EP3303540A1

EP3303540A1 - Acyl hydrazones for use as enzyme stabilizers

Info

Publication number: EP3303540A1
Application number: EP16724661.0A
Authority: EP
Inventors: André HÄTZELT; Timothy O'connell
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2015-06-08
Filing date: 2016-05-25
Publication date: 2018-04-11
Also published as: DE102015210416A1; WO2016198259A1

Abstract

The present invention relates to detergents and cleaning agents containing at least one protease and at least one acyl hydrazone compound of the formula (1) which acts as a protease inhibitor and therefore is a suitable enzyme stabilizer, and to the use of said compounds as enzyme stabilizers in protease-containing detergents and cleaning agents. The invention also relates to the corresponding washing and cleaning methods and to the use of the detergents and cleaning agents according to the invention.

Description

Acylhydrazones as enzyme stabilizers

The present invention relates to detergents and cleaners containing at least one enzyme and at least one acylhydrazone, which acts as a protease inhibitor and is thus a suitable enzyme stabilizer, as well as the use of these acylhydrazones as enzyme stabilizers in enzyme-containing detergents and cleaners.

The use of enzymes in detergents and cleaners has been established in the art for decades. They serve to extend the range of services of the funds concerned according to their specific activities. These include in particular hydrolytic enzymes such as proteases, amylases, lipases and cellulases. The first three hydrolyze proteins, starches and fats and thus contribute directly to soil removal. Cellulases are used in particular because of their tissue effect. Another group of washing and cleaning agent enzymes are oxidative enzymes, in particular oxidases, which, if appropriate, in combination with other components, are preferably used to bleach soiling or to produce the bleaching agents in situ. In addition to these enzymes, which are subjected to constant optimization, further enzymes are constantly being made available for use in detergents and cleaners in order to be able to optimally address particular soiling, such as pectinases, β-glucanases, mannanases or other hemicellulases (glycosidases) Hydrolysis in particular of special vegetable polymers.

The enzymes that are the longest-established and contained in virtually all modern, high-performance detergents and cleaners are proteases that serve to break up proteinaceous soiling on the items to be cleaned. However, they also hydrolyze themselves (autoproteolysis) and all other proteins contained in the agents concerned, i. especially enzymes, and therefore have a reduced storage stability in detergent formulations. Due to the reduced storage stability, the washing performance drops markedly after storage and moreover, aesthetic parameters can also change. This is particularly problematic in gel or liquid and especially in water-containing formulations, because in these with the water contained both the reaction medium and the hydrolysis reagent is provided.

One goal in the development of detergent formulations is to stabilize the enzymes contained, especially during storage. Below that is the protection against understood various unfavorable influences, such as against denaturation or decay by physical influences or oxidation. One focus of these developments is the protection of the contained proteins and / or enzymes against proteolytic cleavage. This can be done by the construction of physical barriers, such as by encapsulation of the enzymes in special enzyme granules or by packaging the means in two- or multi-chamber systems. The other many pathway is to add chemical compounds that inhibit the proteases and thus act collectively as stabilizers for proteases and the other proteins and enzymes contained. It must be reversible protease inhibitors, since the protease activity is only temporarily, especially during storage, but not be suppressed during the cleaning process.

As detergency and detergent proteases various protease classes are established, for example metalloproteases. However, among the detergent and detergent proteases, subtilisin-type proteases (subtilases, subtilopeptidases, EC 3.4.21.62) occupy an outstanding position due to their favorable enzymatic properties such as stability or pH optimum. They are attributed to the serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases, that is, they hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. For an overview of this family, see for example the article "Subtilases: Subtilisin-like Proteases" by R. Siezen, pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996. Subtilases are naturally formed by microorganisms; Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.

Boron compounds, such as, for example, borax, boric acids, boronic acids or their salts or esters, are currently used as enzyme inhibitors in the prior art. These include, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or esters of the compounds mentioned. A particularly good protection results when boric acid derivatives are used together with polyols, since these can then form a complex stabilizing the enzyme. However, regardless of their stabilizing effect, the boric acid derivatives have a significant disadvantage: many of them, such as borate, form undesirable by-products with some other detergent ingredients, so that they are no longer available in the agents concerned for the desired cleaning purpose, or even remain as an impurity on the laundry. In addition, due to legal and toxicological / ecotoxicological reasons, the use of boron compounds, in particular their release, should be viewed critically. The object of the present invention was therefore to identify boron-free compounds which act as protease inhibitors and are suitable for use as enzyme stabilizers in detergents and cleaners and which guarantee a storage stability comparable to boron-containing stabilizers. Here, the use in total liquid, gel or pasty detergents and cleaning agents of particular interest, and including in particular those containing water.

This object is achieved by washing or cleaning agents which comprise at least one protease and at least one enzyme stabilizer, the at least one enzyme stabilizer comprising an acylhydrazone of the formula (1)

in E or Z configuration or a protonated or deprotonated analog thereof, wherein Ri is selected from the group consisting of CF3 or Ci-C28 alkyl, C2-C28 alkenyl, C2-C22 alkynyl, C ₃ -Ci ₂ cycloalkyl, C ₃ -C ₂ -cycloalkenyl, C 7 -C ₉ aralkyl, C3-C ₂ o-heteroalkyl, C3-C12 cycloheteroalkyl, which are substituted with one or more electron withdrawing groups; or phenyl or naphthyl substituted with one or more electron-withdrawing groups;

R2 and R3 are independently selected from the group consisting of hydrogen, unsubstituted or substituted Ci-C28-alkyl, C2-C28-alkenyl, C2-C22-alkynyl, C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C7-C9 Aralkyl, C3-C20 heteroalkyl, C3-C12 cycloheteroalkyl, C5-C16 heteroaralkyl, unsubstituted or substituted phenyl or naphthyl or unsubstituted or substituted heteroaryl; or R2 and R3, together with the carbon atom to which they are attached, form an unsubstituted or substituted 5-, 6-, 7-, 8- or 9-membered ring, which may include other heteroatoms; and

R4 is selected from the group consisting of hydrogen, Ci-C28-alkyl, C2-C28-alkenyl, C2-C22 alkynyl, _{_C3-Ci2} cycloalkyl, _{_C3-Ci2} cycloalkenyl, _C7-C9 aralkyl , C ₃ -C ₂ o-Heteroalkyl, C ₃ -C 12 -cycloheteroalkyl, C 5 -C 16 -heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl.

Likewise provided by the present invention is the use of a washing or cleaning agent according to the invention for washing textiles or cleaning solid surfaces. Another aspect of the invention relates to processes for the cleaning of textiles or hard surfaces, wherein in at least one process step, a washing or cleaning agent according to the invention is applied.

Finally, the present invention is also directed to the use of the acylhydrazones of formula (I) described herein for stabilizing an enzyme in a protease-containing detergent or cleaner.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. All percentages are by weight unless otherwise specified. Numeric ranges specified in the format "from x to y" include the above values.If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints, also be recorded.

Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.

The enzyme stabilizers used according to the invention are acylhydrazone compounds of the formula 1)

as defined above. These can be in E or Z configuration. Also included are protonated or deprotonated analogs of these compounds, ie compounds which are distinguished from the compounds defined according to formula (1) by the absence or additional presence of one or more protons (H ⁺ ).

By electron-withdrawing substituents herein are meant those substituents having an -I and / or -M effect in aromatic ring systems. When R4 is hydrogen, the enzyme stabilizer of formula (1) may be in one of its tautomeric forms or as a mixture of its tautomeric forms.

Suitable substituents for the alkyl, heteroalkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, phenyl, naphthyl, aralkyl, heteroaralkyl and cycloheteroalkyl groups are, in particular, C 1 -C 4 -alkyl; Ci-C4-alkoxy; hydroxy; sulfo; sulfato; Halogen; cyano; nitro; carboxy; amino; N-mono- or N, N-di-C 1 -C 4 -alkylamino wherein the alkyl group is unsubstituted or substituted by hydroxy; N-phenylamino; N-naphthylamino, wherein the amino groups may be present as quaternary amino groups; phenyl; Phenoxy or naphthyloxy. Preference is given to hydroxyl, halogen and O-C4-alkoxy.

Generally preferred are unsubstituted alkyl, heteroalkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, phenyl, naphthyl, aralkyl, heteroaralkyl and cycloheteroalkyl.

Cyclic compounds preferably consist of 5-, 6- or 7-membered rings, with 6-membered rings being preferred. Aryl refers to aromatic ring systems wherein the ring atoms are carbon, and preferably refers to phenyl or naphthyl.

The Ci-Cis-alkyl radicals mentioned for the compounds of the formula (1) are straight-chain or branched alkyl radicals which are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, ferf Butyl, pentyl, hexyl, heptyl or octyl.

Preference is given to C 1 -C 12 -alkyl radicals, in particular C 1 -C 5 -alkyl radicals and particularly preferably C 1 -C 4 -alkyl radicals. The alkyl radicals mentioned may be unsubstituted or substituted, where the substituents are selected from the group consisting of hydroxy, C 1 -C 4 alkoxy, sulfo and sulfato, in particular hydroxy. The corresponding unsubstituted alkyl radicals are preferred. Very particular preference is given to methyl and ethyl, in particular methyl.

Examples of aryl radicals which are suitable for compounds of the formula (1) are phenyl and naphthyl, each unsubstituted or substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy , Amino, N-mono- or N, N-di-C 1 -C 4 -alkylamino, wherein the alkyl group is unsubstituted or substituted by hydroxy, N-phenylamino, N-naphthylamino, wherein the amino group may be a quaternary amino group, phenyl, phenoxy or naphthyloxy, in particular C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, phenyl and hydroxy, preferably phenyl.

The C 1 -C 6 -alkylene groups mentioned for compounds of formula (1) are straight-chain or branched alkylene radicals selected from the group consisting of methylene, ethylene, n-propylene and n-butylene which are substituted or unsubstituted, the substituents being preferably selected from hydroxy and C 1 -C 4 -alkoxy. In the case of compounds of the formula (1), the halogen is preferably chlorine, bromine or fluorine, chlorine being particularly preferred.

C3-C12 cycloalkyl refers to saturated, cyclic hydrocarbons. C 3 -C 12 -cycloalkyl is preferably selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1-adamantyl and 2-adamantyl.

C 2 -C 18 alkenyl is preferably selected from the group consisting of vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1, 3-butadien-2-yl , 2-Penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-butene-1 -yl, 1, 4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl and dodecenyl.

C3-C12 cycloalkenyl refers to unsaturated hydrocarbon radicals having one or more double bonds, and are preferably selected from the group consisting of 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl , 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4 (10) -thujen-10-yl, 2-norbornen-1-yl, 2, 5-norbornadien-1-yl and 7J-dimethyl-2,4-norcaradien-3-yl.

C 7 -C 9 Aralkyl is preferably selected from the group consisting of benzyl, β-phenylethyl, and α, α-dimethylbenzyl.

C 5 -C 16 heteroaralkyl denotes a C 1 -C 8 -alkyl group which is substituted by a C 4 -C 8 -heteroaryl group, preferably by a C 5 -C 12 -heteroaryl group.

C5-C6 heteroaryl preferably denotes pyridine or pyrimidine.

Ri is preferably (1) - (CH2) kN ⁺ (RiooR'iooR "ioo) 3A ^~, wherein ^A" is an anion and k is an integer from 1 to 4; or (2) phenyl substituted with 1 to 5 electron withdrawing substituents selected from the group consisting of -O-C (O) ORioo, -COOR100, -C (O) N (RiooR'ioo), -C (0) -Rioo, -CN, -NO 2, -SO3R100, -CF _3, F, Cl, Br, I, -N (RiooR'iooR "ioo) 3 ⁺ ^A", -N (RioiR'ioi) and

wherein R100, R'100, R "100 are independently selected from the group consisting of hydrogen, Ci-Cis-alkyl, and phenyl, wherein methyl is preferred, or two of the radicals R100, R'100, R" 100, together with the nitrogen atom to which they are attached form a 5- or 6-membered ring which may contain another nitrogen atom; ^{* is} the link; A an anion is; R101 and R'101 are independently selected from the group consisting of -C (0) -Rioo, -C (O) N (RiooR'ioo) and -C (O) ORioo; or (3) R1 forms a group selected together with the electron-withdrawing substituent

In a preferred embodiment, the enzyme stabilizer has the general formula (2)

in which

R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen, unsubstituted or substituted Ci-C28-alkyl, Ci-C28-alkoxy, C2-C28-alkenyl, C2-C22 alkynyl, C ₃ -C ₂ cycloalkyl, C ₃ -C ₂ -cycloalkenyl, C 7 -C ₉ aralkyl, C3-C ₂ o-heteroalkyl, C3-C12 cycloheteroalkyl, C5-Ci6-heteroalkyl, and unsubstituted or substituted phenyl or naphthalene methyl, wherein the substituents radicals are selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, hydroxyl, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono or N, N-di-Ci- C4-alkylamino which is unsubstituted or substituted on the alkyl group by hydroxy, N-phenylamino, N-naphthylamino, wherein the amino group may be a quaternary amino group, phenyl, phenoxy and naphthyloxy; or R1, R2, R3 and R4 are independently selected from the group consisting of OR11, NR11R12 and halogen; or R 1 and R 2, R 2 and R 3, or R 3 and R 4 are joined together and form one, two or three carbocyclic or heterocyclic rings which may be interrupted or interrupted by one or more -O-, -S- or NRi 3 groups, or further connected to other aromatic rings and / or substituted with one or more C 1 -C 6 -alkyl groups;

R5 is selected from the group consisting of hydrogen, unsubstituted or substituted Ci-C ₂ 8 alkyl, C ₂ -C ₂ 8 alkenyl, C ₂ -C ₂ 2-alkynyl, _{_C3-Ci2} cycloalkyl, C ₃ - _Ci2 cycloalkenyl, C7-C9 Aralykl, C3-C2o-heteroalkyl, C3-Ci2-cycloheteroalkyl, C5-Ci6-heteroalkyl, unsubstituted or substituted phenyl and unsubstituted or substituted heteroaryl, wherein the substituents for the radicals are selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono- or N, N-di-C 1 -C 4 -alkylamino, which is unsubstituted or may be substituted with hydroxy on the alkyl group, N- Phenylamino, N-naphthylamino, wherein the amino group may be a quaternary amino group, phenyl, phenoxy and naphthyloxy;

R6 is selected from the group consisting of hydrogen, unsubstituted or substituted Ci-C ₂ 8 alkyl, C ₂ -C ₂ 8 alkenyl, C ₂ -C ₂ 2-alkynyl, _{_C3-Ci2} cycloalkyl, C ₃ - _Ci2 cycloalkenyl, C7-C9 aralkyl, C3-C ₂ o-heteroalkyl, C3-Ci ₂ cycloheteroalkyl, C5-Ci6-heteroalkyl, unsubstituted or substituted phenyl or naphthyl, and unsubstituted or substituted heteroaryl, wherein the substituents for the Radicals are selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, hydroxyl, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono- or N, N-di-C 1 -C 4 -Alkylamino, which may be unsubstituted or substituted on the alkyl group by hydroxy, N-phenylamino, N-naphthylamino, wherein the amino group may be a quaternary amino group, phenyl, phenoxy and naphthyloxy;

R7 is selected from the group consisting of

, each with an anion A ^~ ,

where k is an integer from 1 to 4, A ^'is an anion of an organic or inorganic acid, R 10 is selected from the group consisting of hydrogen, Ci-C ₂ 8 alkyl, C ₂ -C ₂ 8 alkenyl, C ₂ -C ₂₂ alkynyl, C ₃ -C ₂ cycloalkyl, _{_C3-Ci2} cycloalkenyl, _C7-C9 aralkyl, C ₃ -C ₂ o-heteroalkyl, C ₃ -C ₂ - cycloheteroalkyl and C5-Ci6 Heteroalkyl, wherein RH and Ri _{2 are} independently selected from the group consisting of hydrogen, Ci-Cis-alkyl and phenyl; or RH and Ri ₂ , together with a nitrogen atom to which they are attached, a 5- or 6- form a membered ring which may contain another nitrogen, oxygen or sulfur atom; and Ri _{3 represents} hydrogen or Ci-Cis-alkyl.

In a further preferred embodiment, the stabilizer has the general formula (2), wherein R ₁ , R ₂ , R ₃ and R _{4 are} independently selected from the group consisting of hydrogen, unsubstituted or substituted C ₁ -C 8 -alkyl, C ₁ -C ₂ 8 alkoxy, C ₂ -C ₂ 8 alkenyl, C ₂ -C ₂₂ - alkynyl, C ₃ -C ₂ cycloalkyl, _{_C3-Ci2} cycloalkenyl, _C7-C9 aralkyl, C ₃ -C ₂₀ - Heteroalkyl, C ₃ -C 12 -cycloheteroalkyl, C 5 -C 16 -heteroalkyl and unsubstituted or substituted phenyl or naphthyl, where the substituents for the radicals are selected from the group consisting of C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, hydroxyl, Sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono or N, N-di-Ci-C4-alkylamino, which is unsubstituted or substituted on the alkyl group with hydroxy, N-phenylamino, N-naphthylamino, wherein the amino group may be a quaternary amino group, phenyl, phenoxy and naphthyloxy; or R 1, R _2, R ₃ and R4 are independently selected from the group consisting of OR11, NRnRi ₂ and halogen; or R 1 and R _2, R ₂ and R _3, or R ₃ and R 4 are connected together and carbocyclic one, two or three or form heterocyclic rings which may be interrupted or interrupted by one or more -O-, -S- or NRi3- groups, or may be further connected to other aromatic rings and / or substituted with one or more Ci-C6-alkyl groups;

Rs is selected from the group consisting of hydrogen, unsubstituted or substituted Ci-C ₂ 8 alkyl, C ₂ -C ₂ 8 alkenyl, C ₂ -C ₂ 2-alkynyl, _{_C3-Ci2} cycloalkyl, C ₃ - _Ci2 cycloalkenyl, C7-C9 Aralykl, C3-C ₂ o-heteroalkyl, C3-Ci ₂ cycloheteroalkyl, C5-Ci6-heteroalkyl, unsubstituted or substituted phenyl and unsubstituted or substituted heteroaryl, where the Substituents for the radicals are selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, hydroxyl, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono- or N, N-di-C 1 -C 4 -alkyl. Alkylamino, which may be unsubstituted or substituted on the alkyl group with hydroxy, N-phenylamino, N-naphthylamino, wherein the amino group may be a quaternary amino group, phenyl, phenoxy and naphthyloxy;

R6 is selected from the group consisting of hydrogen, unsubstituted or substituted Ci-C ₂₈ alkyl, C ₂ -C ₂₈ alkenyl, C ₂ -C ₂₂ alkynyl, C ₃ -C ₂ cycloalkyl, C ₃ -C ₂ - cycloalkenyl, C7-C9 aralkyl, C3-C ₂ o-heteroalkyl, C3-Ci ₂ cycloheteroalkyl, C5-Ci6-heteroalkyl, unsubstituted or substituted phenyl or naphthyl, and unsubstituted or substituted heteroaryl, wherein the substituents are selected for the radicals from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, hydroxyl, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono- or N, N-di-C 1 -C 4 -alkylamino, which may be unsubstituted or substituted by hydroxy on the alkyl group, N-phenylamino, N-naphthylamino wherein the amino group may be a quaternary amino group, phenyl, phenoxy and naphthyloxy;

R7 is - _(CH2) kN ⁺ (RiooR'iooR "ioo) 3A is ^_, where k is an integer from 1 to 4, A ^'is an anion of an organic or inorganic acid, and R100, R'100, R" are independently selected from the group consisting of hydrogen, Ci-Cis-alkyl, and phenyl, with methyl being preferred.

In the above embodiments, the anion A ^"is preferably selected from the group consisting of RCOO ^" , ClO, BF ₄ ^" , PF ₆ ^" , RSOs ^" , RSO (preferably CF 3 SO 3), SC ^2" , OCN ^" , SCN ^" , NO 3 , F-, Cr, Br, I-, RO-, CIC ^", HS0 ₄ ^{2 ',} ₄ Ρ0 ^3", HP0 ₄ ^2', H ₂ P0 ₄ ^{2 ',} ₃ C0 ^{2 "and} ^HCO" wherein R is selected is selected from the group consisting of hydrogen, unsubstituted and substituted C ₁ -C 4 -alkyl and substituted aryl In particular, A ^"is selected from the group consisting of RSO's ^" , OCN ^" , SCN ^" , NO 3, F, I and Cl ^" . A ^" is preferably Cl ^" .

For anions with a charge greater than -1, the addition of cations selected from the group consisting of H ⁺ , Na ⁺ , K ⁺ and NH4 ^{+ leads} to charge balancing.

In both phenyl rings, Rs-Rs can be independently selected from the groups listed above. So R5 in one ring can be a different rest than in the other ring. This also applies to R6-Rs. In particularly preferred embodiments, the enzyme stabilizer is a compound of the formula (3) or (4)

(3) (4)

Under a detergent or cleaning agent according to the invention are all means that are suitable for washing or cleaning of particular textiles and / or solid surfaces. Other suitable ingredients are described in detail below.

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

Without wishing to be bound by theory, it is assumed according to the invention that the compounds relevant to the invention form a complex with the protease to be inhibited / stabilized according to the invention. This probably looks like that the invention-relevant compound is incorporated in the substrate binding pocket of the protease and is non-covalently bound there. In this way, the active site of the protease is blocked by the compound which is not hydrolyzable by this enzyme and is not available for hydrolysis of other added proteins. This is a reversible bond, i. for a balance between association and dissociation. The equilibrium coefficient of this reaction is called the inhibition constant or K.

The first advantage of the invention relevant connections over the prior art is that they have as elements only C, H, N and O and in particular are free of boron. Thus, they do not form the undesirable, toxic boron-derived by-products with other detergent or cleaning ingredients.

The enzymes contained in the detergents and cleaners show on addition of the boron-free compounds according to the invention a significantly improved lifetime compared to stabilizer-free formulations. The inhibition of enzyme activity, in particular inhibition of the protease activity by addition of acylhydrazone compounds of the formula (1), however, is comparably effective with boron-containing stabilizers. The protease and optionally other proteins contained, in particular other enzymes are protected in this way against proteolysis by this enzyme (stabilized against proteolysis) and are thus fully efficient even after storage. On the other hand, at the moment of dilution of the agent according to the invention with water for the preparation of an aqueous washing or cleaning liquor, the binding equilibrium is shifted in the direction of dissociation so that the complex dissolves and the majority of the protease relevant to the invention can become proteolytically active.

Further objects of the present invention relate to:

the use of a compound described above as a reversible inhibitor and / or stabilizer of a protease, in the context of a detergent or cleaning agent formulation;

A washing or cleaning process in which a protease is inhibited which is inhibited and / or stabilized with a compound described above;

the use of a washing or cleaning agent according to the invention for washing and / or cleaning textiles and / or hard surfaces; such as

the use of a protease and a compound described above for the preparation of a detergent or cleaner.

In detergents or cleaners according to the invention, which in one embodiment are in predominantly solid form and in another embodiment in predominantly liquid, pasty or gel form, the enzyme, i. the protease in an amount of 0.001-2% by weight, preferably 0.05-1% by weight, and the acylhydrazone of the formula (I) in an amount of 0.001-2% by weight, preferably 0.05 -1 wt .-%, based on the total weight of the detergent or cleaning agent contained in this.

In various embodiments, the enzyme and the enzyme stabilizer may be pre-formulated in an enzyme composition, wherein the enzyme is present in the enzyme composition in an amount of 0.001-2% by weight, preferably 0.05-1% by weight, and the acylhydrazone of the formula ( I) in an amount of 0.001-2 wt .-%, preferably 0.05-1 wt .-%, based on the total weight in the enzyme composition. This enzyme composition, which is also a constituent of the present invention, can then be used in detergents or cleaners according to the invention in amounts which lead to the above-mentioned final concentrations in the washing or cleaning agent.

In addition to the enzyme stabilizer according to the abovementioned general formula, an agent according to the invention may contain at least one further stabilizer, in particular a polyol, such as glycerol or 1,2-ethylene glycol, and / or an antioxidant.

The protease stabilized or reversibly inhibited according to the invention is preferably a serine protease, in particular a subtilase, more preferably a subtilisin. The subtilisin may be a wild-type enzyme or a subtilisin variant, wherein the wild-type enzyme or the starting enzyme of the variant is preferably selected from one of the following: the alkaline protease from Bacillus amyloliquefaciens (ΒΡΝ '),

the alkaline protease from Bacillus licheniformis (subtilisin Carlsberg),

the alkaline protease PB92,

Subtilisin 147 and / or 309 (Savinase)

the alkaline protease from Bacillus lentus, preferably from Bacillus lentus (DSM 5483),

the alkaline protease from Bacillus alcalophilus (DSM 1 1233),

the alkaline protease from Bacillus gibsonii (DSM 14391) or an at least 70% identical alkaline protease,

the alkaline protease from Bacillus sp. (DSM 14390) or an at least 98.5% identical alkaline protease, and

the alkaline protease from Bacillus sp. (DSM 14392) or an at least 98.1% identical alkaline protease.

Compositions according to the invention may contain, in addition to the protease, one or more further enzymes, in particular from the following group: one or more further proteases, amylases, hemicellulases, cellulases, lipases and oxidoreductases.

The compositions described herein include all conceivable types of detergents or cleaners, both concentrates and neat agents, for use on a commercial scale, in the washing machine or in hand washing or cleaning. These include detergents for textiles, carpets, or natural fibers, for which the term detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term detergent is used, ie in addition to manual and machine Dishwashing agents, for example, scouring agents, glass cleaners, toilet scenters, etc. The washing and cleaning agents in the invention also include washing aids which are added to the actual detergent in the manual or machine textile laundry to achieve a further effect. Furthermore, laundry detergents and cleaners in the context of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example to dissolve stubborn soiling, and also agents which are in one of the actual Textile laundry downstream step to 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.

Embodiments of the present invention include all solid, powdered, liquid, gelatinous or pasty administration forms of the agents described herein, which if appropriate can also consist of several phases and in compressed or uncompressed form Form can be present. The agent can be present as a free-flowing powder, in particular with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l or 600 g / l to 850 g / l. The solid dosage forms of the composition also include extrudates, granules, tablets or pouches. Alternatively, the agent can also be liquid, gelatinous or pasty, for example in the form of a non-aqueous liquid washing or dishwashing detergent or a non-aqueous paste or in the form of an aqueous liquid washing or dishwashing detergent or a water-containing paste. Furthermore, the agent may be present as a one-component system. Such funds consist of one phase. Alternatively, an agent can also consist of several phases. Such an agent is therefore divided into several components.

The detergents or cleaners described herein, which may be in the form of powdered solids, in densified particulate form, as homogeneous solutions or suspensions, may further additionally contain all known ingredients customary in such compositions, preferably containing at least one further ingredient in the composition. In particular, the agents described herein may contain surfactants, builders, bleaches or bleach activators. In addition, they may contain water-miscible organic solvents, sequestering agents, electrolytes, pH regulators and / or further auxiliaries, such as optical brighteners, graying inhibitors, foam regulators, as well as dyes and fragrances, and combinations thereof.

Advantageous ingredients of agents described herein are disclosed in International Patent Application WO2009 / 121725, beginning on page 5, penultimate paragraph, and ending on page 13, after the second paragraph. This disclosure is incorporated herein by reference and the disclosure is incorporated herein by reference.

A further subject of the invention is a method for the cleaning of textiles or hard surfaces, which is characterized in that in at least one method step a means described herein is used.

These include both manual and mechanical processes, with mechanical processes being preferred. Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned and washed off after the contact time, or that the items to be cleaned are otherwise treated with a detergent or a solution or dilution of this product. The same applies to processes for cleaning all other materials than textiles, especially hard surfaces. All conceivable washing or cleaning methods can be enriched in at least one of the method steps by the use of a washing or cleaning agent described herein and then represent embodiments of the present invention. Another subject of the invention is the use of an agent described herein for cleaning or washing textiles or for cleaning hard surfaces.

Yet another subject of the invention is the use of the compounds described herein for stabilizing an enzyme in a protease-containing detergent or cleaner.

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

example

Example 1 :

The storage stability of protease-containing detergents and cleaning agents in the presence of acylhydrazone compounds was investigated for use as enzyme stabilizers. For this purpose, the acylhydrazone compounds in the presence of 1, 2-propanediol were each formulated at 1% (w / w) in a detergent or cleaner formulation (see Table 2). Then the protease (1% PUR) was added to the formulation and the formulation stored at 30 ° C.

In parallel reactions, the proteolytic activity of 1% protease (PUR) in 4% PG (1, 2-propanediol), 85% matrix (see Table 1) and in half of the batches after incubation with 1% of the candidate Compound (data in w / w)) in the formulation, as indicated in Table 1, by the release of the chromophore para-nitroaniline from the substrate succinyl alanine-alanine-proline-phenylalanine-para-nitroanilide (AAPFpNA; Bachem L- 1400). The release of pNA causes an increase in absorbance at 410 nm, the time course of which is a measure of the enzymatic activity. The measurement was carried out at a temperature of 25 ° C, at pH 8.6 and a wavelength of 410 nm. The measuring time was 5 min at a measuring interval of 20 to 60 seconds.

For evaluation, the initial values for the proteolytic activity of the agent in question are compared with the values determined after storage. The higher the activity remaining after storage, the better the protease obtained is inactivated during storage and the better the compound in question is suitable as a stabilizer according to the invention. The stabilizing effect of each tested compound is therefore measured as a relative percentage increase in protease residual activity.

Table 1: Formulation for activity test

Ingredient Amount (wt%)

demineralized water rest

Citric acid 1, 42623

Defoamer (10%) 0.008

Fatty alcohol ether sulphate (70%) 5,6

Fatty alcohol ether 4.4

Alkylbenzenesulfonic acid 4.4

(96%)

C12-18 fatty acid 2,4

NaOH (50%) 0.95

Glycerol (99.5%) 2 Phosphate (DTPMP-Na ₇ H ₃ ) 0.2

(32%)

Preservative 0.10

Ethanol (93%) 1

The pH of the formulation was adjusted to 8.4 by the NaOH. The formulation was clear and colorless.

As candidate compounds were tested:

Compound A Compound B

Table 2: Measured protease residual activity of the candidate compounds

Tl [h] 0 22 96 168 334 674

1% PUR, without stabilizer, 4% PG, 85% matrix 100.0% 82.8% 61, 0% 39.6% 23.0% 1 1, 5%

1% PUR, 1% B (OH) ₃ , 4% PG, 85% Matrix 100.0% 92.7% 85.5% 72.2% 67, 1% 69.9%

1% PUR, 1% Compound A, 85% Matrix 100.0% 89.8% 73.0% 61, 2% 46.5% 31, 1%

1% PUR, 1% Compound B, 4% PG, 85% Matrix 100.0% 93.4% 76.2% 65.3% 51, 6% 36.5%

Claims

claims

1. washing and cleaning agent containing at least one protease and at least one enzyme stabilizer, wherein the at least one enzyme stabilizer an acylhydrazone of the formula (1)

in E or Z configuration or a protonated or deprotonated analog thereof, wherein

Ri is selected from the group consisting of CF 3 or C ₁ -C 28 alkyl, C ₂ -C 28 alkenyl, C ₂ -C _{2 2} alkynyl, C ₃ -C 12 cycloalkyl, C ₃ -C 12 cycloalkenyl, C 7 -C ₉ -Aralkyl, C3-C ₂ o-heteroalkyl, C3-C12-cycloheteroalkyl, which are substituted with one or more electron-withdrawing groups; or phenyl or naphthyl substituted with one or more electron-withdrawing groups;

R2 and R3 are independently selected from the group consisting of hydrogen, unsubstituted or substituted Ci-C28-alkyl, C2-C28-alkenyl, C2-C22-alkynyl, C3-Ci2-cycloalkyl, _{_C3-Ci2} cycloalkenyl, C7 -C ₉ aralkyl, C3-C ₂ o-heteroalkyl, C3-C12 cycloheteroalkyl, C5-Ci6-heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl; or R2 and R3, together with the carbon atom to which they are attached, form an unsubstituted or substituted 5-, 6-, 7-, 8- or 9-membered ring, which may include other heteroatoms; and

R4 is selected from the group consisting of hydrogen, Ci-C28-alkyl, C2-C28-alkenyl, C ₂ -C ₂ 2-alkynyl, _{_C3-Ci2} cycloalkyl, _{_C3-Ci2} cycloalkenyl, C7-C ₉ -Aralkyl, C3-C ₂ o-heteroalkyl, C ₃ - Ci2-cycloheteroalkyl, C5-Ci6-heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl.

2. Washing and cleaning agent according to claim 1, characterized in that

(i) in the compounds of the formula (1) the substituents for the alkyl, heteroalkyl,

Cycloalkyl, alkenyl, cycloalkenyl, alkynyl, phenyl, naphthyl, aralkyl, heteroaralkyl and cycloheteroalkyl groups are selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, hydroxyl, sulfo, sulfato, Halogen, cyano, nitro, carboxyl, amino, N-mono- or N, N-di-Ci-C4-alkylamino, wherein the alky is unsubstituted or substituted by hydroxy, N-phenylamino, N-naphthylamino, wherein the amino groups are a quaternary amino group may be phenyl, phenoxy and naphthyloxy, especially hydroxyl, halogen and C 1 -C 4 alkoxy;

(ii) in the compounds of formula (1) the alkyl, heteroalkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, phenyl, naphthyl, aralkyl, heteroaralkyl and cycloheteroalkyl groups are unsubstituted; or

(iii) in the compounds of formula (1) the cyclic groups consist of 5-, 6- or 7-membered rings, in particular 6-membered rings.

3. Washing and cleaning agent according to claim 1 or 2, characterized in that

(i) in the compounds of the formula (1) the C 1 -C 6 -alkyl radicals are straight-chain or branched alkyl radicals, in particular selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, fer-butyl, or straight-chain or branched pentyl, hexyl, heptyl or octyl,

(ii) in the compounds of formula (1) the aryl radicals are phenyl or naphthyl, each unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N mono- or N, N-di-C 1 -C 4 -alkylamino, where the alkyl group is unsubstituted or substituted by hydroxy, N-phenylamino, N-naphthylamino, where the amino groups may be a quaternary amino group, phenyl, phenoxy or naphthyloxy , in particular C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, phenyl or hydroxy, preferably phenyl;

(iii) in the compounds of the formula (1) the C 1 -C 6 -alkylene groups are straight-chain or branched alkylene radicals, in particular C 1 -C 4 -alkylene groups selected from among methylene, ethylene, n-propylene and n-butylene, which are each substituted or unsubstituted, wherein the substituents are preferably selected from hydroxy and C 1 -C 4 alkoxy;

(iv) in the compounds of the formula (1) the C 3 -C 12 -cycloalkyl groups are saturated, cyclic hydrocarbons, in particular C 3 -C 12 -cycloalkyl, more preferably selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1 Adamantyl and 2-adamantyl;

(v) in the compounds of formula (1) the C2-Cis-alkenyl groups are selected from vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1, 3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3 Methyl 2-buten-1-yl, 1, 4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl and dodecenyl;

(vi) in the compounds of formula (1) the halogen is preferably chlorine, bromine or fluorine, in particular chlorine.

(vii) in the compounds of the formula (1) the C 3 -C 12 -cycloalkenyl groups have one or more double bonds, in particular selected from 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl , 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4 (10) -thujen-10-yl, 2-norbornen-1-yl, 2, 5-norbornadien-1-yl and 7,7-dimethyl-2,4-norcaradien-3-yl. (viii) in the compounds of formula (1), the C7-C9 aralkyl groups are selected from benzyl, β-phenylethyl and α, α-dimethylbenzyl;

(ix) in the compounds of the formula (1) the C5-C16-heteroaralkyl groups are selected from C 1 -C 8 -alkyl groups which are substituted by a C 4 -C 8 -heteroaryl group, preferably by a C 5 -C 6 -heteroaryl group; and or

(x) in the compounds of formula (1) the Cs-Ce heteroaryl groups are selected from pyridine and pyrimidine.

4. Washing and cleaning agent according to one of claims 1-3, characterized in that in the compounds of formula (1) Ri

(i) - (CH2) kN ⁺ (RiooR'iooR "ioo) ^3A", wherein A ^"is an anion and k is a number from 1 to 4; or

(ii) phenyl substituted with 1 to 5 electron withdrawing substituents selected from the group consisting of -O-C (O) ORioo, -COOR100, -C (O) N (RiooR'ioo), -C (0) -Rioo, -CN, -NO 2, -SO3R100, -CF _3, F, Cl, Br, I,

-N (RiooR'iooR "ioo) 3 ⁺ A ^" , -N (Rioi R'ioi) and ; or

(iii) together with the electron-withdrawing substituent a group selected from

in which

R100, R'100, R "are independently selected from the group consisting of hydrogen, Ci-Cis-alkyl and phenyl, preferably methyl, or wherein two of the radicals R100, R'100, R" 100, together with a nitrogen atom to which they are attached form a 5- or 6-membered ring which may contain another nitrogen atom;

R101 and R'101 are independently selected from the group consisting of - C (0) -Rioo, -C (O) N (RiooR'ioo) and -C (O) ORioo;

*

the point of attachment and A ^"is an anion; and

the anion A ^"is preferably selected from the group consisting of ^RCOO" CIO4 ^", ^BF4", PF ₆ ^", RSO3-, RSO4- (preferably CF3SO3) ² S0 _^4", OCN ^", ^SCN", N0 ₃ ^", P, Cl ^" , Br, I ^" , RO ^" , CIO4, HSO4 ² , PO4 ³ , HPO4 ² , H2PO4 ² , CO3 ² and HCO3, particularly preferably RS0 ₃ ^" , OCN ^" , SCN ^" , NO 3 ^" , F ^" , I ^" and Cl ^- , most preferably Cl ^- , wherein R is selected from the group consisting of hydrogen and unsubstituted or substituted Ci-Cis-alkyl.

5. Washing and cleaning agent according to one of claims 1 to 4, characterized in that the enzyme stabilizer is an acylhydrazone of the formula (2):

(2)

in which

R 1, R 2, R 3 and R 4 are independently selected from the group consisting of hydrogen, unsubstituted or substituted C ₁ -C 28 -alkyl, C ₁ -C -alkoxy, C ₂ -C -alkenyl, C ₂ -C ₂ -alkynyl, C ₃ _Ci2 cycloalkyl, _{_C3-Ci2} cycloalkenyl, _C7-C9 aralkyl, C3-C20 heteroalkyl, C3-Ci2-cycloheteroalkyl, C5-Ci6-heteroalkyl, and unsubstituted or substituted phenyl or naphthyl, wherein the substituents for the radicals are selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, hydroxyl, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono or N, N-di-C 1 -C 4 -Alkylamino which is unsubstituted or substituted on the alkyl group by hydroxy, N-phenylamino, N-naphthylamino, where the amino group may be a quaternary amino group, phenyl, phenoxy and naphthyloxy; or R1, R2, R3 and R4 are independently selected from the group consisting of OR11, NR11R12 and halogen; or R 1 and R 2, R 2 and R 3, or R 3 and R 4 are joined together and form one, two or three carbocyclic or heterocyclic rings which may be interrupted or interrupted by one or more -O-, -S- or NR 13 -groups, or further connected to other aromatic rings and / or substituted with one or more C 1 -C 6 -alkyl groups;

Rs is selected from the group consisting of hydrogen, unsubstituted or substituted Ci-C ₂ 8 alkyl, C ₂ -C ₂ 8 alkenyl, C ₂ -C ₂ 2-alkynyl, _{_C3-Ci2} cycloalkyl, C ₃ - _Ci2 cycloalkenyl, C7-C9-Aralykl, C3-C2o-heteroalkyl, C3-Ci2-cycloheteroalkyl, C5-Ci6-heteroalkyl, unsubstituted or substituted phenyl and unsubstituted or substituted heteroaryl, wherein the substituents for the radicals are selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono- or N, N-di-C 1 -C 4 -alkylamino, which is unsubstituted or at the alkyl group may be substituted with hydroxy, N-phenylamino, N-naphthylamino, wherein the amino group may be a quaternary amino group, phenyl, phenoxy and naphthyloxy;

R6 is selected from the group consisting of hydrogen, unsubstituted or substituted Ci-C ₂ 8 alkyl, C ₂ -C ₂ 8 alkenyl, C ₂ -C ₂ 2-alkynyl, _{_C3-Ci2} cycloalkyl, C ₃ - C ₂ -cycloalkenyl, C7-C9-aralykl, C3-C2o-heteroalkyl, C3-C12-cycloheteroalkyl, C5-C16-heteroalkyl, unsubstituted or substituted phenyl or naphthyl, and unsubstituted or substituted heteroaryl, where the substituents for the radicals are selected from the group consisting of Ci-C4-alkyl, Ci-C4-alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono- or N, N-di-Ci-C4-alkylamino, which unsubstituted or substituted on the alkyl group with hydroxy, N-phenylamino, N-naphthylamino, wherein the amino group may be a quaternary amino group, phenyl, phenoxy and naphthyloxy; R7 is selected from the group consisting of

, each with an anion A ^" ,

or R _{7 is} - (CH ₂ ) k N ⁺ (RioRoioRo) 3O-,

wherein k is an integer of 1 to 4, A ^"is an anion of an organic or inorganic acid, R100, R'100, R" 100 are independently selected from the group consisting of hydrogen, Ci-Cis-alkyl, and phenyl where methyl is preferred, R 10 is selected from the group consisting of hydrogen, C ₁ -C 28 -alkyl, C ₂ -C 28 -alkenyl, C ₂ -C 22 -alkynyl, C ₃ -C 12 -cycloalkyl, C ₃ -C 12 -cycloalkenyl, C7 C ₉ aralkyl, C ₃ -C ₂ o heteroalkyl, C ₃ -C 12 cycloheteroalkyl and C 5 -C 16 heteroalkyl; wherein R 1 and R 12 are independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl and phenyl; or RH and R12 together with a nitrogen atom to which they are attached form a 5- or 6-membered ring which may contain another nitrogen, oxygen or sulfur atom; and R 13 is hydrogen or C 1 -C 18 -alkyl,

wherein the anion A ^"is preferably selected from the group consisting of RCOO ^" , CIO4, BF ₄ -, PF ₆ ^" , RSO ₃ -, RSO ₄ - (preferably CF 3 SO 3), S0 ₄ ^2" , OCN ^" , SCN ^" , N0 ₃ ^", P, Cr, Br, ^I," RO ^", CIO, HSO4 ^2," PC ^{3 "HPC} ^2", H2PO4 ² -, C0 ₃ ^{2 "and} HC0 _^3", more preferably RSOs ^", ^OCN", SCN ^" , NO3 ^" , F ^" , I ^" and CI, most preferably Cl ^" , wherein R is selected from the group consisting of hydrogen and unsubstituted or substituted Ci-Cis-alkyl.

6. Washing and cleaning agent according to one of claims 1 to 5, characterized in that the enzyme stabilizer is a compound of formula (3) or (4)

(3) (4)

7. Washing and cleaning agent according to one of claims 1 to 6, characterized in that the at least one protease in an amount of 0.001-2 wt .-%, preferably 0.05- 1 wt .-%, and the at least one enzyme stabilizer in an amount of 0.001-2 wt .-%, preferably 0.05-1 wt .-%, based on the total weight of the detergent or cleaning agent in this are included.

Use of a washing and cleaning agent according to any one of claims 1-7 for washing textiles or cleaning solid surfaces.

Process for the cleaning of textiles or hard surfaces, characterized in that in at least one process step, a washing or cleaning agent according to any one of claims 1-7 is applied.

Use of an acylhydrazone of the formula (1)

(1 ),

in E or Z configuration or a protonated or deprotonated analog thereof, wherein

R4 is selected from the group consisting of hydrogen, Ci-C28-alkyl, C2-C28-alkenyl, C ₂ -C ₂ 2-alkynyl, _{_C3-Ci2} cycloalkyl, _{_C3-Ci2} cycloalkenyl, C7-C ₉ -Aralkyl, C3-C ₂ o-heteroalkyl, C ₃ - Ci2-cycloheteroalkyl, C5-Ci6-heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl

for stabilizing an enzyme in a protease-containing detergent or cleaner.