EP2655587B1 - Préparation tensioactive liquide contenant de la lipase et du phophonate - Google Patents

Préparation tensioactive liquide contenant de la lipase et du phophonate Download PDF

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Publication number
EP2655587B1
EP2655587B1 EP11805804.9A EP11805804A EP2655587B1 EP 2655587 B1 EP2655587 B1 EP 2655587B1 EP 11805804 A EP11805804 A EP 11805804A EP 2655587 B1 EP2655587 B1 EP 2655587B1
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EP
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Prior art keywords
lipase
acid
surfactant preparation
phosphonate
surfactant
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EP11805804.9A
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German (de)
English (en)
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EP2655587A1 (fr
Inventor
Karl-Heinz Maurer
Timothy O'connell
Petra Siegert
Thomas Weber
Susanne Tondera
Hendrik Hellmuth
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL11805804T priority Critical patent/PL2655587T3/pl
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/40—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using enzymes
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/78—Neutral esters of acids of phosphorus
    • 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
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D3/365—Organic compounds containing phosphorus containing carboxyl groups
    • 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 invention is in the field of liquid enzyme-containing surfactant preparations, as used for example in washing, cleaning or disinfecting. More particularly, the invention relates to liquid enzyme-containing surfactant formulations containing defined lipases in combination with a phosphonate, and further proposes uses and methods in which such formulations are employed. The invention further relates to uses of defined lipases in liquid surfactant formulations containing a phosphonate.
  • Surfactant preparations in particular in modern liquid detergents, but also in detergents or disinfectants, often contain phosphonates. They are used, for example, as complexing agents, to prevent precipitation or as a bleach stabilizer. As complexing agents they serve, for example, as water softeners. They can encase cations such as Ca 2+ in the solution and thus alter the chemical behavior of the cation. In the case of calcium, the property of water hardness disappears. Other cations can be complexed and thus protected against chemical reactions. They can also participate as corrosion inhibitors or serve as a stabilizer for peroxides, especially in bleaching agents.
  • complexing agents serve, for example, as water softeners. They can encase cations such as Ca 2+ in the solution and thus alter the chemical behavior of the cation. In the case of calcium, the property of water hardness disappears. Other cations can be complexed and thus protected against chemical reactions. They can also participate as corrosion inhibitors or serve as a stabilizer for peroxides, especially in bleach
  • lipase is increasingly used in surfactant preparations, in particular in detergents or cleaners.
  • a lipase is an enzyme that catalyzes the hydrolysis of ester bonds in lipid substrates, especially in fats and oils. Lipases are therefore a group of esterases. Lipases are generally versatile enzymes that accept a variety of substrates, for example, aliphatic, alicyclic, bicyclic and aromatic esters, thioesters and activated amines. Lipases act against fat residues in the laundry to catalyze their hydrolysis (lipolysis).
  • Lipases with broad substrate spectra are used in particular where inhomogeneous raw materials or substrate mixtures have to be reacted, for example in detergents and cleaners, since soiling may consist of differently structured fats and oils.
  • the lipases used in the washing or cleaning agents known from the prior art are usually of microbial origin and are usually derived from bacteria or fungi, for example the genera Bacillus, Pseudomonas, Acinetobacter, Micrococcus, Humicola, Trichoderma or Trichosporon. Lipases are usually produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi.
  • EP 443063 is, for example, intended for detergents and cleaners lipase from Pseudomonas sp. ATCC 21808, but not explicitly for use in a phosphonate-containing liquid formulation.
  • JP 1225490 is a lipase from Rhizopus oryzae disclosed.
  • this document also does not disclose a specific liquid surfactant preparation which necessarily contains a phosphonate in combination with a Rhizopus oryzae lipase.
  • WO037097780 discloses combinations of certain lipases with transition metal bleach catalysts to increase cleaning performance.
  • WO2005 / 124012 discloses an enzymatic bleaching system containing phosphonate, at least one oxidase and at least one perhydrolase, and their use in various care and cleaning agents.
  • lipases from Rhizopus oryzae or Mucor javanicus are not mentioned in either document.
  • WO2004 / 053039 discloses detergent compositions containing a combination of an endoglucanase and a Rhizopus oryzae lipase. However, these detergent compositions do not contain phosphonates.
  • DE 102007003143 discloses alkaline proteases from Bacillus gibsonii, and their use in detergents and cleaners, as well as their combination with lipases.
  • a liquid surfactant preparation containing a phosphonate in combination with a lipase from Rhizopus oryzae or Mucor javanicus is also not apparent from this document.
  • lipases are suitable for use in liquid surfactant preparations. Many lipases do not show sufficient catalytic performance or stability in such formulations. In phosphonate-containing liquid surfactant preparations, this problem is even more serious, for example due to the complex-forming properties of the phosphonates or due to unfavorable interactions between the phosphonate and the lipase.
  • lipase-containing liquid surfactant preparations of the prior art in particular those containing phosphonates, have the disadvantage that they often do not have satisfactory lipolytic activity and therefore the surfactant preparation does not show optimal cleaning performance on lipase-sensitive soils.
  • the object of the present invention is to overcome the mentioned disadvantage and to provide a phosphonate-containing liquid surfactant preparation which has a beneficial lipolytic activity.
  • An object of the invention is a liquid surfactant preparation comprising a phosphonate and a lipase which is naturally present in a microorganism, wherein the microorganism is Rhizopus oryzae or Mucorjavanicus.
  • a liquid surfactant preparation which contains the combination of such a lipase with a phosphonate has advantageous cleaning performance on lipase-sensitive soiling.
  • a surfactant preparation exhibits an improved cleaning performance on at least one, preferably on several lipase-sensitive stains, in particular on textiles and / or hard surfaces.
  • a surfactant preparation according to the invention is also advantageously storage-stable.
  • inventive surfactant formulations show an advantageous cleaning performance with respect to at least one lipase-sensitive soiling at temperatures between 10 ° C and 80 ° C, preferably also at low temperatures, for example between 10 ° C and 50 ° C, between 10 ° C and 40 ° C or between 20 ° C and 40 ° C.
  • the present invention is therefore a particularly advantageous selection of a lipase for a phosphonate-containing liquid surfactant preparation.
  • cleaning performance is understood to mean the whitening performance of one or more soiling, in particular laundry soiling or scrape dirt, which are sensitive to degradation by the lipase.
  • soiling in particular laundry soiling or scrape dirt
  • examples of such stains are carbon black / mineral oil, carbon black / olive oil, pigment / oil or skin fat (sebum) / carbon black, in each case for example on cotton fabric, in particular as indicated below.
  • both the surfactant preparation which comprises the lipase or the washing or cleaning liquor formed by this surfactant preparation, and the lipase itself have a respective cleaning performance.
  • the cleaning performance of the lipase thus contributes to the cleaning performance of the surfactant preparation or the washing or cleaning liquor formed by the surfactant preparation.
  • the cleaning performance is preferably determined as indicated below.
  • Washing or cleaning liquor is understood as meaning the use solution containing the surfactant preparation which acts on textiles or fabrics (wash liquor) or hard surfaces (cleaning liquor) and thus comes into contact with the soiling present on textiles or fabrics or hard surfaces.
  • the washing or cleaning liquor arises when the washing or cleaning process begins and the surfactant preparation, in particular the detergent or cleaning agent, for example, in a washing machine, dishwasher or other suitable container is diluted with water.
  • a lipase contained in a surfactant preparation according to the invention has a lipolytic activity, that is, it is capable of hydrolysis (lipolysis) of lipids such as glycerides or cholesterol esters.
  • the lipase contained in a surfactant preparation according to the invention is naturally present in a microorganism of the species Rhizopus oryzae or Mucor javanicus. Naturally present in this context means that the lipase is a separate enzyme of the microorganism.
  • the lipase can thus be expressed in the microorganism from a nucleic acid sequence which is part of the chromosomal DNA of the microorganism in its wild-type form.
  • nucleic acid sequence is therefore present in the wild-type form of the microorganism and / or can be isolated from the wild-type form of the microorganism from this.
  • a lipase or the nucleic acid sequence coding for it in the microorganism would be incorporated into the microorganism by means of genetic engineering have been deliberately introduced so that the microorganism would have been enriched to the lipase or the coding for them nucleic acid sequence.
  • a lipase naturally present in a microorganism of the genus Rhizopus oryzae or Mucor javanicus may well have been produced recombinantly from another organism.
  • the fungus Rhizopus oryzae belongs to the class of Zygomycetes (subclass Incertae sedis), herein to the order Mucorales and here again to the family Mucoraceae and the genus Rhizopus.
  • the fungus Mucorjavanicus also belongs to the class of Zygomycetes (subclass Incertae sedis), herein to the order Mucorales and here again to the family Mucoraceae, then herein to the genus Mucor.
  • the names Rhizopus oryzae and Mucorjavanicus are the biological species names within the respective genus.
  • Phosphonates are salts and organic compounds, especially esters, of phosphonic acid.
  • M' stands for a monovalent metal.
  • inorganic phosphonates are also referred to as primary and secondary phosphites, respectively.
  • Inorganic phosphonates are formed, for example, by reaction of phosphonic acid HP (O) (OH) 2 , in particular the stable tautomeric form of phosphorous acid with a (primary) or two (secondary) equivalents of base, for example alkali metal hydroxide.
  • organic P-substituted phosphonates which have a phosphorus-carbon bond (phosphorus-organic compounds).
  • Organic P-substituted phosphonates are formed, for example, by the Michaelis-Arbusov reaction. Many of these phosphonates are soluble in water. Some technically important phosphonates also carry amino group (s). Some of these aminophosphonates have structural similarities to complexing agents such as EDTA, NTA or DTPA and have a similar function.
  • Particularly preferred phosphonates in the context of the present invention are 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotrimethylenephosphonic acid (ATMP), nitrilotrimethylenephosphonic acid (NTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP, DETPMP or DTPNT), ethylenediamine tetramethylenephosphonic acid (EDTMP) and 2-phosphonobutane.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • ATMP aminotrimethylenephosphonic acid
  • NTMP nitrilotrimethylenephosphonic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid
  • DETPMP DETPMP or DTPNT
  • ETMP ethylenediamine tetramethylenephosphonic acid
  • 2-phosphonobutane 2-phosphonobutane.
  • 1,2,4-tricarboxylic acid PBS-AM, also referred to as 3-carboxy-3-phosphonoadipic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid sodium
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • Such phosphonates are available, for example, under the trade names Dequest® 2066 and Dequest® 2010 (each from Thermphos).
  • the surfactant preparation is characterized in that the lipase has an amino acid sequence which corresponds to the amino acid sequence shown in SEQ ID NO. 1 amino acid sequence is at least 80% identical. More preferably, the amino acid sequence is at least 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95% %, 96%, 97%, 98%, 99% and most preferably 100% identical to that shown in SEQ ID NO. 1 indicated amino acid sequence.
  • SEQ ID NO. 1 is the sequence of a mature (mature) lipase from Rhizopus oryzae.
  • Lipases which are very particularly preferred according to the invention are the lipase enzymes obtainable from the company Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE® and Lipase F® (also Lipase JV®).
  • the Lipase F® is naturally present in Rhizopus oryzae.
  • the lipase M-AP10® is naturally present in Mucor javanicus.
  • a lipase to a liquid surfactant preparation which comprises a phosphonate, in particular one as described above, provides a particularly advantageous lipolytic activity in this preparation.
  • surfactant preparations are sufficiently stable on storage, in particular with regard to their remaining lipolytic activity after storage, in particular after a storage period of 1 to 5 weeks, 1 to 4 weeks, 1.5 to 3 weeks and particularly preferably after 2 weeks.
  • nucleic acid or amino acid sequences is determined by a sequence comparison. Such a comparison is made by assigning similar sequences in the nucleotide sequences or amino acid sequences to each other. This sequence comparison is preferably carried out based on the BLAST algorithm established and commonly used in the prior art (cf., for example, US Pat Altschul, SF, Gish, W., Miller, W., Myers, EW & Lipman, DJ (1990) "Basic local alignment search tool.” J. Mol. Biol. 215: 403-410 , and Altschul, Stephan F., Thomas L. Madden, Alejandro A. Schaffer, Jinghui Zhang, Hheng Zhang, Webb Miller, and David J.
  • T-Coffee cf., for example Notredame et al. (2000): T-Coffee: A novel method for multiple sequence alignments. J. Mol. Biol. 302, 205-217 ) or programs based on these programs or algorithms.
  • Clustal cf., for example, Chenna et al. (2003): Multiple sequence alignment with the Clustal series of programs.
  • T-Coffee cf., for example Notredame et al. (2000): T-Coffee: A novel method for multiple sequence alignments. J. Mol. Biol.
  • sequence comparisons and alignments are preferably created with the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the default parameters specified.
  • nucleic acid or amino acid sequence can be small and comprise only a few nucleotides or amino acids. Often, such small regions exert essential functions for the overall activity of the protein. It may therefore be useful to relate sequence matches only to individual, possibly small areas. Unless stated otherwise, identity or homology information in the present application, however, refers to the total length of the respectively indicated nucleic acid or amino acid sequence.
  • the detergent for the washing system is a liquid detergent composed as follows (all figures in weight percent): 0.3-0.5% xanthan gum, 0.2-0.4% anti-foaming agent, 6-7% glycerol, 0.3-0.5% ethanol, 4-7% FAEOS (fatty alcohol ether sulfate), 24-28% nonionic surfactants, 1% boric acid, 1-2% sodium citrate (dihydrate), 2-4% soda , 14-16% coconut fatty acids, 0.5% HEDP (1-hydroxyethane-1,1-diphosphonic acid), 0-0.4% PVP (polyvinylpyrrolidone), 0-0.05% optical brightener, 0-0.001% Dye, remainder demineralized water.
  • the lipase is used in this regard in a concentration of 0.0001-0.06 wt .-%, preferably from 0.001 to 0.006 wt .-%, in the detergent, based on active protein.
  • the dosage of the liquid detergent is between 2.0 and 9.0, preferably between 2.5 and 8.0, between 3.0 and 7.0 and more preferably 3.5 grams per liter of wash liquor. Washing takes place in a pH range between pH 8 and pH 10.5, preferably between pH 8 and pH 9.
  • the lipase activity in the wash liquor is not equal to zero at the start of washing.
  • the degree of whiteness i. the brightening of the stains, as a measure of the cleaning performance is determined by optical measurement methods, preferably photometrically.
  • a suitable device for this purpose is for example the spectrometer Minolta CM508d.
  • the devices used for the measurement are previously calibrated with a white standard, preferably a supplied white standard.
  • the activity-like use of the respective lipase ensures that even if the ratio of active substance to total protein (the values of the specific activity) diverge, the respective enzymatic properties, for example the cleaning performance of certain soils, are compared. In general, a low specific activity can be compensated by adding a larger amount of protein.
  • the lipase activity is determined in a customary manner, preferably as described in Bruno Stellmach, "Methods of determination enzymes for pharmacy, food chemistry, engineering, biochemistry, biology, medicine” (Steinkopff Verlag Darmstadt, 1988, p 172ff).
  • lipase-containing samples are added to an olive oil emulsion in emulsifier-containing water and incubated at 30 ° C and pH 9.0. This fatty acids are released. These will be with an autotitrator over 20min. titrated continuously with 0.01 N sodium hydroxide solution so that the pH remains constant (“pH-stat titration"). Based on the sodium hydroxide consumption, the determination of the lipase activity takes place by reference to a reference lipase sample.
  • lipases are formed as so-called pre-proteins, ie together with a propeptide and / or a signal peptide. Often the prodrug and / or signal peptide are N-terminal sequences. In the course of the folding and / or secretion process of the protein Cleaved signal and / or propeptide, so that after the cleavage of the pro- and / or signal peptide, the then mature lipase exerts its catalytic activity without the originally present N-terminal amino acids.
  • the mature (mature) lipases ie the enzymes processed after their preparation, are preferred over the preproteins.
  • the lipases may also be modified by the cells producing them after production of the polypeptide chain, for example, by attachment of sugar molecules, formylations, aminations, etc. Such modifications are post-translational modifications and may, but do not, have an effect on the function of the lipase.
  • the lipase contained in a surfactant preparation according to the invention may be adsorbed to carriers and / or embedded in encapsulating substances in order to protect them against premature inactivation. In the washing or cleaning liquor, ie under conditions of use, the lipase is then released and can develop their lipolytic action.
  • the surfactant preparation is characterized in that the phosphonate is contained in an amount of 0.01 to 4 wt .-%. Further preferred amounts of the phosphonate contained in the surfactant preparation are from 0.01 to 3% by weight, from 0.01 to 2.5% by weight, from 0.02 to 2.4% by weight, from 0, 02 to 2 wt .-%, from 0.03 to 1.5 wt .-% or from 0.05 to 1 wt .-%.
  • the lipase is preferably contained in a surfactant preparation according to the invention in each case in an amount of from 1 ⁇ 10 -8 to 5% by weight, based on active protein. More preferably, the lipase is in an amount of 1 x 10 -7 -3 wt .-%, from 0.00001 to 1 wt .-%, from 0.0002 to 0.8% wt .-% and particularly preferably from 0 , 0008-0.4% wt .-% in a surfactant preparations according to the invention, based on active protein.
  • 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 Aktivenzymproteinehalt can by means of "Active Site” titration of the lipase preparation according to Rotticci et al .: "An active-site titration method for lipases” (Biochim Biophys Acta 1483 (1), pages 132-140 ).
  • a surfactant preparation is to be understood as meaning any type of composition which comprises at least one surfactant.
  • a composition contains a surfactant as described below.
  • liquid or flowable administration forms can serve as liquid surfactant preparations.
  • "Flowable" in the context of the present application are preparations which are pourable and can have viscosities of up to several tens of thousands of mPas. The viscosity can be measured by conventional standard methods (for example, Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 5 to 10,000 mPas.
  • Preferred surfactant formulations have viscosities of 10 to 8000 mPas, with values between 120 to 3000 mPas being particularly preferred.
  • a liquid surfactant preparation in the context of the present invention can therefore also be gelatinous or paste-like, it can be in the form of a homogeneous solution or suspension, and can be sprayed or packaged in other conventional dosage forms, for example.
  • a liquid surfactant preparation according to the invention can be used as such or after dilution with water, in particular for the cleaning of textiles and / or hard surfaces.
  • Such dilution can be readily made by diluting a measured amount of the surfactant preparation in a further amount of water in certain weight ratios of surfactant preparation: water and optionally shaking this dilution to ensure uniform distribution of the surfactant formulation in the water.
  • Possible weight or volume ratios of the dilutions are from 1: 0 surfactant preparation: water to 1: 10,000 or 1: 20000 surfactant preparation: water, preferably from 1:10 to 1: 2000 surfactant preparation: water.
  • a surfactant preparation in the sense of the present invention can therefore also be the washing or cleaning liquor itself.
  • the surfactant preparation is a washing, cleaning or disinfecting agent.
  • the detergents include all conceivable types of detergents, in particular detergents for textiles, carpets or natural fibers. They can be provided for manual and / or machine application.
  • the detergents also include washing aids, which are added to the actual detergent in the manual or machine textile washing, in order to achieve a further effect.
  • Detergents include all agents for cleaning and / or disinfecting hard surfaces also found in all of the above dosage forms, manual and automatic dishwashing detergents, carpet cleaners, abrasives, glass cleaners, toilet scavengers, etc.
  • Textile pre- and post-treatment agent Finally, on the one hand are such means with which the laundry is brought into contact before the actual laundry, for example, for solving stubborn dirt, on the other hand, those in one of the actual textile laundry downstream step the laundry further desirable properties such as pleasant handle , Give crease-free or low static charge.
  • the fabric softeners are calculated. Disinfectants are, for example, hand disinfectants, surface disinfectants and instrument disinfectants, which may also occur in the mentioned dosage forms.
  • a disinfectant preferably causes a germ reduction by a factor of at least 10 4 , that is to say that of originally 10,000 proliferating germs (so-called colony-forming units - CFU) survived no more than a single, with viruses in this regard are not considered as germs, since they have no cytoplasm and have no own metabolism.
  • Preferred disinfectants cause a germ reduction by a factor of at least 10 5 .
  • surfactant (s) it is possible to use anionic, nonionic, zwitterionic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.
  • the total surfactant content of the liquid surfactant preparation is preferably below 60% by weight, and more preferably below 45% by weight, based on the total liquid surfactant formulation.
  • Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C12-14 alcohols containing 3 EO, 7 EO or 4 EO, C9-11 alcohol containing 7 EO, C 13-5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrowed Homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C 16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
  • the surfactant preparation contains a C 12-18 fatty alcohol with 7 EO or a C 13-15 oxo alcohol with 7 EO as nonionic surfactant.
  • the content of nonionic surfactants is preferably 3 to 40 wt .-%, preferably 5 to 30 wt .-% and in particular 7 to 20 wt .-%, each based on the total surfactant.
  • the surfactant preparation may also contain anionic surfactants.
  • the anionic surfactant used is preferably sulfonates, sulfates, soaps, alkyl phosphates, anionic silicone surfactants and mixtures thereof.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable.
  • anionic surfactants are soaps.
  • Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants including the soaps may be in the form of their sodium, potassium or magnesium or ammonium salts.
  • the anionic surfactants are in the form of their sodium salts.
  • Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine or methylethylamine.
  • the content of a surfactant preparation of anionic surfactants can be from 1 to 40% by weight, preferably from 5 to 30% by weight and very particularly preferably from 10 to 25% by weight, based in each case on the total surfactant preparation.
  • surfactant preparations in particular of liquid detergents or cleaners containing a lipase, in particular such as described above, in particular at a temperature between 10 ° C and 80 ° C and preferably at comparatively low temperatures, in particular between 10 ° C and 50 ° C, between 10 ° C and 40 ° C, between 10 ° C and 30 ° C and / or between 20 ° C and 40 ° C.
  • the substances indicated are anionic or polyanionic substances, ie these substances carry at least one and preferably several negative charges. It is preferably a polymer having at least one negatively charged monomer, preferably having a plurality of negatively charged monomers. According to the invention, this polymer is therefore a negatively charged polymer.
  • polymers of organic acids or their salts in particular polyacrylates and / or poly-sugar acids and / or polyarcylate copolymers and / or poly-sugar copolymers, are preferred.
  • further preferred compounds are polyacrylic sulfonates or polycarboxylates and their salts, copolymers or salts of the copolymers.
  • Acusol 587D polyacrylic sulfonate, Rohm & Haas / Dow Chemical Company
  • Acusol 445N polycarboxylate sodium salt, Rohm & Haas / Dow Chemical Company
  • Acusol 590 polyacrylate copolymer; Rohm & Haas / Dow Chemical
  • Acusol 916 polyarcrylate sodium salt, Rohm & Haas / Dow Chemical Company
  • Sokalan CP42 modified polycarboxylate sodium salt, BASF Company
  • Sokalan PA 30CL polycarboxylate sodium salt, BASF Company
  • Dequest P 9000 polymaleic acid, Thermphos Company
  • alginic acid Poly-2-acrylamido-2-methyl-1-propane-sulfonic acid, poly-4-styrene sulfonic acid-co-maleic acid sodium salt, poly-acrylamido-co-acrylic acid sodium salt, poly-me
  • the substances indicated are cationic or polycationic substances, i. these substances carry at least one and preferably several positive charges. It is preferably a polymer having at least one positively charged monomer, preferably having a plurality of positively charged monomers. According to the invention, this polymer is therefore a positively charged polymer.
  • preferred compounds in this regard are salts of polyamines, polyethylene imines or their copolymers, salts of polyallylamines, salts of Polydiallyldimethylammonium compounds or poly (acrylamide-co-diallyldimethylammonium compounds.
  • under iii. specified substances are substances which have at least one hydroxyl and / or polyhydroxyl group and preferably more hydroxyl and / or polyhydroxyl groups.
  • Preferred in this regard are, for example, polyvinyl alcohols, for example those which are available under the trade name Mowiol (Kremer Pigmente GmbH & Co. KG).
  • a specific substance to one or more of the above groups i. to iii. may be associated.
  • it may be an anionic polymer having one or more hydroxyl and / or polyhydroxyl group (s).
  • Such a substance is then associated with the groups i. and iii.
  • the surfactant preparation is characterized by further comprising at least one other ingredient selected from the group consisting of builder, peroxygen compound, bleach activator, nonaqueous solvent, acid, water soluble salt, thickener, disinfecting ingredient, and the like Combinations thereof.
  • the addition of one or more of the further ingredient (s) proves to be advantageous, as this further improved cleaning performance and / or disinfection is achieved.
  • the improved cleaning performance and / or disinfection is based on a synergistic interaction of at least two ingredients.
  • Builders which may be present in the surfactant preparation include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Organic builders which may be present in the surfactant preparation are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA) and derivatives thereof and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • soluble builders such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol, preferably in the liquid surfactant preparation.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which Polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, surfactant preparations.
  • Peroxygen compounds which are suitable for use in surfactant preparations according to the invention are, in particular, organic peracids or persalts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, such as perborate, percarbonate, persilicate and / or persulphate Caroat belong into consideration. If a preparation contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, especially from 5% to 30% by weight. The addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • organic peracids or persalts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters
  • TAED
  • the hydrophilic substituted acyl acetals and the acyl lactams are also preferably used.
  • combinations of conventional bleach activators can be used.
  • Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-producing bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, the total surfactant preparation, be contained when using percarboxylic acid as the sole bleach, but preferably completely.
  • sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes may also be present as so-called bleach catalysts.
  • the surfactant preparations according to the invention are liquid and preferably contain water as the main solvent.
  • non-aqueous solvents may be added to the surfactant preparation. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range.
  • the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diisopropylene glycol monomethyl ether, di-isopropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol
  • the surfactant formulation contain a polyol as a nonaqueous solvent.
  • the polyol may in particular comprise glycerol, 1,2-propanediol, 1,3-propanediol, ethylene glycol, diethylene glycol and / or dipropylene glycol.
  • the surfactant formulation contains a mixture of a polyol and a monohydric alcohol.
  • Non-aqueous solvents may be used in the surfactant preparation in amounts of between 0.5 and 15% by weight, but preferably below 12% by weight.
  • the surfactant formulation s systemic and environmentally acceptable acids, especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also, mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are present in the surfactant preparations in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • a surfactant preparation according to the invention may further contain one or more water-soluble salts which serve, for example, for adjusting the viscosity.
  • These may be inorganic and / or organic salts.
  • Useful inorganic salts are preferably selected from the group consisting of colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used.
  • the inorganic salt is selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof.
  • Useful organic salts are, for example, colorless water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and / or transition metal salts of the carboxylic acids.
  • the salts are selected from the group comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.
  • a surfactant preparation according to the invention may contain one or more thickeners.
  • the thickener is selected from the group comprising xanthan, guar, carrageenan, agar-agar, gellan, pectin, locust bean gum and mixtures thereof. These compounds are effective thickeners even in the presence of inorganic salts.
  • the surfactant formulation contains xanthan gum as a thickener because xanthan effectively thickened even in the presence of high salt concentrations and prevents macroscopic separation of the continuous phase.
  • the thickener stabilizes the continuous, low surfactant phase and prevents macroscopic phase separation.
  • acrylic and methacrylic (co) polymers include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to "International Dictionary of Cosmetic Ingredients” of "The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers.
  • CFA Cosmetic, Toiletry and Fragrance Association
  • Such polyacrylic acids are available, inter alia, under the trade names Polygel® and Carbopol®.
  • acrylic acid copolymers are suitable: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with C 1-4 alkanols, esters (INCI acrylates copolymer), for example, among the Trade names Aculyn®, Acusol® or Tego® Polymer are available; (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C 10-30 alkyl acrylates with one or more Monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C 1-4 alkanols formed ester (INCI acrylates / C 10-30 alkyl acrylate crosspolymer) include and are available, for example, under the trade name Carbopol®.
  • Other suitable polymers are (meth) acrylic acid (co) polymers of the Sokalan® type.
  • the surfactant preparation according to the invention contains a (meth) acrylic acid (co) polymer in combination with a further thickener, preferably xanthan.
  • the surfactant preparation can contain from 0.05 to 1.5% by weight and preferably from 0.1 to 1% by weight, based in each case on the total surfactant preparation, of thickening agent.
  • the amount of thickener used depends on the type of thickener and the desired degree of thickening.
  • ingredients which have an antimicrobial or antiviral activity are understood to be a disinfectant ingredient.
  • the germicidal effect is dependent on the content of the disinfecting ingredient in the surfactant preparation, wherein the germicidal effect decreases with decreasing content of disinfecting ingredient or increasing dilution of the surfactant preparation.
  • a preferred disinfecting ingredient is ethanol or propanol. These monohydric alcohols are commonly used in disinfectants and detergents because of their solvent properties and their germicidal activity.
  • the term "propanol” includes both the 1-propanol (n-propanol) and the 2-propanol ("isopropanol”).
  • Ethanol and / or propanol for example, in an amount of from 10 to 65 wt .-%, preferably 25 to 55 wt .-% in the surfactant preparation.
  • Another preferred disinfecting ingredient is tea tree oil.
  • the tea tree oil is obtained by steam distillation from the leaves and branch tips of these trees and is a mixture of about 100 substances; its main constituents include (+) - terpinene-4-ol, ⁇ -terpinene, terpinolene, terpineol, pinene, myrcene, phellandrene, p-cymene, limonene and 1,8-cineole.
  • Tea tree oil is contained, for example, in an amount of 0.05 to 10% by weight, preferably 0.1 to 5.0% by weight, in the virucidal treatment solution.
  • Another preferred disinfecting ingredient is lactic acid.
  • the lactic acid or 2-hydroxypropionic acid is a fermentation product produced by various microorganisms. She is weakly active in antibiotics. Lactic acid is for example, in amounts of up to 10 wt .-%, preferably 0.2 to 5.0 wt .-% in the surfactant preparation.
  • disinfectant ingredients are, for example, active compounds from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides.
  • active compounds from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols,
  • preferred active ingredients are selected from the group comprising 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2 '.
  • Preferred quaternary surface active compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group.
  • disinfectant essential oils can be used, which at the same time provide for a scenting of the virucidal treatment solution.
  • particularly preferred active compounds are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite and mixtures thereof.
  • Such another disinfecting ingredient is, for example, in an amount of 0.01 to 1 wt .-%, preferably 0.02 to 0.8 wt .-%, in particular 0.05 to 0.5 wt .-%, particularly preferably 0 , 1 to 0.3 wt .-%, most preferably 0.2 wt .-% in the surfactant preparation.
  • Liquid surfactant preparations according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • Surfactant preparations according to the invention may contain as enzymatic constituents exclusively a lipase as described. Alternatively, they may also contain other hydrolytic enzymes or other enzymes in a concentration useful for the effectiveness of the surfactant formulation. In a further embodiment of the invention, therefore, the surfactant preparation comprises at least one further enzyme. In principle, all the enzymes established in the prior art for this purpose can be used in this regard.
  • Preferred as further enzymes all enzymes which can develop a catalytic activity in a surfactant preparation according to the invention can be used, in particular a protease, amylase, cellulase, hemicellulase, mannanase, pectinase, tannase, xylanase, xanthanase, .beta.-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreductase or another Lipase, as well as their mixtures.
  • a protease amylase, cellulase, hemicellulase, mannanase, pectinase, tannase, xylanase, xanthanase, .beta.-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreducta
  • each further enzyme is in an amount of 1 x 10 -7 -3 wt%, from 0.00001 to 1 wt%, from 0.00005 to 0.5 wt%, from 0.0001 to 0.1 wt .-% and particularly preferably from 0.0001 to 0.05 wt .-% in inventive surfactant preparations, based on active protein.
  • the enzymes show synergistic cleaning performance against certain stains or stains, ie the enzymes contained in the surfactant preparation support each other in their cleaning performance.
  • subtilisin type those of the subtilisin type are preferable.
  • 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 and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaard, Denmark.
  • 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, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, sold under the trade name Protosol® by Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® by 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.
  • the proteases are also used with particular preference Bacillus gibsonii and Bacillus pumilus disclosed in international patent applications WO2008 / 086916 and WO2007 / 131656 ,
  • Amylases which can be synthesized according to the invention are, for example, the ⁇ -amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens or from Bacillus stearothermophilus, and in particular also their further developments improved for use in detergents or cleaners.
  • the enzyme from Bacillus licheniformis is available from the company Novozymes under the name Termamyl® and from the company Danisco / Genencor under the name Purastar®ST.
  • this ⁇ -amylase is available from the company Novozymes under the trade name Duramyl® and Termamyl®ultra, from the company Danisco / Genencor under the name Purastar®OxAm and from the company Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
  • the Bacillus amyloliquefaciens ⁇ -amylase is sold by the company Novozymes under the name BAN®, and variants derived from the Bacillus stearothermophilus ⁇ -amylase under the names BSG® and Novamyl®, also from the company Novozymes. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp.
  • a 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948).
  • CCTase cyclodextrin glucanotransferase
  • fusion products of all the molecules mentioned can be used.
  • the further developments of the ⁇ -amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are suitable.
  • Further advantageously usable commercial products are, for example, the amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter also from the company Novozymes.
  • variants of these enzymes obtainable by point mutations can be used according to the invention.
  • amylases are disclosed in International Publications WO 00/60060 . WO 03/002711 . WO 03/054177 and WO07 / 079938 , whose disclosure is therefore expressly referred to, or whose disclosure in this regard is therefore expressly incorporated into the present patent application. Further, amylases which can be synthesized according to the invention are preferably .alpha.-amylases.
  • lipases or cutinases which can be synthesized according to the invention, which are contained in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors, are the lipases which are originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold for example by the company Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
  • the lipases or cutinases can be used whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Other important commercial products are the preparations M1 Lipase.RTM. And Lipomax.RTM.
  • Lipase MY-30®, Lipase OF® and Lipase PL® to mention also the product Lumafast® from the company Genencor.
  • Detergents or cleaning agents according to the invention may also contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects.
  • These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect.
  • Cellulases (endoglucanases, EG) which can be synthesized according to the invention comprise, for example, the fungal cellulase preparation rich in endoglucanase (EG) or its further developments, which is offered by the company Novozymes under the trade name Celluzyme®. Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kD EG or 43 kD EG from Humicola insolens DSM 1800. Further commercial products of this company are Cellusoft®, Renozyme® and Celluclean®.
  • cellulases available from the company AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, which are based, at least in part, on the 20 kD-EG of melanocarpus.
  • Other cellulases from AB Enzymes are Econase® and Ecopulp®.
  • Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp. CBS 670.93 is available from the company Danisco / Genencor under the trade name Puradax®.
  • Other usable commercial products of the company Danisco / Genencor are "Genencor detergent cellulase L" and IndiAge®Neutra.
  • cellulases are Thielavia terrestris cellulase variants described in International Publication WO 98/12307 Cellulases from Melanocarpus, in particular Melanocarpus albomyces, disclosed in the international publication WO 97/14804 Cellulases of the EGIII type from Trichoderma reesei disclosed in the European patent application EP 1 305 432 and variations obtainable therefrom, in particular those disclosed in the European patent applications EP 1240525 and EP 1305432 , as well as cellulases, which are disclosed in international publications WO 1992006165 .
  • WO 96/29397 and WO 02/099091 On their respective disclosure is therefore expressly referenced or their disclosure in this regard is therefore expressly included in the present patent application.
  • Suitable enzymes for this purpose are available, for example, under the name Gamanase® and Pektinex AR® from Novozymes, under the name Rohapec® B1L from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA ,
  • the ⁇ -glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes.
  • Hemicellulases which are particularly preferred according to the invention are mannanases which are sold, for example, under the trade names Mannaway® by the company Novozymes or Purabrite® by the company Genencor.
  • a surfactant preparation according to the invention may also contain oxidoreductases, for example oxidases, oxygenases, catalases (which react as peroxidase at low H 2 O 2 concentrations), peroxidases, such as halo-, chloro-, bromo-, lignin-, glucose- or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases).
  • Suitable commercial products are Denilite® 1 and 2 from Novozymes.
  • advantageous systems for enzymatic perhydrolysis can be applied to the applications WO 98/45398 A1 .
  • WO 2005/056782 A2 such as WO 2004/058961 A1 directed.
  • a combined enzymatic bleaching system comprising an oxidase and a perhydrolase describes the application WO 2005/124012 .
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
  • the enzymes to be used according to the invention may also be formulated together with accompanying substances, for example from the fermentation, or with stabilizers and incorporated in such a formulation in a surfactant preparation according to the invention.
  • a further subject of the invention is the use of a surfactant preparation according to the invention for the removal of stains, in particular of lipase-sensitive stains, on textiles or hard surfaces, ie for the cleaning of textiles or of hard surfaces.
  • surfactant preparations according to the invention may be used, in particular because of the combination of phosphonate and lipase, advantageously in order to remove impurities from textiles or from hard surfaces.
  • Embodiments of this subject invention include, for example, hand washing, manual removal of stains from textiles or hard surfaces, or use in conjunction with a machine process.
  • a further subject of the invention is a process for the cleaning of textiles or hard surfaces or for disinfection, wherein in at least one process step a surfactant preparation according to the invention is used.
  • the invention furthermore relates to a process, in particular a washing, cleaning or disinfecting process, in which a wash liquor which comprises a phosphonate and a lipase which is naturally present in a microorganism, the microorganism being Rhizopus oryzae or Mucorjavanicus, is contacted with a lipase-sensitive soil or germ on a textile or hard surface.
  • a wash liquor which comprises a phosphonate and a lipase which is naturally present in a microorganism, the microorganism being Rhizopus oryzae or Mucorjavanicus
  • Processes for cleaning textiles are generally characterized in that one or more cleaning-active substances are applied to the items to be cleaned and washed off after the action time.
  • the cleaning product is treated with the surfactant preparation or the wash liquor formed by it, preferably for a certain minimum duration, for example 5, 10, 15, 20, 25, 30, 40, 50 or 60 minutes.
  • the germ to be killed is brought into contact with the surfactant preparation or the wash liquor formed by it, preferably for a certain minimum duration, for example 5, 10, 15, 20, 25, 30, 40, 50 or 60 minutes.
  • a method according to the invention is characterized in that the lipase is present in the wash liquor in a concentration of 0.0000003 to 0.0004 wt .-%, preferably from 0.0000005 to 0.0003 wt .-%, wherein the Details are based on active protein in the wash liquor.
  • a method according to the invention is characterized in that it is carried out at a temperature between 10 ° C and 80 ° C, preferably between 10 ° C and 70 ° C and more preferably between 20 ° C and 60 ° C.
  • Lipases provided according to the invention are advantageously usable in surfactant preparations according to the invention and processes, in particular washing, cleaning or disinfection processes. They can therefore be used advantageously to provide lipolytic activity in corresponding preparations.
  • Another object of the invention is the use of a lipase naturally present in a microorganism, wherein the microorganism is Rhizopus oryzae or Mucorjavanicus, for providing a lipolytic activity in a liquid surfactant preparation further comprising a phosphonate.
  • Another object of the invention is the use of a lipase, which is naturally present in a microorganism, wherein the microorganism is Rhizopus oryzae or Mucor javanicus, for the removal of lipase-sensitive stains on textiles or hard surfaces or for disinfection in a wash liquor, which further comprises a phosphonate.
  • the detergent base formulation used was a phosphonate-containing liquid detergent of 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 (fatty alcohol ether sulfate), 24-28% nonionic surfactants, 1% boric acid, 1-2% sodium citrate (dihydrate), 2-4% soda, 14-16% coconut oil.
  • This detergent base formulation was added to the following series of lipases for the various series of experiments in an activity-identical manner to 0.35% by weight of Lipex 100L (lipase preparation from Novozymes (batch 4 as reference): Lipase M-AP10® (batch 1), Lipase LE ® (batch 2) and Lipase F® (also Lipase JV®, batch 3), all available from Amano Pharmaceuticals.

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

Claims (10)

  1. Préparation tensioactive liquide comprenant un phosphonate et une lipase présente naturellement dans un microorganisme, ce microorganisme étant Rhizopus oryzae ou Mucor javanicus.
  2. Préparation tensioactive selon la revendication 1 caractérisée en ce que le phosphonate est sélectionné dans le groupe constitué de l'acide 1-hydroxyéthane-1,1-diphosphonique (HEDP), l'acide amino-tris méthylène phosphonique (ATMP), l'acide nitrilotriméthylène phosphonique (NTMP), l'acide diéthylènetriamine-pentaméthylènephosphonique (DTMP, DETMP ou DTPNT), l'acide éthylènediaminetétraméthylène phosphonique (EDTMP), l'acide 2-phosphonobutane-1,2,4-tricarboxylique (PBS-AM) et des combinaisons de ceux-ci.
  3. Préparation tensioactive selon la revendication 1 ou 2 caractérisée en ce que la lipase présente une séquence d'acide aminé identique à au moins 80 % à la séquence d'acide aminé indiquée en SEQ ID NO.1.
  4. Préparation tensioactive selon l'une quelconque des revendications 1 à 3 caractérisée en ce que le phosphonate est présent dans une proportion de 0,01 à 4 % en poids, et/ou en ce que la lipase est présente dans une proportion de 1 x 10-8 à 5 % en poids, par rapport à la protéine active.
  5. Préparation tensioactive selon l'une quelconque des revendications 1 à 4 caractérisée en ce qu'elle est un produit lavant, nettoyant ou désinfectant.
  6. Préparation tensioactive selon l'une quelconque des revendications 1 à 5 caractérisée en ce qu'elle comprend de plus un composant sélectionné parmi
    i. une substance anionique et/ou polyanionique, et/ou
    ii. une substance cationique et/ou polycationique, et/ou
    iii. une substance présentant un ou plusieurs groupe(s) hydroxyle et/ou polyhydroxyle.
  7. Préparation tensioactive selon l'une quelconque des revendications 1 à 6 caractérisée en ce qu'elle comprend de plus au moins un autre ingrédient sélectionné dans le groupe constitué d'un adjuvant, d'un composé peroxygéné, d'un activateur de blanchiment, d'un solvant non aqueux, d'un acide, d'un sel soluble dans l'eau, d'un agent épaississant, d'un ingrédient désinfectant, et des combinaisons de ceux-ci, et/ou en ce qu'elle comprend au moins une autre enzyme, en particulier une protéase, amylase, cellulase, hémicellulase, mannanase, pectinase, tannase, xylanase, xanthanase, β-glucosidase, carraghénase, perhydrolase, oxidase, oxidoréductase ou une lipase, ainsi que, de préférence, des mélanges de celles-ci.
  8. Procédé de nettoyage de textiles ou de surfaces dures, ou de désinfection, caractérisé en ce qu'une préparation tensioactive selon l'une quelconque des revendications 1 à 7 est appliquée à au moins une étape du procédé.
  9. Procédé, en particulier procédé de lavage, de nettoyage ou de désinfection, dans lequel une liqueur de lavage comprenant un phosphonate et une lipase présente naturellement dans un microorganisme, ce microorganisme étant Rhizopus oryzae ou Mucor javanicus, est mise en contact avec une salissure sensible à la lipase ou un germe sur un textile ou une surface dure.
  10. Utilisation d'une lipase présente naturellement dans un microorganisme, ce microorganisme étant Rhizopus oryzae ou Mucorjavanicus pour la génération d'une activité lipolytique dans une préparation tensioactive liquide laquelle comprend de plus un phosphonate, ou pour l'élimination de salissures sensibles à la lipase sur des textiles ou des surfaces dures ou pour la désinfection dans une liqueur de lavage, laquelle comprend de plus un phosphonate.
EP11805804.9A 2010-12-21 2011-12-13 Préparation tensioactive liquide contenant de la lipase et du phophonate Active EP2655587B1 (fr)

Priority Applications (1)

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PL11805804T PL2655587T3 (pl) 2010-12-21 2011-12-13 Ciekłe kompozycje tensydów zawierające lipazę i fosfonian

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DE102010063743A DE102010063743A1 (de) 2010-12-21 2010-12-21 Flüssige Tensidzubereitung enthaltend Lipase und Phosphonat
PCT/EP2011/072513 WO2012084582A1 (fr) 2010-12-21 2011-12-13 Préparation tensioactive liquide contenant de la lipase et du phophonate

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EP (1) EP2655587B1 (fr)
KR (1) KR101928587B1 (fr)
DE (1) DE102010063743A1 (fr)
ES (1) ES2634512T3 (fr)
HU (1) HUE035746T2 (fr)
MX (1) MX2013007116A (fr)
PL (1) PL2655587T3 (fr)
WO (1) WO2012084582A1 (fr)

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CN105829518B (zh) * 2013-12-20 2020-11-03 诺维信公司 用于用脂肪酶进行处理的组合物和工艺
US10208297B2 (en) * 2014-01-22 2019-02-19 Novozymes A/S Polypeptides with lipase activity and polynucleotides encoding same for cleaning
DE102017202034A1 (de) 2017-02-09 2018-08-09 Henkel Ag & Co. Kgaa Lipasen mit erhöhter Thermostabilität
EP3772540A1 (fr) 2019-08-08 2021-02-10 Henkel AG & Co. KGaA Lipases à thermostabilité accrue

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MX2013007116A (es) 2013-08-27
DE102010063743A1 (de) 2012-06-21
PL2655587T3 (pl) 2017-10-31
KR101928587B1 (ko) 2018-12-12
EP2655587A1 (fr) 2013-10-30
KR20130135272A (ko) 2013-12-10
US20130266552A1 (en) 2013-10-10
ES2634512T3 (es) 2017-09-28
WO2012084582A1 (fr) 2012-06-28
HUE035746T2 (en) 2018-05-28

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