EP3613838A1 - Washing or cleaning agent with improved protease performance - Google Patents

Abstract

The present invention relates to detergents and cleaning agents which contain boric acid and / or a derivative thereof and at least one protease as described herein, and the use of boric acid and / or a derivative thereof to increase the cleaning performance of a protease-containing washing or cleaning agent, the use of detergents and cleaning agents and the corresponding washing and cleaning processes.

Description

The present invention relates to detergents and cleaning agents which contain boric acid and / or a derivative thereof and at least one protease as described herein, and the use of boric acid and / or a derivative thereof to increase the cleaning performance of a protease-containing washing or cleaning agent, the use of detergents and cleaning agents and the corresponding washing and cleaning processes.

The use of enzymes in detergents and cleaning agents has been established in the prior art for decades. They serve to expand the range of services of the relevant funds according to their specific activities. These include in particular hydrolytic enzymes such as proteases, amylases, lipases and cellulases. The first three mentioned hydrolyze proteins, starch and fats and thus contribute directly to the removal of dirt. Cellulases are used especially because of their tissue effect. Another group of detergent and cleaning agent enzymes are oxidative enzymes, in particular oxidases, which, when used in conjunction with other components, are preferably used to bleach stains or to produce the bleaching agents in situ. In addition to these enzymes, which are subject to continuous optimization, further enzymes are constantly being made available for use in detergents and cleaning agents in order to be able to optimally tackle special soiling, such as pectinases, β-glucanases, mannanases or other hemicellulases (glycosidases) Hydrolysis especially of special vegetable polymers.

The longest established enzymes, which are contained in practically all modern, high-performance detergents and cleaning agents, are proteases and in particular serine proteases, which, according to the invention, also include the subtilases. They serve to break down protein-containing soiling on the items to be cleaned.

Various protease classes have been established as washing and cleaning agent proteases, for example metalloproteases. However, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) occupy an outstanding position among the detergent and cleaning agent proteases due to their favorable enzymatic properties such as stability or optimum pH. They are assigned to the serine proteases due to the catalytically active amino acids. They act as non-specific endopeptidases, which means that they hydrolyze any acid amide bonds that are inside peptides or proteins. Their pH optimum is usually in the clearly alkaline range. An overview of this family can be found in the article " Subtilases: Subtilisin-like Proteases "by R. Siezen, page 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996 , Subtilases are naturally formed by microorganisms; Among these, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.

In general, only selected proteases are suitable for use in liquid surfactant-containing preparations. Many proteases do not show sufficient catalytic performance in such preparations. For the use of proteases in cleaning agents, a high catalytic activity under conditions such as those that occur during a wash cycle is therefore particularly desirable.

From the international patent publications WO 2010/020475 and WO 2010/020476 it is known that certain substances can increase the performance of hydrolytic enzymes, in particular proteases. In these publications, amino acids, polyamino acids and anionic / polyanionic polymers are mentioned as such substances.

Modern detergents and cleaning agents also contain protease stabilizers which stabilize the proteases over longer periods of time, such as occur during storage. Various classes of substances are used as stabilizers, including Boric acid and its derivatives or peptide inhibitors. It is generally assumed that the stabilizers mentioned bind reversibly in the catalytic center of the protease and thereby inhibit the proteolytic activity. For this reason, many detergents and cleaning agents, in particular liquid detergents, contain boric acid / borate as an enzyme stabilizer, typically in a concentration of up to about 1% by weight.

Surprisingly, it has now been found that boric acid and its derivatives, in addition to the stabilizing effect at higher concentrations from about 1.5% by weight, also have a performance-increasing effect on special proteases in the washing or cleaning agent.

1. (i) Borsäure oder ein Derivat davon in einer Gesamtmenge von 1,5 bis 4,0 Gew.-%, vorzugsweise 2,0 bis 3,0 Gew.-% bezogen auf das Gesamtgewicht des Wasch- oder Reinigungsmittels; und
2. (ii) mindestens eine Protease, wobei die Protease eine Aminosäuresequenz umfasst, die mindestens 80 % Sequenzidentität mit der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge aufweist, wobei die Protease mindestens die Aminosäuresubstitution 99E, vorzugsweise mindestens die Substitutionen 3T, 4I, 99E, 199I, jeweils bezogen auf die Nummerierung gemäß SEQ ID NO:1 aufweist.

In a first aspect, the invention therefore relates to a detergent or cleaning agent, preferably liquid detergent

1. (i) boric acid or a derivative thereof in a total amount of 1.5 to 4.0% by weight, preferably 2.0 to 3.0% by weight, based on the total weight of the washing or cleaning agent; and
2. (ii) at least one protease, the protease comprising an amino acid sequence which has at least 80% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length, the protease at least the amino acid substitution 99E, preferably at least the substitutions 3T, 4I, 99E, 199I, each based on the numbering according to SEQ ID NO: 1.

• die Verwendung von Borsäure oder einem Derivat davon zur Steigerung der Reinigungsleistung eines protease-haltigen Wasch- oder Reinigungsmittels, vorzugsweise Flüssigwaschmittels, wobei die die Protease eine Aminosäuresequenz umfasst, die mindestens 80 % Sequenzidentität mit der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge aufweist, wobei die Protease mindestens die Aminosäuresubstitution 99E, vorzugsweise mindestens die Substitutionen 3T, 4I, 99E, 199I, jeweils bezogen auf die Nummerierung gemäß SEQ ID NO:1 aufweist und die Borsäure oder das Derivat davon in einer Menge von 1,5 bis 4,0 Gew.-%, vorzugsweise 2,0 bis 3,0 Gew.-%, bezogen auf das Gesamtgewicht des Wasch- oder Reinigungsmittels eingesetzt wird;
• die Verwendung eines Wasch- oder Reinigungsmittels wie hierin beschrieben, zum Waschen von Textilien oder Reinigen von festen Oberflächen; und
• ein Verfahren zur Reinigung von Textilien oder harten Oberflächen, dadurch gekennzeichnet, dass in mindestens einem Verfahrensschritt ein Wasch- oder Reinigungsmittel wie hierin beschrieben angewendet wird

Further objects of the present invention relate to:

• the use of boric acid or a derivative thereof to increase the cleaning performance of a protease-containing detergent or cleaning agent, preferably liquid detergent, the protease comprising an amino acid sequence which has at least 80% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length the protease has at least the amino acid substitution 99E, preferably at least the substitutions 3T, 4I, 99E, 199I, each based on the numbering according to SEQ ID NO: 1, and the boric acid or the derivative thereof in an amount of 1.5 to 4 , 0 wt .-%, preferably 2.0 to 3.0 wt .-%, based on the total weight of the detergent or cleaning agent is used;
• the use of a detergent or cleaning agent as described herein for washing textiles or cleaning solid surfaces; and
• a method for cleaning textiles or hard surfaces, characterized in that a detergent or cleaning agent as described herein is used in at least one process step

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art upon studying the following detailed description and claims. Anyone can
Feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not restricted to these examples. Unless stated otherwise, all percentages are% by weight based on the corresponding composition or the composition. Numerical ranges that are specified in the format "from x to y" include the values mentioned. If several preferred numerical ranges are specified in this format, it goes without saying that all ranges that result from the combination of the different endpoints are also covered.

"At least one" as used herein refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.

According to the invention, a protease is understood to mean all enzymes which are capable of hydrolyzing acid amide linkages of proteins. The proteases which can be used according to the invention are described in detail below.

Boric acid and its derivatives, as used herein, refers to boric acid, the salts and esters of boric acid, in particular alkali metal and alkaline earth metal borates, or the salts or esters of the compounds mentioned. In particular, the alkali metal salts are used as salts, the sodium salts being particularly preferred here.

The proteases used according to the invention are those which are derived from the alkaline protease from Bacillus lentus with the amino acid sequence according to SEQ ID NO: 1. The protease is selected from a protease comprising an amino acid sequence which has at least 80% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length and in each case based on the numbering according to SEQ ID NO: 1 at the position that corresponds to the position 99 corresponds to the amino acid substitution 99E, and optionally additionally at positions 3, 4 and 199, each based on the numbering according to SEQ ID NO: 1, which has amino acid substitutions 3T, 4I and 199I.

In preferred embodiments of the protease used according to the invention, the protease has at least the amino acid substitutions 3T, 4I, 99E and 199I, in each case based on the numbering according to SEQ ID NO: 1.

In the aforementioned embodiments, the rest of the amino acid sequence, i.e. the positions that are not mentioned as substituted correspond to those in SEQ ID NO: 1. Alternatively, the protease can also have further substitutions. It is thus possible, for example, and according to the invention, that the proteases as described above have one (or more) additional amino acid substitution (s) at one or more of the positions which are not positions 3, 4, 99 and, based on the numbering according to SEQ ID NO: 1, correspond.

In one embodiment of the invention, the protease comprises an amino acid sequence which is at least 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87% over the entire length of the amino acid sequence given in SEQ ID NO: 1. , 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% or 98.8% is identical, and in each case based on the numbering according to SEQ ID NO: 1 on the Position which corresponds to position 99, amino acid substitution 99E, and optionally additionally at positions 3, 4 and 199, in each case based on the numbering according to SEQ ID NO: 1, which has amino acid substitutions 3T, 4I and 199I.

In connection with the present invention, the feature means that a protease has the indicated substitutions, that it contains at least one of the corresponding amino acids at the corresponding positions, ie not all of the indicated positions have been mutated otherwise or deleted, for example by fragmentation of the protease.

The identity of nucleic acid or amino acid sequences is determined by a sequence comparison. This sequence comparison is based on the BLAST algorithm established and commonly used in the prior art (cf. for example Altschul, SF, Gish, W., Miller, W., Myers, EW & Lipman, DJ (1990) "Basic local alignment search tool." J. Mol. Biol. 215: 403-410 , and Altschul, Stephan F., Thomas L. Madden, Alejandro A. Schaffer, Jinghui Zhang, Hheng Zhang, Webb Miller, and David J. Lipman (1997): "Gapped BLAST and PSI-BLAST: a new generation of protein database search programs "; Nucleic Acids Res., 25, pp.3389-3402 ) and happens principally in that similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences are assigned to each other. A tabular assignment of the relevant positions is called alignment. Another algorithm available in the prior art is the FASTA algorithm. Sequence comparisons (alignments), in particular multiple sequence comparisons, are created using computer programs. For example, the Clustal series is frequently used (cf. for example Chenna et al. (2003): Multiple sequence alignment with the Clustal series of programs. Nucleic Acid Research 31, 3497-3500 ), T-Coffee (see 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. Sequence comparisons (alignments) are also possible with the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the specified standard parameters, whose AlignX module for sequence comparisons is based on ClustalW. Unless otherwise stated, the sequence identity given herein is determined using the BLAST algorithm.

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

In connection with the present invention, the indication that an amino acid position corresponds to a numerically designated position in SEQ ID NO: 1 therefore means that the corresponding position is assigned to the numerically designated position in SEQ ID NO: 1 in an alignment as defined above.

Functional fragments of the proteases described herein can also be used. "Functional fragments", as used herein, refers to enzymatically active polypeptides which are truncated by at least one, preferably two or more amino acids compared to the reference sequence N- and / or C-terminal. The activity of such fragments is at least 50%, preferably at least 60, 70, 80, 90, 95 or 100% of the activity of the reference enzyme.

1. (a) sie aus einer Protease wie oben beschrieben als Ausgangsmolekül erhältlich ist durch ein- oder mehrfache konservative Aminosäuresubstitution, wobei die Protease an der Position, die der Position 99 entspricht, die Aminosäuresubstitution 99E, sowie optional zusätzlich an den Positionen 3, 4 und 199, jeweils bezogen auf die Nummerierung gemäß SEQ ID NO:1, die Aminosäuresubstitutionen 3T, 4I und 199I aufweist; und/oder
2. (b) sie aus einer Protease wie oben beschrieben als Ausgangsmolekül erhältlich ist durch Fragmentierung, Deletions-, Insertions- oder Substitutionsmutagenese und eine Aminosäuresequenz umfasst, die über eine Länge von mindestens 200, 210, 220, 230, 240, 250, 260, 261, 262, 263, 264, 265, 266, 267 oder 268 zusammenhängenden Aminosäuren mit dem Ausgangsmolekül übereinstimmt, wobei die Protease an der Position, die der Position 99 entspricht, die Aminosäuresubstitution 99E, sowie optional zusätzlich an den Positionen 3, 4 und 199, jeweils bezogen auf die Nummerierung gemäß SEQ ID NO:1, die Aminosäuresubstitutionen 3T, 4I und 199I aufweist.

In various embodiments, the protease is characterized in that

1. (a) it is obtainable as a starting molecule from a protease as described above by single or multiple conservative amino acid substitution, the protease at the position corresponding to position 99, amino acid substitution 99E, and optionally additionally at positions 3, 4 and 199 , each based on the numbering according to SEQ ID NO: 1, which has amino acid substitutions 3T, 4I and 199I; and or
2. (b) it is obtainable as a starting molecule from a protease as described above by fragmentation, deletion, insertion or substitution mutagenesis and comprises an amino acid sequence which is at least 200, 210, 220, 230, 240, 250, 260, 261 in length , 262, 263, 264, 265, 266, 267 or 268 contiguous amino acids coincide with the starting molecule, the protease at the position which corresponds to position 99, the amino acid substitution 99E, and optionally additionally at positions 3, 4 and 199, each based on the numbering according to SEQ ID NO: 1, which has amino acid substitutions 3T, 4I and 199I.

In further refinements of the invention, the protease obtainable using such a method is at least 80%, 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%, or 98.8% identical to the amino acid sequence given in SEQ ID NO: 1 over its entire length.

In washing or cleaning agents according to the invention, which are present in a predominantly solid form in one embodiment and in a predominantly liquid, pasty or gel form in another embodiment, with liquid or gel forms being preferred, this is Enzyme, ie the protease, in an amount of 10 ^-5 to 2% by weight, preferably 0.001 to 1.0% by weight, more preferably 0.005% to 0.8% by weight, in each case based on the total weight of the detergent or cleaning agent contained in this. The quantities given always relate to the active protein and not the enzyme formulation used, which usually contains further constituents.

In various embodiments, the protease may be preformulated in an enzyme composition. The enzyme protein typically makes up only a fraction of the total weight of conventional enzyme preparations. Protease preparations used with preference contain from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight, particularly preferably from 0.4 to 20% by weight and in particular from 0.8 to 10% by weight .-% of the protease, based in each case on active protein and the total weight of the enzyme preparation. This enzyme composition can then be used in detergents or cleaning agents according to the invention and in amounts that lead to the above-mentioned final concentrations in the detergent or cleaning agent.

The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method. In this regard, the active protein concentration is determined by titrating the active centers using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).

An agent according to the invention or an enzyme preparation used according to the invention can contain at least one stabilizer, in particular a polyol, such as glycerol or 1,2-ethylene glycol, and / or an antioxidant, but also inhibitors, such as, for example, boric acid and / or derivatives thereof or peptide inhibitors. If the enzyme preparation contains boric acid and / or derivatives thereof, the amount can already correspond to the desired total amount in the detergent and cleaning agent, or it can be lower, in which case the rest is added separately until the desired concentration.

In the agents described here, the enzymes to be used, for example proteases, can also be made up together with accompanying substances, for example from fermentation. In liquid formulations, the enzymes are preferably used as enzyme liquid formulation (s).

The proteases are generally not provided in the form of the pure protein but rather, as already mentioned above, rather in the form of stabilized, storable and transportable preparations. These pre-made preparations include, for example, those by granulation, extrusion or lyophilization obtained solid preparations or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

In addition to the protease, agents according to the invention can contain one or more further enzymes, in particular from the following group: further proteases, amylases, hemicellulases, cellulases, lipases and oxidoreductases. The use of at least one amylase is particularly preferred.

The amylase (s) is preferably an α-amylase. The hemicellulase is preferably a β-glucanase, a pectinase, a pullulanase and / or a mannanase. The cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase. The oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.

The agents described herein include all conceivable types of washing or cleaning agents, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or for hand washing or cleaning. These include, for example, detergents for textiles, carpets, or natural fibers, for which the term detergent is used. This also includes, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard or solid surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term cleaning agent is used, i.e. in addition to manual and machine dishwashing detergents, for example also abrasives, glass cleaners, WC fragrance washer, etc. The detergents and cleaners in the context of the invention also include auxiliary washing agents which are added to the actual detergent in the case of manual or machine textile washing in order to achieve a further effect. Furthermore, detergents and cleaning agents within the scope of the invention also include textile pretreatment and post-treatment agents, i.e. agents with which the item of laundry is brought into contact before the actual laundry, for example for dissolving stubborn soiling, and also agents which are in one of the actual ones Textile laundry downstream step give the items to be washed further desirable properties such as comfortable grip, freedom from creasing or low static charge. The last mentioned means include fabric softener. In preferred embodiments, however, the agents of the invention are detergents, very particularly preferably liquid detergents, gel formulations also being included here. "Liquid", as used herein, refers to the property that the formulation is flowable, ie pourable, for example from a package, such as a plastic bottle, under conditions of use (20 ° C, 1013 mbar).

Embodiments of the present invention therefore include all liquid dosage forms of the agents described herein, which can optionally also consist of several phases. The dosage forms of the agent include pouches. The agent can be present, for example, in the form of a non-aqueous liquid detergent or dishwashing detergent or in the form of an aqueous liquid detergent or dishwashing detergent, liquid detergents being preferred in each case. Furthermore, the agent can be in the form of a one-component system. Such funds consist of one phase. Alternatively, an agent can consist of several phases. Such an agent is therefore divided into several components.

The detergents or cleaning agents described herein can furthermore additionally contain all known ingredients which are customary in such agents, preferably at least one further ingredient being present in the agent. The agents described herein can in particular contain surfactants, builders, builders, bleaches or bleach activators. They can also contain water-miscible organic solvents, sequestering agents, electrolytes, pH regulators and / or further auxiliaries such as optical brighteners, graying inhibitors, foam regulators, and colorants and fragrances, and combinations thereof.

Advantageous ingredients of agents described herein are disclosed in the international patent application WO2009 / 121725 , starting there on page 5, penultimate paragraph, and ending on page 13 after the second paragraph. Reference is expressly made to this disclosure and the content of the disclosure therein is included in the present patent application.

It is preferred according to the invention if the detergents and cleaning agents, in particular liquid detergents, contain at least one surfactant. Again, it is particularly preferred if, based on the weight of the liquid composition according to the invention, surfactant is present in a total amount of 10 to 70% by weight, in particular 20 to 65% by weight, very particularly preferably 30 to 65% by weight, in particular 30 to 60% by weight ,

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

The at least one anionic surfactant is preferably selected from the group comprising C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, C ₁₂ -C ₁₈ alkanesulfonates, ester sulfonates, alk (en) yl sulfates, fatty alcohol ether sulfates and mixtures thereof. It has been shown that these sulfonate and sulfate surfactants are particularly suitable for producing stable liquid compositions with a flow limit. Liquid compositions comprising C ₉ -C ₁₃ alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant have particularly good, dispersing properties and are therefore preferred. Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are C ₁₂ -C ₁₈ alkanesulfonates and the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates are also suitable anionic surfactants.

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

Also fatty alcohol ether sulfates, such as the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C12- 18-fatty alcohols with 1 to 4 EO are suitable. Alkyl ether sulfates having the formula (A-1) are preferred

R ¹ -O- (AO) _n -SO ₃ ^- X ⁺ (A-1)

In this formula (A-1), R ^{1 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ^{1 of} the formula (A-1) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the Representatives with an even number of carbon atoms are preferred. Particularly preferred radicals R ^{1 of} the formula (A-1) are derived from fatty alcohols with 12 to 18 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 20 carbon atoms ,

AO in formula (A-1) represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n of the formula (A-1) is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n 2, 3, 4, 5, 6, 7 or 8 is very particularly preferred. X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and among them Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X + can be selected from NH4 ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½ Ca 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 agents contain an alkyl ether sulfate selected from fatty alcohol ether sulfates of the formula A-2

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

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

in der
R' und R" unabhängig H oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 C-Atome enthalten, und Y⁺ ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations (insbesondere Na⁺) bedeuten.It is very particularly preferred if the washing and cleaning agent, in particular liquid washing agent, contains at least one anionic surfactant of the formula (A-3)

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

In addition to the anionic surfactant, the agent / composition can also contain soaps. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants and the soaps can be in the form of their sodium, potassium or magnesium or ammonium salts. The anionic surfactants are preferably in the form of their ammonium salts, said ammonium ion being derived from at least one (C ₂ -C ₆ ) -alkanolamine. Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine, monoethanolamine, triethanolamine or methylethylamine.

The composition (preferably together with at least one anionic surfactant) can also have at least one nonionic surfactant. The nonionic surfactant includes alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof. It is again particularly preferred if, based on the weight of the agents according to the invention, non-ionic surfactant is contained in a total amount of 10 to 40% by weight, in particular 15 to 35% by weight.

The nonionic surfactant used is preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 5 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C12-14 alcohols with 4 EO or 7 EO, C9-11 alcohol with 7 EO, C13-15 alcohols with 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO (propylene oxide) groups together in the molecule can also be used according to the invention. Also suitable are a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C ₁₆ -C ₁₈ fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. The washing, cleaning, post-treatment or auxiliary washing agent particularly preferably contains a C ₁₂ -C ₁₈ fatty alcohol with 7 EO or a C ₁₈ -C ₁₅ oxo alcohol with 7 EO as a nonionic surfactant.

R³

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

XO

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

m

für ganze Zahlen von 1 bis 50 stehen.

The detergent and cleaning agent, in particular liquid detergent, particularly preferably contains at least one nonionic surfactant of the formula (N-1)

R ³ -O- (XO) _m -H, (N-1)

in the

R ³

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

XO

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

m

stand for integers from 1 to 50.

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

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

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

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

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

The agents according to the invention preferably additionally contain at least one further active substance. Active substances within the meaning of the present invention are selected in particular from the group of enzymes (apart from the protease used according to the invention), builders / complexing agents, bleaching agents, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, anti-shrink agents, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bitter agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents, softening components and UV absorbers.

At least one active substance is preferably selected from enzymes (in addition to the proteases used according to the invention), optical brighteners, builders, solvents, antiredeposition agents, color transfer inhibitors, preservatives, perfume or mixtures of at least two of the aforementioned active substances.

It is preferred if the liquid composition according to the invention additionally contains at least one enzyme, in particular selected from amylase, lipase, mannanase, cellulase, pectate lyase or mixtures thereof. In addition to the protease described above, other proteases can also be present.

It is further preferred that at least one optical brightener is contained in the agents of the invention, which consists of the substance classes of dis-tyrylbiphenyls, the stilbenes, the 4,4'-diamino-2,2'-stilbene disulfonic acids, the coumarins, the dihydroquinolinones , the 1,3-diarylpyrazolines, the naphthalimides, the benzoxazole systems, the benzisoxazole systems, the benzimidazole systems, the pyrene derivatives substituted by heterocycles and mixtures thereof are selected. These substance classes of optical brighteners have a high stability, a high light and oxygen resistance and a high affinity for fibers.

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

According to the invention, the composition can further comprise builders. Polymeric polycarboxylates, for example, are suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g / mol.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn be preferred from this group.

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

As builders, which can be contained in the composition according to the invention, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are to be mentioned in particular. As an additional Builders are particularly suitable organic builders, for example the polycarboxylic acids which can be used in the form of their sodium salts or also as acids, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, especially glutamic acid-N, N-diacetic acid (GLDA) and methylglycine-N, N-diacetic acid (MGDA), as well as mixtures of these. Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g / mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve water solubility, the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers. Soluble builders, such as acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol, are preferably used in liquid detergents.

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

The composition preferably further contains one or more non-aqueous solvents. Suitable non-aqueous solvents include monohydric or polyhydric alcohols or glycol ethers, such as, for example, ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methyl propanediol, glycerol, glycols, such as diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol , Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, 3-ethoxytrigoxyethyl, 2-butoxytrigoxyethyl, 3-methoxybutyloxy, 3-methoxybutyloxy-2, -4-hydroxymethyl-1,3-dioxolane, propylene glycol t-butyl ether, di-n-octyl ether and low molecular weight polyalkylene glycols, such as PEG 400, and mixtures of these solvents.

The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-ether, n-butyl butyl Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, Propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene-glycol-t-butyl ether, di-n-octyl ether and solvent di-n-octyl ether.

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

Antiredeposition agents which can be used are in particular based on (co) polymers based on polyethyleneimine, based on polyvinyl acetate and polyethylene glycol or on the basis of terephthalic acid polyesters, preferably in mixtures with antiredeposition agents.

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

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

It is preferred that the color transfer inhibitor is a polymer or copolymer of cyclic amines such as vinyl pyrrolidone and / or vinyl imidazole. Polymers useful as a color transfer inhibitor include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol and vinylimidazole copolymers of vinylpyridolide as well as mixtures thereof. Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) are particularly preferably used as color transfer inhibitors. The polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53 available. The copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000. A PVP / PVI copolymer is commercially available, for example, from BASF under the name Sokalan® HP 56. Another extremely preferred color transfer inhibitor is polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, under the name Sokalan® HP 66 from BASF are.

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

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

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

According to the invention, the term (C ₂ to C ₆ ) alkanolamine is understood to mean 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 hydroxyl 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 preferred to use at least one (C ₂ to C ₆ ) alkanolamine with exactly one amino group. Again, this is preferably a primary amine.

The agent according to the invention preferably contains at least one (C ₂ to C ₆ ) alkanolamine selected from 2-aminoethan-1-ol (monoethanolamine), tris (2-hydroxyethyl) amine (triethanolamine), 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-aminopentane 4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol, 2-amino-2-methylpropane-1,3- diol (especially under 2-aminoethan-1-ol, 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propan-1,3-diol), or mixtures thereof. Monoethanolamine has proven to be a particularly suitable alkalizing agent.

Such a (C ₂ to C ₆ ) alkanolamine or its salt is particularly preferably present in a total amount of 1 to 20% by weight, preferably 2 to 15% by weight, in the washing and cleaning agents according to the invention, in each case related to the basic form.

According to the invention, liquid compositions are preferred, in particular liquid single and multi-component detergents. These can be pre-portioned in a container (pouch) made of water-soluble material. The container for a multi-component detergent comprises at least two spatially separated chambers (multi-chamber pouch), for example 2, 3, 4, 5, 6 or 7 chambers. These chambers are separated from one another in such a way that the liquid compositions of the detergent contained do not come into contact with one another. This separation can be done, for example, by a wall made of the same material as the container itself.

It is therefore preferred according to the invention to assemble a liquid multi-component detergent in a container made of water-soluble material with at least two separate chambers, the at least one first liquid composition in at least one chamber and the at least one second liquid chamber in at least one different chamber Composition.

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

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

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

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

In one embodiment of the invention, the water-soluble material comprises mixtures of different substances. Such mixtures enable the mechanical properties of the container to be adjusted and can influence the degree of water solubility.

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

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

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

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98 to 99 mol% or 87 to 89 mol -%, so still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

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

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

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

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

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

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

Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to the desired values. PVAL films are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

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

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

Preferred water-soluble materials are characterized in that they comprise hydroxypropylmethyl cellulose (HPMC) which have a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9, and has a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

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

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

H- [O-CH ₂ -CH ₂ ] _n -OH

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

Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

In the context of the present invention, preference is given to water-soluble materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.

Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights (MW): approx. 20 to 30% straight-chain amylose (MW approx. 50,000 to 150,000) and 70 to 80% branched-chain Amylopectin (MW approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with around 300 to 1,200 glucose molecules due to the binding in the 1,4-position, the chain in the amylopectin branches to an knot-like structure after an average of 25 glucose units through 1,6 binding with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which can be obtained from polymer-analogous reactions from starch are also suitable for the production of water-soluble containers in the context of the present invention. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ 0 ₅ ) and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The water-soluble material can have other additives. These are, for example, plasticizers, such as, for example, dipropylene glycol, ethylene glycol or diethylene glycol, water or disintegrating agents.

Polyvinyl alcohol is particularly preferably used as the water-soluble material. On the one hand, this is easy to process and inexpensive to maintain. In addition, it is particularly soluble in water and thus enables the container to be used in a variety of ways.

It is preferred according to the invention if at least one bittering agent is contained in the water-soluble material to increase product safety.

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

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

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

Suitable glycosides are, for example, flavonoids such as quercetin or naringin or iridoid glycosides such as aucubin and in particular secoiridoid glycosides such as amarogentin, dihydrofoliamentin, gentiopicroside, gentiopicrin, swertiamarin, sweroside, gentioflavoside, centauroside, methiafinicin or centapurin, harpagin, or harpagin.

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

Suitable isoprenoids include, for example, sequiterpene lactones such as absinthin, artabsin, cnicin, lactucin, lactucopikrin or salonitenolide, monoterpene ketones (thujones) such as, for example, α-thujone or β-thujone, tetranortriterpenes (limonoids) such as desoxylimones, isoxylinonic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoic acid, limonoid acid , Obacunon, Obacunonic acid, Nomilin or Nomilinsäure, Terpenes like Marrubin, Premarrubin, Carnosol, Carnosolsäure or Quassin.

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

Suitable alkaloids are, for example, quinine hydrochloride, quinine hydrogen sulfate, quinine dihydrochloride, quinine sulfate, columbine and caffeine.

Suitable amino acids include, for example, threonine, methionine, phenylalanine, tryptophan, arginine, histidine, valine and aspartic acid.

Particularly preferred bitter substances are quinine sulfate (bitter value = 10,000), naringin (bitter value = 10,000), sucrose octaacetate (bitter value = 100,000), quinine hydrochloride, denatonium benzoate (bitter value> 100,000,000) and mixtures thereof, very particularly preferably denatonium benzoate (for example available as Bitrex®) ,

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

Another object is the use of a washing or cleaning agent described herein for washing textiles or cleaning solid surfaces, in particular in washing and cleaning processes.

Another object is a method for cleaning textiles or hard or solid surfaces, which is characterized in that an agent described here is used in at least one process step, in particular in such a way that the protease in an amount of from 40 µg to 4g, preferably from 50 µg to 3 g, particularly preferably from 100 µg to 2 g and very particularly preferably from 200 µg to 1 g.

In various embodiments, such processes are characterized in that the protease is used at a temperature of 0-100 ° C., preferably 0-60 ° C., more preferably 20-45 ° C. and most preferably at 40 ° C.

This includes both manual and machine processes, with machine processes being preferred. Processes for cleaning textiles are generally characterized in that various cleaning-active substances are applied to the items to be cleaned and washed off after the contact time in several process steps, or in that the items to be cleaned are treated in some other way with a detergent or a solution or dilution of this agent. The same applies to processes for cleaning materials other than textiles, especially hard or solid surfaces. All conceivable washing or cleaning processes can be enriched in at least one of the process steps by the use of a washing or cleaning agent described herein and then represent embodiments of the present invention.

All facts, objects and embodiments that are described for means described herein are also applicable to the aforementioned methods and uses. Therefore, reference is expressly made to the disclosure at the appropriate point at this point, with the note that this disclosure also applies to the methods and uses described above.

Examples Example 1: Activity determination of the protease

The following detergent matrix A was used: Table 1: Detergent matrix used (A) Chemical name % By weight in the formulation Water demin. ad 100 alkyl benzene sulfonic acid 20 C _12-18 fatty alcohol _ether sulfate with 2 EO 5 C _12-18 fatty acid Na salt 3 C ₁₂ - ₁₄ fatty alcohol ether with 7EO 10 Phosphonate (HEDP) 2 citric acid 3 Opt. Brightener (stilbene type) 0.1 NaOH 1 Monoethanolamine 8th 1,2-propylene glycol 12 Enzymes (amylase, mannanase, lipase, pectinase) 0.95 perfume 1.00 dye 0.1

The following formulations were produced (all figures in% by weight) Table 2: Formulations E1 E2 V1 V2 WM matrix A 96.5 96.5 96.5 96.5 Protease (according to the invention) 2 2 - - reference protease 2 2 boric acid 1.5 2.0 1.5 2.0 water 0.5 - 0.5 -

The amount of NaOH was chosen so that a pH of 8.0 was reached.

The enzyme according to the invention was an enzyme with the amino acid sequence according to SEQ ID NO: 1 and the substitutions 3T, 4I, 99E, 199I. The protease "Vinzon® 150 L" (7% by weight active protease enzyme), available from Novozymes, served as the reference protease.

The formulations were freshly produced and examined directly for cleaning performance at a washing temperature of 20 ° C with 28 enzyme-sensitive soils in order to exclude the enzyme-stabilizing effect of boric acid during long storage. After washing and drying, the reflectance of the stains was measured individually in Y units ("Datacolor Spectraflash 600" color measuring device). The wash test was repeated 5 times and average Y values for the individual stains were added and added to obtain a total Y value. The results are shown in Table 3: Table 3: Results of the washing test E1 981 E2 1002 V1 990 V2 989

It can be seen that formulation E2 according to the invention gives the highest Y values, which indicates the best performance in this comparison. Furthermore, the increase from E1 to E2 indicates that with the same enzyme concentration, an increase in the enzyme performance results from an increase in the boric acid concentration. The comparative formulas show that increasing the boric acid concentration in the reference enzyme does not improve the performance.

Claims (8)

Containing detergents or cleaning agents, preferably liquid detergents (i) boric acid or a derivative thereof in a total amount of 1.5 to 4.0% by weight, preferably 2.0 to 3.0% by weight, based on the total weight of the washing or cleaning agent; and (ii) at least one protease, the protease comprising an amino acid sequence which has at least 80% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length, the protease at least the amino acid substitution 99E, preferably at least the substitutions 3T, 4I, 99E, 199I, each based on the numbering according to SEQ ID NO: 1. Detergent or cleaning agent according to claim 1, characterized in that the protease in an amount of 10 ^-5 to 2 wt .-%, preferably 0.001 to 1.0 wt .-%, more preferably 0.005 wt .-% to 0.8 % By weight, based in each case on the total weight of the washing or cleaning agent, is contained therein. Washing or cleaning agent according to one of claims 1 or 2, characterized in that the agent further contains at least one anionic surfactant, preferably at least one anionic surfactant selected from the group of C _9-13 alkyl benzene sulfonates (LAS) and fatty alcohol ether sulfates (FAEOS), particularly preferably combinations of the above. Washing or cleaning agent according to one of claims 1 to 3, characterized in that the agent further contains at least one nonionic surfactant, preferably a nonionic surfactant selected from the group of fatty alcohol ethers (FAEO). Washing or cleaning agent according to one of claims 1 to 4, characterized in that the agent further contains at least one further active ingredient, in particular selected from the group of enzymes, builders / complexing agents, bleaching agents, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes , Foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, anti-shrink agents, anti-crease agents, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids and softening agents, anti-softening agents, anti-softening agents and anti-emulsifying agents, anti-softening agents and anti-emulsifying agents, anti-softening agents and anti-softening agents , Use of boric acid or a derivative thereof to increase the cleaning performance of a protease-containing detergent or cleaning agent, preferably liquid detergent, the protease comprising an amino acid sequence which has at least 80% sequence identity with the amino acid sequence given in SEQ ID NO: 1 over its entire length , wherein the protease has at least the amino acid substitution 99E, preferably at least the substitutions 3T, 4I, 99E, 199I, in each case based on the numbering according to SEQ ID NO: 1, and the boric acid or the derivative thereof in an amount of 1.5 to 4, 0 wt .-%, preferably 2.0 to 3.0 wt .-%, based on the total weight of the detergent or cleaning agent is used. Use of a washing or cleaning agent according to one of claims 1 to 5, for washing textiles or cleaning solid surfaces. Process for cleaning textiles or hard surfaces, characterized in that a washing or cleaning agent according to one of claims 1 to 5 is used in at least one process step.