 wt .-%, in particular 20 to 30 wt .-% component c) of the detergent according to the invention.

In a preferred embodiment, in each case based on the weight of the respective phase contains a first continuous phase 65 wt .-% to 95 wt .-%, in particular 70 wt .-% to 80 wt .-% of component d) of the detergent according to the invention and a second continuous phase 5 to 35 wt .-%, in particular 20 to 30 wt .-% of component d) of the detergent according to the invention.

In a preferred embodiment, in each case based on the total weight of component e), a first continuous phase contains 0 wt .-% to 5 wt .-%, in particular 0 wt .-% to 2 wt .-%, particularly preferably 0 to 1 wt .-% component e) of the detergent according to the invention and a second continuous phase 95 to 100 wt .-%, in particular 98 to 100 wt .-%, particularly preferably 99 to 100 wt .-% of component e) of the detergent according to the invention.

• – 1 Gew.-% bis 20 Gew.-%, insbesondere 5 Gew.-% bis 15 Gew.-% Komponente a) des erfindungsgemäßen Waschmittels,
• – 65 Gew.-% bis 95 Gew.-%, insbesondere 70 Gew.-% bis 80 Gew.-% Komponente c) des erfindungsgemäßen Waschmittels,
• – 0,01 Gew.-% bis 6 Gew.-%, insbesondere 0,1 Gew.-% bis 3 Gew.-% Komponente e) des erfindungsgemäßen Waschmittels,

und eine zweite kontinuierliche Phase

• – 20 bis 50 Gew.-%, insbesondere 30 bis 45 Gew.-% Komponente a) des erfindungsgemäßen Waschmittels,
• – 5 bis 35 Gew.-%, insbesondere 20 bis 30 Gew.-% Komponente c) des erfindungsgemäßen Waschmittels,
• – 7 Gew.-% bis 25 Gew.-%, insbesondere 8 Gew.-% bis 20 Gew.-% Komponente e) des erfindungsgemäßen Waschmittels.

In a particularly preferred embodiment, in each case based on the weight of the respective phase contains a first continuous phase

• From 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight, of component a) of the detergent according to the invention,
• From 65% by weight to 95% by weight, in particular from 70% by weight to 80% by weight, of component c) of the detergent according to the invention,
• From 0.01% by weight to 6% by weight, in particular from 0.1% by weight to 3% by weight, of component e) of the detergent according to the invention,

and a second continuous phase

• From 20 to 50% by weight, in particular from 30 to 45% by weight, of component a) of the detergent according to the invention,
• From 5 to 35% by weight, in particular from 20 to 30% by weight, of component c) of the detergent according to the invention,
• - 7 wt .-% to 25 wt .-%, in particular 8 wt .-% to 20 wt .-% component e) of the detergent according to the invention.

In this case, it is again preferred if in each case based on the total weight of component d) said first continuous phase 0 wt .-% to 5 wt .-%, in particular 0 wt .-% to 2 wt .-%, particularly preferably 0 to 1 % By weight of component d) of the detergent according to the invention and said second continuous phase contains 95 to 100% by weight, in particular 98 to 100% by weight, particularly preferably 99 to 100% by weight of component d) of the detergent according to the invention.

The liquid detergents in preferred embodiments additionally contain one or more nonaqueous organic solvents. It is preferred that the detergent more than 1 wt.%, Preferably more than 5 wt.% And particularly preferably more than 10 wt.%, Each based on the total amount of detergent, non-aqueous solvent. Particularly preferred liquid detergents contain - based on their weight - 1 to 80 wt.%, Preferably 1 to 65 wt.%, Preferably 1 to 50 wt.%, Particularly preferably 5 to 40 wt.% And especially 10 to 30 wt.% non-aqueous solvents.

Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, the solvents are selected from ethanol, n-propanol, i- Propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, glycols such as diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, propylene glycol t-butyl ether, di-n-octyl ether and low molecular weight polyalkylene glycols, such as PEG 400, and mixtures of these solvents. In a preferred embodiment, the non-aqueous solvent is selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, or mixtures thereof. In a preferred embodiment, the non-aqueous solvent is ethanol, 1,2-propanediol, glycerol or a mixture thereof, most preferably glycerol. At least 1 to 12% by weight of glycerol and 0.1 to 5% by weight of ethanol are added with particular preference.

In addition, the detergent may contain other ingredients that further improve the performance and / or aesthetic properties of the detergent. In the context of the present invention, the detergent preferably additionally contains one or more substances from the group of enzymes, builders / complexing agents, bleaching agents, electrolytes, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, anti-shrinkage agents, anti-wrinkling agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.

If the detergent according to the invention contains bleach, hydrogen peroxide is preferably used as the bleaching agent.

As anti-redeposition agents are in particular polymers terephthalate-PEG-based, such as are commercially available for example under the trade name Texcare ^®, can be used. Alternatively, (co) polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol can also be used, preferably in mixtures with anti-redeposition agents.

Particularly suitable builders are organic builders, for example the polycarboxylic acids which can be used in the form of their sodium salts or else as acids, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, in particular glutamic acid-N, N-diacetic acid (GLDA) and methylglycine-N, N-diacetic acid (MGDA), and mixtures thereof. As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again 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 the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer. In liquid detergents, preference is given to using soluble builders, such as acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol.

In various embodiments of the invention, the liquid detergent may further contain oxalic acid in amounts, based on the total weight of the liquid detergent, of up to 15% by weight, in particular 1-12% by weight. The oxalic acid can further enhance the effectiveness of the detergent in removing rust stains.

• 1) Herstellen einer homogenen Lösung der Zitronensäure in dem mindestens einen nichtionischen Tensid oder einer Mischung aus dem mindestens einen nichtionischen Tensid und dem nichtwässrigen, organischen Lösungsmittel; und
• 2) Hinzufügen von Wasser und des Alkalisierungsmittels, ggf. unter Kühlung, sowie der optionalen übrigen Bestandteile des Waschmittels, und
• 3) Zugabe des Enzyms/der Enzyme Hierbei kann die Herstellung in beliebiger Reihenfolge der Schritte 1) und 2) erfolgen.

The detergents described herein can be prepared by methods known in the art. In one aspect, the invention also relates to methods of making the detergents described herein. Such methods may include, for example, the steps of:

• 1) preparing a homogeneous solution of the citric acid in the at least one nonionic surfactant or a mixture of the at least one nonionic surfactant and the nonaqueous organic solvent; and
• 2) adding water and the alkalizing agent, optionally with cooling, and the optional remaining components of the detergent, and
• 3) Addition of the Enzyme (s) Here, the preparation can be carried out in any order of steps 1) and 2).

The detergents described herein may be filled into a water-soluble wrapper and thus be part of a water-soluble wrapper. When the detergent is packaged in a water-soluble casing, it is preferred that the content of water is less than 10% by weight based on the total detergent and that anionic surfactants, if present, are in the form of their ammonium salts or as free acids ,

The neutralization with amines, unlike bases such as NaOH or KOH, does not lead to the formation of water. Thus, low-water detergents can be prepared which are directly suitable for use in water-soluble wraps. The water content can be reduced by suitable salts such as MgSO ₄ , MgCO ₃ , Na ₂ SO ₄ , Na ₂ CO ₃ and mixtures thereof.

A water-soluble packaging contains, in addition to the detergent, a water-soluble coating. The water-soluble coating is preferably formed by a water-soluble film material.

Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.

The thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of 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, may be the same or different.

The water-soluble package comprising the detergent and the water-soluble wrapper may have one or more chambers. The liquid detergent may be contained in one or more chambers, if any, of the water-soluble coating. The amount of liquid detergent preferably corresponds to the full or half dose needed for a wash.

It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 g / mol, preferably 20,000 to 500,000 g / mol, more preferably 30,000 to 100,000 g / mol and especially from 40,000 to 80,000 g / mol.

A suitable for preparing the water-soluble coating sheet material may additionally polymers, selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

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

Suitable water-soluble films for use in the casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films with the label Solublon ^® PT, Solublon ^® GA, Solublon KC ^® or Solublon ^® KL by Aicello Chemical Europe GmbH, or VF-HP film available from Kuraray.

The water-soluble packages may have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.

The water soluble package may include one or more chambers for storing one or more agents. If the water-soluble packaging has two or more chambers, at least one chamber contains a liquid detergent. The other chambers may each contain a solid or a liquid detergent.

All facts, objects and embodiments described for the detergents are also applicable to the use and the washing process, and vice versa.

In a second aspect, the present invention is directed to the use of the liquid laundry detergent of the first subject matter for laundering textiles, especially for removing stains based on deodorant, rust, berry, tea and red wine components and residues.

In a third aspect, the present invention is directed to a washing process wherein a liquid detergent of the first subject of the invention is used. Before the dosage of the detergent according to the invention from a storage container, this must be converted by mechanical action into a homogeneous system. The homogenization is omitted if the agent according to the invention is in the form of a disposable portion in a water-soluble or water-dispersible packaging, in particular in a polyvinyl alcohol-containing film.

It can, as already mentioned, the soiling be pretreated with the liquid detergent according to the invention before the actual washing process and / or first a washing solution can be provided which contains the liquid detergent according to the invention and which is then brought into contact with the textile to be cleaned.

Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent.

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

All embodiments described herein in connection with the detergents of the invention, particularly with regard to the specification of the ingredients, are equally applicable to the described methods and uses, and vice versa.

• 1. Flüssiges Waschmittel, enthaltend bezogen auf das Gewicht des gesamten Waschmittels jeweils in einer Gesamtmenge a) Wasser von 5 bis 35 Gew.%, bevorzugt 8 bis 30 Gew.%, besonders bevorzugt 10 bis 30 Gew.%, ganz besonders bevorzugt 15 bis 25 Gew.%, b) mindestens eine Hydroxycarbonsäure mit 2 bis 8 Kohlenstoffatomen oder deren Salz von 5 bis 30 Gew.%, vorzugsweise 10 bis 30 Gew.%, insbesondere 15 bis 25 Gew.%, c) mindestens ein nichtionisches Tensid von 5 bis 55 Gew.%, vorzugsweise 20 bis 55 Gew.%, insbesondere 35 bis 50 Gew.%, d) mindestens ein Enzym, e) mindestens ein Alkalisierungsmittel von 5 bis 20 Gew.-%, bevorzugt von 7 bis 15 Gew.-%,

wobei das flüssige Waschmittel
i) in Form eines Zweiphasensystems mit zwei separaten kontinuierlichen Phasen mit gemeinsamer Phasengrenze vorliegt und
ii) einen pH-Wert zwischen 2 und 6,5, insbesondere von 3 bis 5,5, besonders bevorzugt von 4,0 bis 6,0, aufweist.

• 2. Flüssiges Waschmittel nach Punkt 1, dadurch gekennzeichnet, dass es 5 bis 30 Gew.%, vorzugsweise 10 bis 30 Gew.%, insbesondere 15 bis 25 Gew.% mindestens einer, aliphatischen Hydroxycarbonsäure mit 3 bis 6 Kohlenstoffatomen, wobei besagte Hydroxycarbonsäure linear oder verzweigt ist, enthält.
• 3. Flüssiges Waschmittel nach Punkt 1 oder 2, dadurch gekennzeichnet, dass mindestens eine Hydroxycarbonsäure ausgewählt aus mindestens einem Vertreter der Gruppe, die gebildet wird aus Zitronensäure, Milchsäure, Weinsäure, Hydroxybernsteinsäure, Salicylsäure.
• 4. Flüssiges Waschmittel nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass das mindestens eine nichtionische Tensid ein Fettalkoholalkoxylat mit der nachstehenden Formel (I) umfasst R¹-O-(AO)_m-H (I), wobei R¹ ein linearer oder verzweigter Alkylrest ist, AO eine Ethylenoxid-(EO) und/oder Propylenoxid-(PO) Gruppierung ist, m eine ganze Zahl von 1 bis 50 ist.
• 5. Flüssiges Waschmittel nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass als Alkalisierungsmittel ausgewählt aus (C₂ bis C₆)-Alkanolamin, Natriumhydroxid, Kaliumhydroxid, Natriumcarbonat, Natriumhydrogencarbonat oder Mischungen daraus, bevorzugt aus (C₂ bis C₆)-Alkanolamin oder Mischungen daraus
• 6. Flüssiges Waschmittel nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass es als (C₂ bis C₆)-Alkanolamin mindestens ein (C₂ bis C₆)-Alkanolamin ausgewählt unter 2-Aminoethan-1-ol (Monoethanolamin), 3-Aminopropan-1-ol, 4-Aminobutan-1-ol, 5-Aminopentan-1-ol, 1-Aminopropan-2-ol, 1-Aminobutan-2-ol, 1-Aminopentan-2-ol, 1-Aminopentan-3-ol, 1-Aminopentan-4-ol, 3-Amino-2-methylpropan-1-ol, 1-Amino-2-methylpropan-2-ol, 3-Aminopropan-1,2-diol, 2-Amino-2-methylpropan-1,3-diol (insbesondere unter 2-Aminoethan-1-ol, 2-Amino-2-methylpropan-1-ol und 2-Amino-2-methyl-propan-1,3-diol), enthält.
• 7. Flüssiges Waschmittel nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass es jeweils bezogen auf das Gewicht der jeweiligen Phase eine erste kontinuierliche Phase mit 1 Gew.-% bis 20 Gew.-%, insbesondere 5 Gew.-% bis 15 Gew.-% Komponente a) des erfindungsgemäßen Waschmittels und eine zweite kontinuierliche Phase mit 20 bis 50 Gew.-%, insbesondere 30 bis 45 Gew.-% Komponente a) des erfindungsgemäßen Waschmittels, enthält.
• 8. Flüssiges Waschmittel nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass es jeweils bezogen auf das Gewicht der jeweiligen Phase eine erste kontinuierliche Phase mit 65 Gew.-% bis 95 Gew.-%, insbesondere 70 Gew.-% bis 80 Gew.-% Komponente c) des erfindungsgemäßen Waschmittels und eine zweite kontinuierliche Phase mit 5 bis 35 Gew.-%, insbesondere 20 bis 30 Gew.-% Komponente c) des erfindungsgemäßen Waschmittels, enthält.
• 9. Flüssiges Waschmittel nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass es jeweils bezogen auf das Gewicht der jeweiligen Phase eine erste kontinuierliche Phase mit 0,01 Gew.-% bis 6 Gew.-%, insbesondere 0,1 Gew.-% bis 3 Gew.-% Komponente e) des erfindungsgemäßen Waschmittels und eine zweite kontinuierliche Phase mit 7 Gew.-% bis 25 Gew.-%, insbesondere 8 Gew.-% bis 20 Gew.-% Komponente e) des erfindungsgemäßen Waschmittels, enthält.
• 10. Flüssiges Waschmittel nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass es jeweils bezogen auf das Gesamtgewicht der Komponente d) eine erste kontinuierliche Phase mit 0 Gew.-% bis 5 Gew.-%, insbesondere 0 Gew.-% bis 2 Gew.-%, besonders bevorzugt 0 bis 1 Gew.-% Komponente d) des erfindungsgemäßen Waschmittels und eine zweite kontinuierliche Phase mit 95 bis 100 Gew.-%, insbesondere 98 bis 100 Gew.-%, besonders bevorzugt 99 bis 100 Gew.-% Komponente d) des erfindungsgemäßen Waschmittels, enthält.
• 11. Flüssiges Waschmittel nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass es bezogen auf sein Gesamtgewicht weniger als 0,5 Gew.-%, insbesondere weniger als 0,1 Gew.-%, besonders bevorzugt weniger als 0,05 Gew.-% Verbindungen der Formel (II) enthält
  
  wobei R¹ und R² jeweils unabhängig voneinander ausgewählt sind aus -OH, -Cl, -F, -Br, substituierten oder unsubstituierten C_1-8 Alkyl- oder Alkenylgruppen, substituierten oder unsubstituierten C_1-8 Heteroalkyl- oder Heteroalkenylgruppen, substituierten oder unsubstituierten Arylgruppen und substituierten oder unsubstituierten Heteroarylgruppen,
• 12. Flüssiges Waschmittel nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass es sich das Mittel in einer wasserunlöslichen, wasserlöslichen oder wasserdispergierbaren Verpackung befindet, insbesondere in einer Polyvinylalkoholhaltigen Folie.
• 13. Verwendung eines wasserarmen bis wasserfreien Flüssigwaschmittels nach einem der Punkte 1 bis 12, zum Waschen von Textilien insbesondere zur Entfernungen von Anschmutzungen, die auf Bestandteilen und Rückständen von Deodorantien, Rost, Beeren, Tee und Rotwein basieren.
• 14. Waschverfahren zum Waschen von Textilien, dadurch gekennzeichnet, dass ein wasserarmes bis wasserfreies Waschmittel nach einem der Punkte 1 bis 12 eingesetzt wird.

Within the scope of a further preferred embodiment, the present invention is characterized by the following points:

• 1. Liquid detergent containing, based on the weight of the total detergent in each case in a total amount a) water of 5 to 35 wt.%, Preferably 8 to 30 wt.%, Particularly preferably 10 to 30 wt.%, Most preferably 15 to 25% by weight, b) at least one hydroxycarboxylic acid having 2 to 8 carbon atoms or a salt thereof of 5 to 30% by weight, preferably 10 to 30% by weight, in particular 15 to 25% by weight, c) at least one nonionic surfactant of 5 to 55% by weight , preferably 20 to 55% by weight, in particular 35 to 50% by weight, d) at least one enzyme, e) at least one alkalizing agent from 5 to 20% by weight, preferably from 7 to 15% by weight,

the liquid detergent
i) is in the form of a two-phase system with two separate continuous phases with common phase boundary, and
ii) has a pH between 2 and 6.5, in particular from 3 to 5.5, particularly preferably from 4.0 to 6.0.

• 2. Liquid detergent according to item 1, characterized in that it is 5 to 30 wt.%, Preferably 10 to 30 wt.%, In particular 15 to 25 wt.% Of at least one aliphatic hydroxycarboxylic acid having 3 to 6 carbon atoms, wherein said hydroxycarboxylic acid linear or branched contains.
• 3. Liquid detergent according to item 1 or 2, characterized in that at least one hydroxycarboxylic acid selected from at least one member of the group, which is formed from citric acid, lactic acid, tartaric acid, malic acid, salicylic acid.
• 4. Liquid detergent according to one of the preceding points, characterized in that the at least one nonionic surfactant comprises a fatty alcohol alkoxylate having the following formula (I) R ^{1 is} -O- (AO) _m -H (I), wherein R ^{1 is} a linear or branched alkyl radical, AO is an ethylene oxide (EO) and / or propylene oxide (PO) moiety, m is an integer from 1 to 50.
• 5. Liquid detergent according to one of the preceding points, characterized in that as alkalizing agent selected from (C ₂ to C ₆ ) alkanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or mixtures thereof, preferably from (C ₂ to C ₆ ) alkanolamine or mixtures thereof
• 6. Liquid detergent according to one of the preceding points, characterized in that as (C ₂ to C ₆ ) alkanolamine at least one (C ₂ to C ₆ ) alkanolamine selected from 2-aminoethane-1-ol (monoethanolamine), 3rd -Aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentane 3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino 2-methylpropane-1,3-diol (especially 2-aminoethan-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methyl-propane-1,3-diol), contains.
• 7. Liquid detergent according to one of the preceding points, characterized in that it is in each case based on the weight of the respective phase, a first continuous phase with 1 wt .-% to 20 wt .-%, in particular 5 wt .-% to 15 wt. -% component a) of the detergent according to the invention and a second continuous phase with 20 to 50 wt .-%, in particular 30 to 45 wt .-% of component a) of the detergent according to the invention contains.
• 8. Liquid detergent according to one of the preceding points, characterized in that it is in each case based on the weight of the respective phase, a first continuous phase with 65 wt .-% to 95 wt .-%, in particular 70 wt .-% to 80 wt. -% component c) of the detergent according to the invention and a second continuous phase with 5 to 35 wt .-%, in particular 20 to 30 wt .-% component c) of the detergent according to the invention contains.
• 9. Liquid detergent according to one of the preceding points, characterized in that in each case based on the weight of the respective phase, a first continuous phase with 0.01 wt .-% to 6 wt .-%, in particular 0.1 wt .-% to 3 wt .-% of component e) of the detergent according to the invention and a second continuous phase with 7 wt .-% to 25 wt .-%, in particular 8 wt .-% to 20 wt .-% of component e) of the detergent according to the invention contains ,
• 10. Liquid detergent according to one of the preceding points, characterized in that it is in each case based on the total weight of component d) a first continuous phase with 0 wt .-% to 5 wt .-%, in particular 0 wt .-% to 2 wt .-%, particularly preferably 0 to 1 wt .-% of component d) of the detergent according to the invention and a second continuous phase with 95 to 100 wt .-%, in particular 98 to 100 wt .-%, particularly preferably 99 to 100 wt. % Component d) of the detergent according to the invention.
• 11. Liquid detergent according to one of the preceding points, characterized in that it is based on its total weight less than 0.5 wt .-%, in particular less than 0.1 wt .-%, particularly preferably less than 0.05 wt. % Of compounds of the formula (II)
  
  wherein R ¹ and R ^{2 are} each independently selected from -OH, -Cl, -F, -Br, substituted or unsubstituted C _1-8 alkyl or alkenyl groups, substituted or unsubstituted C _1-8 heteroalkyl or heteroalkenyl groups, substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups,
• 12. Liquid detergent according to one of the preceding points, characterized in that it is the agent in a water-insoluble, water-soluble or water-dispersible packaging, in particular in a polyvinyl alcohol-containing film.
• 13. Use of a low-water to anhydrous liquid detergent according to any one of items 1 to 12, for washing textiles in particular for the removal of soils based on components and residues of deodorants, rust, berries, tea and red wine.
• 14. A washing process for washing textiles, characterized in that a low-water to anhydrous detergent according to any one of items 1 to 12 is used.

Examples

The following liquid detergents of Table 1 were prepared by mixing the components. Initially, a homogeneous solution of citric acid was prepared in a mixture of the nonionic surfactant and the nonaqueous organic solvent. Dan were added to water and the alkalizing agent and the remaining ingredients of the detergent and blended. Thereafter, the enzymes were added. Table 1: Liquid detergent E1 E2 E3 C _13-15 fatty alcohol with 7 units of ethylene oxide 32,30 31.4 31.1 Secondary C _14-17 alkanesulfonic acid sodium salt - 10.9 - C _12-14 glucamide - - 4.40 glycerin 13.78 12.5 12.50 hydroxypropyl methylcellulose 0.50 - - Citric acid · 1H ₂ O 13.85 12.50 12.50 formic acid - 3.50 2.60 CaCl ₂ .2H ₂ O 3.00 3.00 3.00 Diethylenetriamine penta (methylene phosphonic acid), hepta sodium salt 0.10 0.10 0.10 2-aminoethanol 9.19 9.30 7.30 Tiron 2,3-dihydroxy-1,4-disulfonate - 0.60 0.60 Esters of propanediol, phthalic acid and alphamethyl-omega-hydroxypoly (oxy-1,2-ethanediyl) (CAS 139755-78-5) 3.46 3.60 5.70 protease 1.20 1.20 1.20 amylase 0.40 0.40 0.40 cellulase 0.35 0.35 0.35 lipase 0.40 0.40 0.40 mannanase 0.40 0.40 0.40 Perfume 0,70- 0,70- 0.70 water ad 100 ad 100 ad 100 PH value 5.1 5.0 5.1 Viscosity measurement [mPas] 120 470 380 Optical appearance clear clear clear 2-phase 2-phase 2-phase

The above details of the ingredients are given in wt.%. Viscosity measurements were made with a Brookfield Viscosity Meter, Spindle # 3 at 20 ° C immediately after production. All inventive formulations E1 to E3 were initially single-phase and established after a life of about 2 to 4 hours two continuous phases, which could be reversibly converted into a single-phase system by mechanical action. All phases had a clear appearance. In all formulations E1 to E3, the enzymes could be incorporated storage stable.

The 2 phases of composition E1 were tested for their content of nonionic surfactant, alkanolamine, water and enzyme. The measurement results of the amounts in wt .-% based on the weight of the respective phase are summarized in Table 2: Table 2: Phase analysis of E1 Upper phase: E1 C _13-15 fatty alcohol with 7 units of ethylene oxide 79.20 2-aminoethanol 0.70 protease not detectable amylase not detectable cellulase not detectable lipase only detectable in traces mannanase not detectable water 11.00 Lower phase: C _13-15 fatty alcohol with 7 units of ethylene oxide <0.10 2-aminoethanol 17,60 protease detectable amylase detectable cellulase detectable lipase detectable mannanase detectable water 36,30

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely 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.

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Claims (10)

 Liquid detergent containing, based on the weight of the total detergent in each case in a total amount a) water of 5 to 35% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 30% by weight, very particularly preferably 15 to 25% by weight, b) at least one hydroxycarboxylic acid having 2 to 8 carbon atoms or its salt of 5 to 30% by weight, preferably 10 to 30% by weight, in particular 15 to 25% by weight, c) at least one nonionic surfactant of from 5 to 55% by weight, preferably from 20 to 55% by weight, in particular from 35 to 50% by weight, d) at least one enzyme, e) at least one alkalizing agent of from 5 to 20% by weight, preferably from 7 to 15% by weight, the liquid detergent i) is in the form of a two-phase system with two separate continuous phases with common phase boundary, and ii) has a pH between 2 and 6.5, in particular from 3 to 5.5, particularly preferably from 4.0 to 6.0. Liquid detergent according to claim 1, characterized in that it contains 5 to 30% by weight, preferably 10 to 30% by weight, in particular 15 to 25% by weight of at least one aliphatic hydroxycarboxylic acid having 3 to 6 carbon atoms, said hydroxycarboxylic acid linear or branched is, contains. Liquid detergent according to claim 1 or 2, characterized in that at least one hydroxycarboxylic acid selected from at least one member of the group formed from citric acid, lactic acid, tartaric acid, malic acid, salicylic acid. Liquid detergent according to one of the preceding claims, characterized in that the at least one nonionic surfactant comprises a fatty alcohol alkoxylate having the following formula (I) R ^{1 is} -O- (AO) _m -H (I), wherein R ^{1 is} a linear or branched alkyl radical, AO is an ethylene oxide (EO) and / or propylene oxide (PO) moiety, m is an integer from 1 to 50. Liquid detergent according to one of the preceding claims, characterized in that as alkalizing agent selected from (C ₂ to C ₆ ) alkanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or mixtures thereof, preferably from (C ₂ to C ₆ ) alkanolamine or mixtures it. Liquid detergent according to one of the preceding claims, characterized in that in each case based on the weight of the respective phase, a first continuous phase with 1 wt .-% to 20 wt .-%, in particular 5 wt .-% to 15 wt .-% Component a) of the detergent according to the invention and a second continuous phase with 20 to 50 wt .-%, in particular 30 to 45 wt .-% of component a) of the detergent according to the invention contains. Liquid detergent according to one of the preceding claims, characterized in that in each case based on the weight of the respective phase, a first continuous phase with 65 wt .-% to 95 wt .-%, in particular 70 wt .-% to 80 wt .-% Component c) of the detergent according to the invention and a second continuous phase with 5 to 35 wt .-%, in particular 20 to 30 wt .-% of component c) of the detergent according to the invention contains. Liquid detergent according to one of the preceding claims, characterized in that it is in each case based on the weight of the respective phase, a first continuous phase with 0.01 wt .-% to 6 wt .-%, in particular 0.1 wt .-% to 3 Wt .-% component e) of the detergent according to the invention and a second continuous phase with 7 wt .-% to 25 wt .-%, in particular 8 wt .-% to 20 wt .-% of component e) of the detergent according to the invention contains. Liquid detergent according to one of the preceding claims, characterized in that in each case based on the total weight of component d), a first continuous phase with 0 wt .-% to 5 wt .-%, in particular 0 wt .-% to 2 wt. %, more preferably 0 to 1 wt .-% of component d) of the detergent according to the invention and a second continuous phase with 95 to 100 wt .-%, in particular 98 to 100 wt .-%, particularly preferably 99 to 100 wt .-% component d) of the detergent according to the invention contains. Liquid detergent according to one of the preceding claims, characterized in that it is the agent in a water-insoluble, water-soluble or water-dispersible packaging, in particular in a polyvinyl alcohol-containing film.