EP3380598A1 - Stabilisateurs d'enzymes - Google Patents

Stabilisateurs d'enzymes

Info

Publication number
EP3380598A1
EP3380598A1 EP16795075.7A EP16795075A EP3380598A1 EP 3380598 A1 EP3380598 A1 EP 3380598A1 EP 16795075 A EP16795075 A EP 16795075A EP 3380598 A1 EP3380598 A1 EP 3380598A1
Authority
EP
European Patent Office
Prior art keywords
group
alkyl group
protease
washing
cleaning agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16795075.7A
Other languages
German (de)
English (en)
Other versions
EP3380598B1 (fr
Inventor
André HÄTZELT
Timothy O'connell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Henkel AG and Co KGaA filed Critical 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to detergents and cleaners containing at least one enzyme and at least one organic compound which acts as a protease inhibitor and is thus a suitable enzyme stabilizer, and the use of these compounds as enzyme stabilizer in enzyme-containing detergents and cleaners.
  • enzymes in detergents and cleaners have 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.
  • 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 (glycosidases) Hydrolysis in particular of special vegetable polymers.
  • soiling such as pectinases, ⁇ -glucanases, mannanases or other hemicellulases (glycosidases) Hydrolysis in particular of special vegetable polymers.
  • 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.
  • 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 having aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or esters of the abovementioned compounds.
  • a particularly good protection results when boric acid derivatives are used together with polyols, since these can then form a complex stabilizing the enzyme.
  • 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.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also established for this purpose. Certain organic acids used as builders are capable, as disclosed in WO 97/18287, of stabilizing an enzyme in addition to their builder function.
  • subtilisin-type proteases (subtilases, subtilopeptidases, EC 3.4.21.62) have a prominent 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. Your 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.
  • 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.
  • polyols such as glycerol and 1, 2-propylene glycol have proved to be unfavorable due to their high levels of use necessary concentrations, because the other active ingredients of the respective agents can thus be contained only in correspondingly lower proportions.
  • boric acid derivatives occupy an outstanding position among the serine protease inhibitors, which are effective at comparatively low concentrations.
  • 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.
  • 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.
  • the use in total liquid, gel or pas- tscher washing and cleaning agents was of particular interest, and including in particular those containing water.
  • washing or cleaning agents which comprise at least one protease and at least one enzyme stabilizer, the at least one enzyme stabilizer being selected from compounds of the general structural formula (I)
  • R 1 is a C 1 -C 6 -alkyl group, a C 2 -C 6 -alkenyl group, a C 2 -C 6 -hydroxyalkyl group, a C 1 -C 6 -alkyl-oxy-C 1 -C 6 -alkyl group, a carboxy-C 1 -C 6 -alkyl group, an aryl-Ci-C6- and R 2,
  • R 3, R 4 and R 5 each independently represent hydrogen, a C 1 -C 6 -alkyl group, a halogen atom or a C 1 -C 6 -acyl group.
  • C 1 -C 6 -alkyl radicals are the groups -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH (CH 3 ) 2, -CH (CH 3 ) CH 2 CH 3 , -C (CH 3 ) 3 .
  • Examples of a C2-C6 alkenyl group are a prop-2-enyl group (allyl group), a 2-methylprop-2-enyl group, a but-3-enyl group, a but-2-enyl group, a pent-4-enyl group or a pent-3-enyl group, with the prop-2-enyl group being preferred.
  • Examples of a C 2 -C 6 -hydroxyalkyl group are -CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, -CH 2 CH (OH) CH 3 and
  • Ci-Ce-alkyl-oxy-Ci-Ce alkyl groups are the groups -CH 2 CH 2 OCH 3, - CH 2 CH 2 CH 2 OCH 3, -CH 2 CH 2 OCH 2 CH 3, -CH 2 CH 2 CH 2 OCH 2 CH 3, -CH 2 CH 2 OCH (CH 3 ) 2, -CH 2 CH 2 CH 2 OCH (CH 3 ) 2.
  • Examples of a carboxy-C 1 -C 6 -alkyl group are the carboxymethyl group, the 2-carboxyethyl group or the 3-carboxypropyl group.
  • Examples of aryl-C 1 -C 6 -alkyl groups are the benzyl group and the 2-phenylethyl group.
  • Examples of a heteroaryl-C 1 -C 6 -alkyl group are the pyridin-2-ylmethyl group, the pyridin-3-ylmethyl group, the pyridin-4-ylmethyl group, the pyrimidin-2-ylmethyl group, the pyrrol-1-ylmethyl group, the pyrrole-1 -ylethyl group, the pyrazol-1-ylmethyl group or the pyrazol-1-ylethyl group.
  • Examples of an aryl group are the phenyl group, the 1-naphthyl group or the 2-naphthyl group.
  • Examples of a heteroaryl group are the pyridin-2-yl group, the pyridin-3-yl group, the pyridin-4-yl group, the pyrimidin-2-yl group, the pyrrol-1-yl group, the pyrrol-2-yl group, the pyrazole group.
  • Ci-C6-acyl group examples include acetyl (1-oxo-ethyl), 1-oxo-propyl, 1-oxo-butyl, 1-oxo-pentyl, 1-oxo-2,2-dimethylpropyl and 1-oxo-hexyl ,
  • radical R 1 has the general structure (I) for a C 1 -C 6 -alkyl group, for a C 2 -C 6 -alkenyl group or for a C 2 -C 6 -hydroxyalkyl group stands. It is preferred according to the invention if the radical R 1 is a C 1 -C 6 -alkyl group, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or tert-butyl, and particularly preferably methyl.
  • R2, R3, R4 and R5 are each hydrogen.
  • a further embodiment of the present invention is therefore characterized in that the compound according to formula (I) is a 3-alkyl-1,2-benzoisothiazol-1,1-dioxide.
  • Particularly suitable compounds are selected from 3-methyl, 3-ethyl, 3- (1-propyl) -, 3-isopropyl, 3- (1-butyl) -, 3- (2-butyl) -, and 3- (tert-butyl) -1,2-benzisothiazole-1,1-dioxide, especially 3-methyl-1,2-benzisothiazole-1,1-dioxide.
  • 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.
  • 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.
  • the compounds relevant to the invention form a complex with the protease to be inhibited / stabilized according to the invention.
  • 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.
  • the equilibrium coefficient of this reaction is called the inhibition constant or K.
  • the first advantage of the compounds relevant to the invention over the prior art is that they have favorable inhibition constants with respect to the proteases which can be used in detergents and cleaners.
  • the inhibitors thus bind reversibly, i. they do not interfere with solid and not too loose transient interactions with the enzyme.
  • the majority of the protease relevant to the invention is thus present during storage in the form of a protease-inhibitor complex.
  • 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.
  • the binding equilibrium is shifted in the direction of dissociation so that the complex dissolves and most of the protease relevant protease can become proteolytically active.
  • the second advantage of the compounds relevant to the invention over the prior art is that they have as elements only C, H, N, S and 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. Furthermore, they have a good solubility in water, in particular due to the carboxyl or sulfonyl groups contained, so that they can be easily incorporated into appropriate means and precipitation during storage is avoided.
  • the compounds mentioned probably act as reversible inhibitors because, similar to the substrate of the proteases, they are structurally adapted to the conditions of the binding pocket.
  • a washing or cleaning process in which a protease is inhibited which is inhibited and / or stabilized with a compound described above;
  • washing or cleaning agent for washing and / or cleaning textiles and / or hard surfaces; such as
  • the enzyme i. the protease in an amount of 0.05-5% by weight, preferably 0.05-2% by weight, and the enzyme stabilizer in an amount of 0.05-15% by weight, preferably 0.05- 5 wt .-%, based on the total weight of the washing or cleaning agent contained in this.
  • 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 0.05-15% by weight, preferably 0.05-5% by weight and the enzyme stabilizer in one Amount of 0.05-35 wt .-%, preferably 0.05-10 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.
  • 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:
  • alkaline protease from Bacillus lentus, preferably from Bacillus lentus (DSM 5483),
  • alkaline protease from Bacillus sp. (DSM 14390) or an at least 98.5% identical alkaline protease, and
  • 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 amylase (s) is preferably an ⁇ -amylase.
  • the hemicellulase is preferably a ⁇ -glucanase, a pectinase, a pullulanase and / or a mannanase.
  • the cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase.
  • the oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
  • 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.
  • detergents for textiles, carpets, or natural fibers for which the term detergent is used.
  • dishwashing detergents for dishwashers or manual dishwashing detergents or hard surface cleaners such as metal, Glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term detergent is used, so in addition to manual and automatic dishwasher detergents, for example, scouring agents, glass cleaner, toilet scenters, etc.
  • washing and Cleaning agents in the context of the invention also include washing aids, which are metered into the actual detergent during manual or automatic textile washing in order to achieve a further effect.
  • 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.
  • the fabric softeners are calculated.
  • Embodiments of the present invention include all solid, powdered, liquid, gelatinous or pasty administration forms of agents described herein, which if appropriate can also consist of several phases and can be present in compressed or uncompressed form.
  • 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.
  • 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.
  • the agent may be present as a one-component system. Such funds consist of one phase.
  • 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 at least one further ingredient being present in the composition.
  • the agents described herein may contain surfactants, builders, bleaches or bleach activators.
  • 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.
  • 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.
  • 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.
  • 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.
  • protease-containing detergents and cleaners The storage stability of protease-containing detergents and cleaners in the presence of candidate compounds for use as enzyme stabilizers was investigated.
  • the protease used was the Bacillus lentus alkaline protease (DSM 5483) with the substitution R99E.
  • the candidate compounds (see Table 2) were formulated in parallel reaction mixtures in the presence of 1, 2-propanediol in each case to 1% (w / w) in a detergent formulation (see Table 1). Then the protease was added 1% (w / w) to the formulation and the formulation stored at 30 ° C for 20h, 140h and 234h.
  • the control batch contained only protease and the detergent formulation (and 1% w / w 1, 2-propanediol).
  • the proteolytic activity of the 1% protease was determined from the described reaction mixtures.
  • the release of the chromophore para-nitroaniline from the substrate succinyl alanine-alanine-proline-phenylalanine-para-nitroanilide (AAPFpNA, Bachem L-1400) was determined.
  • 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.
  • the initial values for the proteolytic activity of the agent in question are compared with the values determined after storage.
  • the stabilizing effect of each tested compound is therefore measured as a relative percentage increase in protease residual activity.
  • the pH of the formulation was adjusted to 8.4 by the NaOH.
  • the formulation was clear and colorless.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des lessives et des nettoyants contenant au moins une protéase, et au moins un composé organique de formule (I) qui agit en tant qu'inhibiteur de protéases, et constitue par conséquent un stabilisateur d'enzymes approprié, ainsi que l'utilisation de ces composés en tant que stabilisateurs d'enzymes dans des lessives et des nettoyants contenant des protéases. L'invention concerne également des procédés de lavage et de nettoyage correspondants et l'utilisation des produits décrits.
EP16795075.7A 2015-11-25 2016-11-15 Stabilisateurs d'enzymes Active EP3380598B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015223268.9A DE102015223268A1 (de) 2015-11-25 2015-11-25 Enzymstabilisatoren
PCT/EP2016/077625 WO2017089161A1 (fr) 2015-11-25 2016-11-15 Stabilisateurs d'enzymes

Publications (2)

Publication Number Publication Date
EP3380598A1 true EP3380598A1 (fr) 2018-10-03
EP3380598B1 EP3380598B1 (fr) 2019-08-21

Family

ID=57288445

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16795075.7A Active EP3380598B1 (fr) 2015-11-25 2016-11-15 Stabilisateurs d'enzymes

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US (1) US20180340138A1 (fr)
EP (1) EP3380598B1 (fr)
DE (1) DE102015223268A1 (fr)
WO (1) WO2017089161A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3712236A1 (fr) * 2019-03-20 2020-09-23 Henkel AG & Co. KGaA Amélioration de la solubilité de divers systèmes tensioactifs par application de phosphonates
GB202015368D0 (en) * 2020-09-29 2020-11-11 Reckitt Benckiser Vanish Bv Composition for the removal of stains and malodour
GB202204137D0 (en) * 2022-03-24 2022-05-11 Reckitt Benckiser Vanish Bv Composition for the removal of stains and malodour

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
US5041232A (en) * 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
US5413733A (en) * 1993-07-26 1995-05-09 Lever Brothers Company, Division Of Conopco, Inc. Amidooxy peroxycarboxylic acids and sulfonimine complex catalysts
DK1921147T3 (da) * 1994-02-24 2011-09-19 Henkel Ag & Co Kgaa Forbedrede enzymer og detergenter indeholdende disse
US5741767A (en) 1995-11-16 1998-04-21 Lever Brothers Company, Division Of Conopco, Inc. Peracid based dishwashing detergent composition
DE102007041754A1 (de) * 2007-09-04 2009-03-05 Henkel Ag & Co. Kgaa Polycyclische Verbindungen als Enzymstabilisatoren
DE102008017103A1 (de) 2008-04-02 2009-10-08 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel enthaltend Proteasen aus Xanthomonas
US20110174340A1 (en) * 2010-01-20 2011-07-21 Ecolab USA Low and high temperature enzymatic system
DE102010063458A1 (de) * 2010-12-17 2012-06-21 Henkel Ag & Co. Kgaa Lagerstabiles flüssiges Wasch- oder Reinigungsmittel enthaltend Protease und Amylase

Also Published As

Publication number Publication date
US20180340138A1 (en) 2018-11-29
DE102015223268A1 (de) 2017-06-01
EP3380598B1 (fr) 2019-08-21
WO2017089161A1 (fr) 2017-06-01

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