EP2220204B1 - Détergents contenant des enzymes stabilisées - Google Patents

Détergents contenant des enzymes stabilisées Download PDF

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Publication number
EP2220204B1
EP2220204B1 EP08853177.7A EP08853177A EP2220204B1 EP 2220204 B1 EP2220204 B1 EP 2220204B1 EP 08853177 A EP08853177 A EP 08853177A EP 2220204 B1 EP2220204 B1 EP 2220204B1
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EP
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Prior art keywords
protease
enzyme
washing
cleaning agent
residue
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EP08853177.7A
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German (de)
English (en)
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EP2220204A1 (fr
Inventor
Robin Ghosh
Andreas Michels
Cornelius Bessler
Daniela Lowis
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/362—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase

Definitions

  • the present application relates to detergents and cleaners containing phosphate compounds having aliphatic and / or aromatic radicals which act as enzyme stabilizers.
  • enzymes in detergents and cleaners 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.
  • 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, ⁇ -glucanases, mannanases or other hemicellulases for hydrolysis, in particular more specific vegetable polymers.
  • proteases and in particular serine proteases, which include the subtilases. They cause the degradation of protein-containing stains on the items to be cleaned. However, they also hydrolyze themselves (autoproteolysis) and all other proteins contained in the agents concerned, i. especially other enzymes. This happens especially during the cleaning process, i. in the aqueous wash liquor, if comparatively favorable reaction conditions are present. However, this also happens during the storage of the respective agent, which is why with increasing storage time always a certain loss of enzyme activities, such as the protease activity, accompanied.
  • the enzyme activity in the washing or cleaning agent is inversely proportional to the storage time, with increasing storage time, the enzyme activity decreases more and more. This is particularly problematic in gel or liquid and in particular in water-containing formulations, because in this with the water contained both the reaction medium and the hydrolysis reagent are available.
  • One goal in the development of detergents and cleaners is therefore to stabilize the enzymes contained, especially during storage.
  • the protection understood against 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.
  • Another frequently approached approach is to add chemical compounds to the agents which inhibit the proteases and thus act collectively as stabilizers for the 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.
  • Polyols in particular glycerol and 1,2-propylene glycol, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are established as reversible protease 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 (4-FPBA) or the salts or esters of the abovementioned compounds.
  • 4-FPBA 4-formylphenylboronic acid
  • peptide aldehydes that is oligopeptides with reduced C-terminus, especially those of 2 to 50 monomers, are described for this purpose.
  • peptidic reversible protease inhibitors include ovomucoid and leupeptin.
  • specific, reversible peptide inhibitors and fusion proteins from proteases and specific peptide inhibitors are used for this purpose.
  • polyols such as glycerol and 1,2-propylene glycol have proved to be unfavorable due to their high necessary use concentrations, because the other active ingredients of the respective agents can thus be contained only in proportionally smaller proportions.
  • Boric acid derivatives occupy an outstanding position among the serine protease inhibitors, which are effective at comparatively low concentrations.
  • the international patent application discloses WO 96/21716 A1 that boric acid derivatives acting as protease inhibitors are also suitable for stabilizing enzymes in detergents and cleaners.
  • a selection of particularly powerful stabilizers are disclosed in the international patent application WO 96/41859 A1 ,
  • boric acid derivatives have a decisive disadvantage.
  • Another object of the present invention is to provide boron-free chemical compounds which act as protease inhibitors and are thus suitable as stabilizers for proteases and / or for other enzymes in detergents and cleaners.
  • a washing or cleaning agent should be provided with such a boron-free chemical compound.
  • An object of the invention is a washing or cleaning agent containing an enzyme and a compound of the general structural formula wherein X is an aliphatic or an aromatic radical and Y is an aliphatic or an aromatic radical, wherein the radical X is selected from the group consisting of -CH 2 -CH 2 -CH 3 , phenyl.
  • the washing or cleaning agent is characterized in that the radicals X and Y of the compound are identical, wherein the radical X is selected from the group consisting of: -CH 2 CH 2 CH 3 , phenyl, and the Rest Y as well is selected from the group consisting of: -CH 2 -CH 2 -CH 3 , phenyl.
  • a particularly preferred compound therefore has as radical X and as radical Y a: -CH 2 -CH 2 -CH 3 - group.
  • a further particularly preferred compound accordingly has as radical X and as radical Y a phenyl group.
  • 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.
  • an enzyme is to be understood as meaning a protein which has a specific biocatalytic function.
  • protease is understood as meaning an enzyme which catalyzes the hydrolysis of peptide bonds and is thereby able to cleave peptides or proteins.
  • the present invention encompasses the compounds mentioned in all protonated and / or deprotonated forms.
  • oppositely charged cations H + , Na + , K + or the like
  • anions Cl - , Br - , formate, acetate, etc.
  • the present invention can be realized. Decisive in each case is the interaction between the invention-relevant compound which stabilizes the enzyme and the enzyme to be stabilized according to the invention.
  • the compounds relevant for the invention ie the stabilizing compounds
  • form a complex with the enzyme to be stabilized It is anticipated that non-covalent binding of the stabilizing compound will occur in or at the substrate binding pocket of the enzyme. In this way, the active site of the enzyme is blocked by a compound which is not hydrolyzable by this enzyme and is therefore no longer available for the catalysis of other substrates present.
  • the stabilizing effect of the compound is therefore due to an inhibition of the enzyme. This is a reversible bond, ie a balance between association and dissociation.
  • the equilibrium coefficient of this reaction is called the inhibition constant or K i .
  • the enzyme Due to the reversible binding of the stabilizing compound to the enzyme, the enzyme is inhibited and thus stabilized in the washing or cleaning agent, whereas the complexes are increasingly dissociated by the changed conditions when using the detergent and cleaning agent, for example by dilution of the detergent Washing or cleaning agent in the washing or cleaning solution, by the presence of further and / or higher affinity enzyme substrates or by changing the pH in the washing or cleaning solution.
  • stabilizing and “inhibiting” or “inhibiting” as well as “stabilizer” and “inhibitor” or “inhibitor” are therefore to be regarded as synonymous in the present patent application.
  • a further subject of the invention is a washing or cleaning agent which is characterized in that the compound has an inhibition constant with respect to the enzyme. K i ) of 0.01 to 10 mM.
  • the washing or cleaning agent is characterized in that the stabilizing compound has an inhibition constant (K i ) of 0.03 to 5 mM with respect to the enzyme.
  • [E], [I] and [EI] represent the respective molar equilibrium concentrations of enzyme (E), inhibitor (I) and the enzyme-inhibitor complex (EI). According to this definition, a substance with a small K i is a good inhibitor under the respective test conditions.
  • K i The determination of K i is carried out on the basis of the activity test of the protease in the presence of the corresponding inhibitor.
  • the kinetics of invertin action, Biochem. Z. 49: 333-369 ), the enzymatic parameters K m , and k cat are determined in the presence of various concentrations of the inhibitor.
  • Vmax the maximum reaction rate at substrate saturation
  • K i can be calculated using the Cheng-Prusoff equation ( Equation 2, Cheng Y., Prusoff WH (1973) Biochem. Pharmacol. 22, 3099-3108 ) are determined via the IC 50 value.
  • the determination of the IC 50 via the determination of the catalytic activity to a substrate in the presence of various concentrations of the inhibitor and the fitting of the experimental data to a sigmoidal dose-response with variable slope equation (pseudo-Hill slopes). It is the inhibitor concentration needed to achieve 50% inhibition.
  • K i IC 50 / 1 + S / K d
  • [S] is the substrate concentration in the assay and K d is the dissociation constant for the substrate, which at the IC 50 concentration of the inhibitor can be considered to be identical to K m for the substrate.
  • the K i values that can be determined in this way characterize the compound with respect to the enzyme used.
  • a protease namely the Bacillus lentus alkaline protease F49 (according to WO 95/23221 A1 ) in the presence of an inhibitor. Since this is a typical subtilisin protease, the values obtained with this enzyme are also typical of other serine proteases, in particular other subtilisin proteases. The exact value for an enzyme of interest must be determined in case of doubt based on the specific enzyme.
  • an advantage of the compounds according to the invention which effect the stabilization of at least one enzyme in detergents and cleaners is that they have favorable inhibition constants with respect to the enzymes to be used in detergents and cleaning agents compared with the prior art. This is especially true for proteases, but also for other enzymes. A largely reversible binding of the inhibitors is thus ensured, ie they do not enter into solid and not too loose transient interactions with the enzyme.
  • the majority of the enzymes are thus present in the form of an enzyme-inhibitor complex during storage of the detergents and cleaners.
  • the enzymes, in particular proteases, and optionally other proteins present are protected in this way, for example against catalytic, in particular hydrolytic activities of these enzymes themselves.
  • the compounds relevant to the invention are functional enzyme inhibitors according to the task formulated and thus enzyme stabilizers for detergents and cleaners.
  • compounds according to the invention have a low volume requirement in comparison with established prior art enzyme stabilizers, for example with respect to polyols.
  • Another advantage of the invention relevant compounds over the prior art is that they have as elements only carbon (C), hydrogen (H), phosphorus (P) and oxygen (O) and in particular are free of boron. Thus, they do not form the undesirable boron-derived by-products with other detergent or cleaning ingredients.
  • the compounds mentioned are presumed to act as reversible inhibitors because they structurally resemble the substrate of the enzymes, concerning proteases, in particular with regard to the acid amide bond to be hydrolyzed.
  • the enzymes preferably proteolytic enzymes, can thus be inhibited by the compounds relevant to the invention. This applies in particular to serine proteases, as shown by the examples of the present application with the positive effect of the described compounds on the basis of subtilisins.
  • the enzyme is in particular in a content of 2 .mu.g to 20 mg per g of the composition, preferably from 5 ⁇ g to 17.5 mg per g of the agent, more preferably from 20 ⁇ g to 15 mg per g of the agent, most preferably from 50 ⁇ g to 10 ⁇ g of the agent.
  • the compound, ie the stabilizer is contained in agents according to the invention in particular in a content of up to 50 mg per g of the agent, preferably up to 10 mg, more preferably up to 7 mg, very particularly preferably up to 5 mg per g of the agent. Furthermore, it is preferred that the amount of the compound contained in the agent, ie the stabilizing the enzyme Compound, based on the stabilized enzyme of 0.01 to 100 x the inhibition constant K i , preferably 0.1 to 10 x K i , more preferably 1 to 5 x K i .
  • the molar ratio of the stabilizing compound to the enzyme is preferably 1: 1 to 1000: 1, in particular from 1: 1 to 500: 1, particularly preferably from 1: 1 to 100: 1, very particularly preferably from 1: 1 1 to 20: 1.
  • Another object of the invention are detergents or cleaners characterized in that the enzyme is selected from the group consisting of: protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ⁇ -glucosidase, carrageenase, oxidase, Oxidoreductase, lipase, esterase or mixtures thereof.
  • the washing or cleaning agent is characterized in that the enzyme is a protease, preferably a serine protease, more preferably a subtilase and most preferably a subtilisin.
  • proteolytic enzymes due to their enzymatic activity, proteolytic enzymes lead to the hydrolysis of proteins, such as enzymes and peptides, which are contained in the composition, be it other proteins or enzymes or also the proteases themselves. Hydrolysis of the protease by its own proteolytic activity becomes referred to as autoproteolysis.
  • the degree of storage stability of all proteins / enzymes contained in a protein / enzyme composition is thus dependent, in particular, on the proteolytic activity of a protease within this composition.
  • subtilisins BPN 'and Carlsberg examples of such proteases are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K which can no longer be assigned to the subtilisins in the narrower sense and the proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsv ⁇ rd, Denmark.
  • the subtilisins 147 and 309 are sold under the trade names Esperase®, and Savinase® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP® protease variants derived.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® from Genencor , under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • proteases are particularly well stabilized or reversibly inhibited by the compounds described.
  • certain variants of proteases i. also variants of said proteases, stabilized by these compounds particularly advantageous.
  • Such protease variants are part of the invention described below.
  • a protease stabilized or reversibly inhibited according to the invention can be a wild-type enzyme or a protease variant.
  • wild-type enzyme is to be understood that the enzyme is present in a naturally occurring organism or in a natural habitat can be isolated from this.
  • enzymes are modifiable and sometimes selectively modified, in particular in order to adapt their properties to the intended uses or to influence their catalytic activity. These changes often occur by altering the amino acid sequence of the enzyme. Such changes can be targeted and thus local or random, for example, by random mutagenesis done.
  • An enzyme variant is understood as meaning enzymes which have been generated from an initial enzyme, for example a wild-type enzyme, by altering the amino acid sequence.
  • the alteration of the amino acid sequence is preferably carried out by mutations, wherein amino acid substitutions, deletions, insertions or combinations thereof may be made.
  • the incorporation of such mutations into proteins is well known in the art and to those skilled in the art of enzyme technology. In principle, all enzymes can be changed in this way.
  • Protease variants are preferred according to the invention. These were generated from an initial protease, for example a wild-type protease, by altering the amino acid sequence, preferably amino acid substitutions, deletions, insertions or combinations thereof.
  • the starting protease does not necessarily have to be a naturally occurring wild-type protease; a protease known from the prior art in which changes have already been made can also be further developed and therefore again serve as an initial protease for generating further protease variants.
  • proteases described above may be used unchanged in agents according to the invention and be stabilized by the compounds described. However, they can also be the starting enzyme for a variant which is then contained in an agent according to the invention and stabilized by the compounds described.
  • the washing or cleaning agent is therefore characterized in that the protease was obtained from an initial protease by at least one change of an amino acid, the change being a substitution, insertion or deletion of an amino acid, and adding it to the parent protease Amino acid level is at least 90%, preferably at least 92.5%, more preferably at least 95% and most preferably at least 97.5% identical.
  • sequence comparisons are known to the person skilled in the art of enzyme technology.
  • sequence comparisons for example, the identity or homology values are determined for sequences to be compared.
  • Such a comparison is accomplished by associating similar sequences in the nucleotide or amino acid sequences of the proteins of interest. This is called homologization.
  • a tabular assignment of the respective positions is referred to as alignment.
  • alignments are created using computer programs, such as the algorithms FASTA or BLAST; This procedure is for example by DJ Lipman and WR Pearson (1985) in Science, Vol. 227, pp. 1435-1441 described.
  • a summary of all matching positions in the compared sequences is called a consensus sequence.
  • Such a comparison also allows a statement about the similarity or homology of the compared sequences to each other. This is represented in percent identity, that is the proportion of identical nucleotides or amino acid residues at the same or in an alignment corresponding positions. A broader concept of homology includes the conserved amino acid substitutions in this value. It then speaks of percent similarity. Such statements can be made about whole proteins or genes or only over individual areas.
  • homologous regions of different proteins are defined by matches in amino acid sequence. These can also be identified by identical function. It goes as far as complete identities in the smallest areas, so-called boxes, which contain only a few amino acids and usually perform essential functions for the overall activity.
  • the functions of the homologous regions are to be understood as the smallest partial functions of the function carried out by the entire protein, such as, for example, the formation of individual hydrogen bonds for the complexation of a substrate or transition complex.
  • sequence comparisons or alignments also serve to determine mutually corresponding positions in different molecules.
  • positions in the respective amino acid or nucleic acid sequence correspond to one another, even if the respective sequences have, for example, different total lengths or different domains or partial sequences or if additional amino acids or nucleotides are present within a sequence are.
  • a specific position in a first sequence can therefore be concretely assigned to a corresponding position in a second sequence, whereby it is quite possible for the positions corresponding to one another to be located at different locations in the molecule.
  • different amino acid residues may be present at the corresponding positions. Therefore, for such sequence comparisons or for the determination Specifically specified a position, which position it is and which enzyme is assumed, that is, which counting method of determining position is to be based.
  • the amino acid sequence of the mature protein of the alkaline protease from Bacillus lentus DSM 5483 is used for determining the position, which is described in International Published Patent Application WO 91/02792 A1 and has a length of 269 amino acid residues (referred to in the present application as Bacillus lentus alkaline protease).
  • the washing or cleaning agent is characterized in that the protease was obtained from an initial protease by at least one change of an amino acid, the change being a substitution or insertion of an amino acid in that region of the amino acid sequence corresponding to the positions 95 to 103 of the alkaline protease from Bacillus lentus is assigned in an alignment.
  • Such a protease variant is particularly preferably a variant with an insertion of a single amino acid according to one or more of the positions 95, 96, 97, 98, 99, 100, 101, 102 and / or 103 and very particularly preferably between positions 97 and 98 and / or positions 99 and 100.
  • the washing or cleaning agent is characterized in that the protease has been obtained from an initial protease by at least one modification of an amino acid which corresponds to the positions 3, 4, 36, 42, 43, 47, 56, 61, 69 , 87, 96, 99, 101, 102, 104, 114, 118, 120, 130, 139, 141, 142, 154, 157, 188, 193, 199, 205, 211, 224, 229, 236, 237, 242 , 243, 250, 253, 255 and 268 of the Bacillus lentus alkaline protease in an alignment, wherein the alteration is a substitution, insertion or deletion of an amino acid.
  • an amino acid change relative to the parent molecule occurs in one or more of the following positions: 3, 4, 43, 61, 188, 193, 199, 211, 224, 250 and 253 (count according to Bacillus lentus alkaline protease), more preferably with one or more of the amino acid substitutions X3T, X4I, X43V, X61A, X188P, X193M, X199I, X211L, X211D, X211E, X211G, X211N or X211Q, X224V, X250G and / or X253N.
  • the protease is a variant with a point mutation in position 211, preferably with a substitution of a single amino acid in this position, particularly preferably with the amino acid substitution X211 L.
  • the above position information relate turn to those amino acid residues that are assigned to the said positions of the alkaline protease from Bacillus lentus in an alignment.
  • Detergents or cleaning agents according to the invention may contain only one enzyme. Alternatively, they may also contain other enzymes in a concentration effective for the effectiveness of the agent.
  • a further subject of the invention thus represents agents which further comprise one or more further enzymes, wherein in principle all enzymes established in the prior art for these purposes can be used.
  • enzymes which can be used as further enzymes are all enzymes which can develop catalytic activity in the agent according to the invention, in particular proteases, amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, ⁇ -glucosidases, carrageenases, oxidases, oxidoreductases, lipases or esterases and preferably mixtures thereof.
  • 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.
  • Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -8 to 5 percent by weight, based on active protein.
  • the enzymes are from 0.001 to 5% by weight, more preferably from 0.01 to 5% by weight, even more preferably from 0.05 to 4% by weight and most preferably from 0.075 to 3.5% by weight.
  • the protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ).
  • the further enzymes particularly preferably support the effect of the agent, for example the cleaning performance of a washing or cleaning agent, with regard to certain stains or stains.
  • the enzymes show synergistic effects with respect to their action against certain stains or stains, ie the enzymes contained in the middle composition mutually support each other in their cleaning performance. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the composition according to the invention.
  • the enzymes used in agents of the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi ,
  • the enzyme (s) and the stabilizing compound are preferably combined with one or more of the following ingredients: nonionic, anionic and / or cationic surfactants, bleaches, bleach activators, bleach catalysts, builders and / or cobuilders, acids, alkaline substances, Hydrotropes, solvents, thickeners, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, corrosion inhibitors, in particular silver protectants (silver corrosion inhibitors), soil release agents, color transfer (or transfer) inhibitors, foam inhibitors, abrasives, dyes, fragrances, perfumes, antimicrobial agents, UV protectants or absorbents, antistatic agents, pearlescing agents and skin protection agents, further stabilizers, in particular enzyme stabilizers, and other components known from the prior art.
  • a further subject of the invention therefore is washing or cleaning agents which are characterized in that they contain at least one further component which is selected from the group consisting of surfactants, builders, acids, alkaline substances, hydrotropes, solvents, thickeners, bleaching agents, Dyes, perfumes, corrosion inhibitors, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, silver corrosion inhibitors, dye transfer inhibitors, foam inhibitors, abrasives, UV absorbers, solvents, antistatic agents, pearlescers and skin protection agents.
  • surfactants builders, acids, alkaline substances, hydrotropes, solvents, thickeners, bleaching agents, Dyes, perfumes, corrosion inhibitors, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, silver corrosion inhibitors, dye transfer inhibitors, foam inhibitors, abrasives, UV absorbers, solvents, antistatic agents, pearlescers and skin protection agents.
  • Agents according to the invention preferably comprise at least one complexing agent and / or builder substances, the builder being in particular a zeolite builder, and / or a nonionic surfactant, the nonionic surfactant preferably being a hydroxy mixed ether, and / or optical Brightener, wherein the optical brightener is diphenyl compounds, in particular distyryl biphenyl derivatives, and / or stilbentriazine derivatives.
  • the ingredients to be selected as well as the conditions under which the agent is used should be optimized for the respective cleaning problem.
  • the usual temperatures for detergents and cleaners in the range of 10 ° C for manual agents over 20 ° C, 30 ° C, 40 ° C and 60 ° C up to 95 ° for mechanical means or in technical applications. Since the temperature is usually infinitely adjustable in modern washing machines and dishwashers, all intermediate stages of the temperature are included.
  • the ingredients of the respective agents are coordinated. Synergies are preferred in terms of cleaning performance. Particularly preferred in this regard are synergies which are present in a temperature range between 20.degree. C. and 60.degree. C., since the enzyme or the enzymes contained in the agents according to the invention are also catalytically active in this temperature range.
  • the washing or cleaning agent is characterized in that it contains at least one further stabilizer.
  • the stabilizer (s) is one or more polyols, in particular glycerol or 1,2-ethylene glycol, an antioxidant, lactate or one or more lactate derivatives or combinations thereof. It is likewise preferably one or more of those enzyme-stabilizing or inhibiting compounds which are described in the international patent applications WO 07/113241 A1 or WO 02/008398 are disclosed.
  • Another object of the invention is the use of a compound of the general structural formula wherein X is an aliphatic or an aromatic radical and Y is an aliphatic or an aromatic radical, as a reversible inhibitor of an enzyme in a washing or cleaning agent. Because, as already stated above, cause these compounds due to their mechanism of action as a reversible inhibitor advantageous stabilization of the enzyme in the washing or cleaning agent.
  • the use is characterized in that the radicals X and Y are identical.
  • the radical X is selected from the group consisting of: -CH 2 -CH 2 -CH 3 , phenyl.
  • the radical Y is selected from the group consisting of: -CH 2 -CH 2 -CH 3 , phenyl.
  • the enzyme is selected from the group consisting of: protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ⁇ -glucosidase, carrageenase, oxidase, Oxidoreductase, lipase, esterase or mixtures thereof.
  • the enzyme is particularly preferably a protease, preferably a serine protease, more preferably a subtilase and particularly preferably a subtilisin.
  • Another object of the invention is therefore the use of an enzyme and a compound of the general structural formula wherein X is an aliphatic or an aromatic radical and Y is an aliphatic or an aromatic radical, for the preparation of a washing or cleaning agent.
  • the compound is one in which the radicals X and Y are identical and / or the radical X is selected from the group consisting of: -CH 2 -CH 2 -CH 3 , phenyl, and / or the Rest Y is selected from the group consisting of: -CH 2 -CH 2 -CH 3 , phenyl.
  • this invention is characterized in that the enzyme is selected from the group consisting of: protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ⁇ -glucosidase, carrageenase, oxidase, oxidoreductase, lipase, esterase or mixtures thereof.
  • the enzyme is particularly preferably a protease, preferably a serine protease, more preferably a subtilase and particularly preferably a subtilisin.
  • Another object of the invention is a washing or cleaning process in which an enzyme acts, which is inhibited and / or stabilized with a compound of the general structural formula wherein X is an aliphatic or an aromatic radical and Y is an aliphatic or an aromatic radical.
  • the compound is one in which the radicals X and Y are identical and / or the radical X is selected from the group consisting of: CH 2 -CH 2 -CH 3 , phenyl, and / or the radical Y is selected from the group consisting of: -CH 2 -CH 2 -CH 3 , phenyl.
  • these compounds cause due to their mechanism of action as a reversible inhibitor advantageous stabilization of the enzyme in the washing or cleaning agent, so that for the washing or cleaning process, a higher enzyme activity is available in comparison with a detergent or cleaning agent in which the enzyme was not stabilized.
  • this subject matter of the invention is characterized in that the enzyme is selected from the group consisting of: protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ⁇ -glucosidase, carrageenase, oxidase, oxidoreductase, lipase, Esterase or mixtures thereof.
  • the enzyme is particularly preferably a protease, preferably a serine protease, more preferably a subtilase and particularly preferably a subtilisin.
  • the washing or cleaning method is further characterized in that a washing or cleaning agent according to the invention is used, as described above.
  • washing or cleaning agents according to the invention can advantageously be used for cleaning purposes.
  • a further subject of the invention is therefore the use of a washing or cleaning agent, as described above, for washing and / or cleaning textiles and / or hard surfaces.
  • the compounds resulted in a residual activity of the protease of less than 60%.
  • V1 is the strongest and thus most suitable protease inhibitor or stabilizer, followed by V2.
  • the residual activities of the protease were 45% for V1 and 56% for V2.
  • a liquid detergent was prepared with the following composition (all figures in percent by weight): 0.3-0.5% xanthan gum, 0.2-0.4% anti-foaming agent, 6-7% glycerol, 0.3 -0.5% ethanol, 4-7% FAEOS, 24-28% nonionic surfactants, 1% boric acid, 1-2% sodium citrate (dihydrate), 2-4% soda, 14-16% coconut fatty acids, 0.5 % HEDP, 0-0.4% PVP, 0-0.05% optical brightener, 0-0.001% dye, balance: demineralized water.
  • This formulation was admixed with the inhibiting compounds of Example 1 to be tested and 1,275,000 HPE / I B. lentus alkaline protease F 49.
  • the protease activity (Henkel protease units) reported in HPE was calculated after van Raay, Saran and Verbeek, according to the publication " For the determination of the proteolytic activity in enzyme concentrates and enzyme-containing detergents, dishwashing detergents and cleaners "in Tenside (1970), Volume 7, pp. 125-132 , certainly.
  • the initial values for the proteolytic activity of the agent in question were compared with the values determined after storage. The higher the activity remaining after storage, the better the protease contained was inactivated during storage and the better the compound in question is suitable as a stabilizer according to the invention.

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Claims (15)

  1. Agent de lavage ou de nettoyage contenant une enzyme et un composé répondant à la formule développée générale
    Figure imgb0018
     dans laquelle X représente un résidu aliphatique ou un résidu aromatique et Y représente un résidu aliphatique ou un résidu aromatique, le résidu X étant choisi parmi le groupe constitué par : un groupe -CH2-CH2-CH3,
    un groupe phényle,
    en particulier un composé dans lequel les résidus X et Y sont identiques et/ou le résidu Y est choisi parmi le groupe constitué par : un groupe -CH2-CH2-CH3, un groupe phényle.
  2. Agent de lavage ou de nettoyage selon la revendication 1, caractérisé en ce que le composé présente, vis-à-vis de l'enzyme, une constante d'inhibition (Ki) de 0,01 à 10 mM, en particulier une constante d'inhibition (Ki) de 0,03 à 5 mM.
  3. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que l'enzyme est présente en une teneur de 2 µg à 20 mg par gramme de l'agent, de préférence de 5 µg à 17,5 mg par g de l'agent, de manière particulièrement préférée de 20 µg à 15 mg par g de l'agent, de manière tout particulièrement préférée de 50 µg à 10 mg de l'agent ;
    et/ou en ce que le composé est présent en une teneur s'élevant jusqu'à 50 mg par g de l'agent, de préférence jusqu'à 10 mg, de manière particulièrement préférée jusqu'à 7 mg, de manière tout particulièrement préférée jusqu'à 5 mg par gramme de l'agent ;
    et/ou en ce que le rapport molaire du composé à l'enzyme s'élève de 1:1 à 1.000:1, en particulier de 1:1 à 500:1, de manière particulièrement préférée de 1:1 à 100:1, de manière tout particulièrement préférée de 1:1 à 20:1.
  4. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la quantité du composé que contient l'agent, rapportée à l'enzyme stabilisée s'élève de 0,01 à 100 x la constante d'inhibition Ki, de préférence de 0,1 à 10 x Ki, de manière particulièrement préférée de 1 à 5 x Ki.
  5. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 4, sous une forme principalement solide, ou bien sous une forme principalement liquide, pâteuse ou de gel.
  6. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'enzyme est choisie parmi le groupe constitué par : les protéases, les amylases, les cellulases, les hémicellulases, les mannanases, les tannases, les xylanases, les xanthanases, les β-glucosidases, les carraghénases, les oxydases, les oxydoréductases, les lipases, les estérases, ou leurs mélanges.
  7. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'enzyme est une protéase, de préférence une sérine protéase, de manière plus préférée une subtilase et de manière particulièrement préférée une subtilisine.
  8. Agent de lavage ou de nettoyage selon la revendication 7, caractérisé en ce que la protéase est obtenue à partir d'une protéase de départ via au moins une modification d'un acide aminé, la modification représentant une substitution, une insertion ou une délétion d'un acide aminé, et en ce qu'elle est identique à la protéase de départ, sur le plan des acides aminés, à concurrence d'au moins 90 %, de préférence d'au moins 92,5 %, de manière particulièrement préférée d'au moins 95 % et de manière tout particulièrement préférée d'au moins 97,5 % ;
    et/ou en ce que la protéase est obtenue à partir d'une protéase de départ via au moins une modification d'un acide aminé, la modification étant une substitution ou une insertion d'un acide aminé dans la zone de la séquence d'acides aminés à laquelle sont attribuées dans une mise en alignement les positions 95 à 103 de la protéase alcaline issue de Bacillus lentus ;
    et/ou en ce que la protéase est obtenue à partir d'une protéase de départ via au moins une modification d'un acide aminé auquel sont attribuées dans une mise en alignement les positions 3, 4, 36, 42, 43, 47, 56, 61, 69, 87, 96, 99, 101, 102, 104, 114, 118, 120, 130, 139, 141, 142, 154, 157, 188, 193, 199, 205, 211, 224, 229, 236, 237, 242, 243, 250, 253, 255 et 268 de la protéase alcaline issue de Bacillus lentus, la modification représentant une substitution, une insertion ou une délétion d'un acide aminé.
  9. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'il contient au moins un stabilisateur supplémentaire, en particulier un stabilisateur à propos duquel il s'agit d'un ou de plusieurs polyols, en particulier du glycérol ou du 1,2-éthylèneglucol, d'un antioxydant, d'un lactate ou d'un ou de plusieurs dérivés de lactate, ou encore de leurs combinaisons.
  10. Utilisation d'un composé répondant à la formule développée générale
    Figure imgb0019
     dans laquelle X représente un résidu aliphatique ou un résidu aromatique et Y représente un résidu aliphatique ou un résidu aromatique, le résidu X étant choisi parmi le groupe constitué par : un groupe -CH2-CH2-CH3, un groupe phényle, à titre d'inhibiteur réversible d'une enzyme dans un agent de lavage ou de nettoyage ;
    en particulier un composé dans lequel les résidus X et Y sont identiques et/ou le résidu Y est choisi parmi le groupe constitué par : un groupe -CH2-CH2-CH3, un groupe phényle.
  11. Utilisation d'une enzyme, en particulier d'une enzyme qui est choisie parmi le groupe constitué par: les protéases, les amylases, les cellulases, les hémicellulases, les mannanases, les tannases, les xylanases, les xanthanases, les β-glucosidases, les carraghénases, les oxydases, les oxydoréductases, les lipases, les estérases, ou leurs mélanges, et d'un composé répondant à la formule développée générale
    Figure imgb0020
     dans laquelle X représente un résidu aliphatique ou un résidu aromatique et Y représente un résidu aliphatique ou un résidu aromatique, le résidu X étant choisi parmi le groupe constitué par : un groupe -CH2-CH2-CH3, un groupe phényle, pour la préparation d'un agent de lavage ou de nettoyage ; en particulier un composé dans lequel les résidus X et Y sont identiques et/ou le résidu Y est choisi parmi le groupe constitué par : un groupe -CH2-CH2-CH3, un groupe phényle.
  12. Utilisation selon la revendication 11, caractérisée en ce que l'enzyme est une protéase, de préférence une sérine protéase, de manière plus préférée une subtilase et de manière particulièrement préférée une subtilisine.
  13. Procédé de lavage ou de nettoyage, dans lequel on met en oeuvre une enzyme, en particulier une enzyme qui est choisie parmi le groupe constitué par: les protéases, les amylases, les cellulases, les hémicellulases, les mannanases, les tannases, les xylanases, les xanthanases, les β-glucosidases, les carraghénases, les oxydases, les oxydoréductases, les lipases, les estérases, ou leurs mélanges, qui est inhibée et/ou stabilisée avec un composé répondant à la formule développée générale
    Figure imgb0021
     dans laquelle X représente un résidu aliphatique ou un résidu aromatique et Y représente un résidu aliphatique ou un résidu aromatique, le résidu X étant choisi parmi le groupe constitué par : un groupe -CH2-CH2-CH3, un groupe phényle, en particulier un composé dans lequel les résidus X et Y sont identiques et/ou le résidu Y est choisi parmi le groupe constitué par : un groupe -CH2-CH2-CH3, un groupe phényle.
  14. Procédé de lavage ou de nettoyage, caractérisé en ce qu'on met en oeuvre un agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 9.
  15. Utilisation d'un agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 9, pour le lavage et/ou le nettoyage de textiles et/ou de surface dures.
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