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WO2024175293A1 - Detergents and cleaning agents comprising dispersin - Google Patents

Detergents and cleaning agents comprising dispersin Download PDF

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Publication number
WO2024175293A1
WO2024175293A1 PCT/EP2024/051748 EP2024051748W WO2024175293A1 WO 2024175293 A1 WO2024175293 A1 WO 2024175293A1 EP 2024051748 W EP2024051748 W EP 2024051748W WO 2024175293 A1 WO2024175293 A1 WO 2024175293A1
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WO
WIPO (PCT)
Prior art keywords
textiles
cleaning
agent
dispersin
amino acid
Prior art date
Application number
PCT/EP2024/051748
Other languages
German (de)
French (fr)
Inventor
Mirko Weide
Michael KANDZIA
Original Assignee
Henkel Ag & 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
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Publication of WO2024175293A1 publication Critical patent/WO2024175293A1/en

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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
    • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N63/00—Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
    • A01N63/50—Isolated enzymes; Isolated proteins
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/24—Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402—Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y302/00—Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01—Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01052—Beta-N-acetylhexosaminidase (3.2.1.52)
    • 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

Definitions

  • the invention is in the field of washing and cleaning agents, in particular enzyme-containing washing and cleaning agents, and relates to the use of a dispersin or an agent containing a dispersin for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably a pre-portioned textile detergent comprising at least one dispersin and at least one fragrance. Also part of the invention are the corresponding washing and/or cleaning methods and the use of the agents described herein for cleaning textiles and for improving the hygiene of textiles. The invention also relates to corresponding agents and methods.
  • enzymes in detergents have been established in the state of the art for decades. They serve to expand the performance spectrum of the agents in question according to their special activities. These include in particular hydrolytic enzymes such as proteases, amylases, lipases and cellulases. The first three mentioned hydrolyze proteins, starch and fats and thus contribute directly to the removal of dirt. Cellulases are used in textile detergents in particular because of their effect on fabrics.
  • Another group of detergent enzymes are oxidative enzymes, in particular oxidases, which, if necessary in conjunction with other components, preferably serve to bleach soiling and/or to generate the bleaching agents in situ.
  • the packaging and supply of detergents and cleaning agents are subject to constantly changing requirements. For some time now, the main focus has been on the convenient dosing of detergents and cleaning agents by the consumer and the simplification of the work steps required to carry out a washing or cleaning process.
  • a technical solution is pre-portioned detergents or cleaning agents, for example foil bags with one or more receiving chambers for solid and/or liquid detergents and cleaning agents.
  • a trend relevant to the production of these foil bags is the Miniaturization of these film bags.
  • the background to this development is not only greater consumer acceptance due to simplified handling, but also sustainability aspects, for example in relation to transport volumes and costs and the amount of packaging used.
  • the concentration of modern washing and cleaning agents requires a progressive optimization of existing recipes and the development of new, more effective recipes.
  • One goal of these developments, which usually rely on known washing and cleaning active ingredients, is to achieve an increase in the washing or cleaning performance of the recipes while maintaining or reducing the dosage.
  • bad smell means a smell that is not desired on surfaces, in particular household surfaces, dishes, textiles and cleaned objects, in particular cleaned textiles and cleaned dishes.
  • the cleaned object should smell fresh and clean without a bad smell clinging to it.
  • a wide variety of causes can cause an unpleasant smell, so-called bad smell, on surfaces, in particular household surfaces, as well as on washed textiles and/or cleaned hard surfaces, in particular dishes.
  • household surface means, for example, surfaces in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, wash basins or sinks, toilet bowls, cisterns, toilet rims, siphons, water pipes and/or lines, water inlets and/or outlets.
  • Bad smells are known to be a problem, especially with textiles and washing machines. But bad smells can also be found in dishwashers.
  • microbial bio-deposits i.e. microbial bad smells as a result of from microbial biodeposits.
  • Another example of unpleasant odors is sweat or body odor that clings to an object that has come into contact with people or animals.
  • Bad odors are not only found in the washing machine, but also on freshly washed, still damp laundry, as well as on dry laundry, and on numerous other surfaces, particularly household surfaces and dishes. This also includes so-called re-blooming, i.e. the re-blooming of the bad odor when the laundry is worn due to body heat and/or moisture.
  • Deposits, biodeposits, biosoils, bodysoils and the like do not only lead to bad odors, but can also become visible as soiling on textiles and/or surfaces, particularly household surfaces and dishes, e.g. in the form of deposits, grease, encrustations, yellowing, armpit stains and graying. Due to their typically adhesive texture, biodeposits and the like also allow other bad odor and/or dirt particles to adhere. However, bad smells can also be present before the microbial deposits lead to visible contamination.
  • bio-soil does not only mean biofilms in the narrow sense, such as microbial deposits, biofilms or the like, which can be formed by any microorganisms whose cells adhere to each other and/or to a surface, e.g. to textiles, tableware or a hard surface or another type of surface, but also more generally any bio-soils, bio-soils, biological deposits or the like including, but not limited to, degradation and deposition products of microorganisms that adhere to a surface, e.g. to textiles, tableware or a hard surface or another type of surface. These adherent cells are often embedded in a self-produced matrix of extracellular polymeric substance (EPS).
  • EPS extracellular polymeric substance
  • Biofilm EPS is a polymeric conglomerate that generally consists of extracellular DNA, proteins and polysaccharides. Biofilms can form on living or non-living surfaces.
  • the microbial cells growing in a biofilm are physiologically different from the planktonic cells of the same organism, which, in contrast, are solitary cells that float or can swim in a liquid medium.
  • Bacterial cells living in a biofilm usually have significantly different properties than planktonic bacterial cells of the same species, because the dense and protected environment of the film allows them to cooperate and interact in different ways.
  • An advantage of this environment for the microorganisms is increased resistance to detergents and antibiotics, because the dense extracellular matrix and outer cell layer protect the interior of the community.
  • Biofilm-producing bacteria on textiles include, for example, the following species: Acinetobacter sp., Aeromicrobium sp., Brevundimonas sp., Microbacterium sp., Micrococcus luteus, Pseudomonas sp., Staphylococcus epidermidis and Stenotrophomonas sp.
  • Biofilm-forming bacteria found on hard surfaces include the following species: Acinetobacter sp., Aeromicrobium sp., Brevundimonas sp., Microbacterium sp., Micrococcus luteus, Pseudomonas sp, Staphylococcus epidermidis, Staphylococcus aureus and Stenotrophomonas sp.
  • EP 3892708, WO 2021/122117, WO 2021/122118, WO 2021/122120, WO 2021/122121 and WO 2022/008387 describe washing and cleaning agents containing dispersin and enzymes. It has also been described that dispersin can degrade biofilm and EPS, for example.
  • fragrances have side effects such as allergenic properties that can manifest themselves in the form of skin rashes.
  • fragrances have been increasingly used in the form of fragrance microcapsules, although it is known that microcapsules are considered microplastics and are therefore potentially harmful to the environment.
  • fragrances are expensive and add to the overall cost of detergents and cleaning agents.
  • the dispersin according to the invention reliably removes microbial deposits, bio-deposits and the like from textiles, dishes and other surfaces, especially household surfaces. What is particularly surprising is that this effect not only leads to the removal of microbial deposits that are visible to the naked eye, but also to the removal of deposits that are not visible to the naked eye, i.e. cleaning of the textiles at the fiber level (and not just at the yarn level), i.e. deep cleaning.
  • the deep cleaning effect can also be shown and examined at the fiber level, for example using scanning electron microscope images.
  • deep cleaning as used herein means the dissolution or removal of visible and invisible components of organic substances, e.g.
  • biofilms including e.g. polysaccharides, PNAG (poly-N-acetyl-glucosamine)), body oils or other components contained in organic substances, not only at the level visible to the naked eye, but also the dissolution or removal of microbial deposits not visible to the naked eye, in particular biodeposits and the like between individual fibers of textiles.
  • the deep clean effect also reduces or eliminates the consequences of microbial deposits, e.g. bad smells, and improves the hygiene of the associated treated textiles and/or surfaces, since the removal of microbial deposits, bio-deposits and the like also removes microbes adhering to them, e.g. bacteria.
  • the invention therefore relates, in a first aspect, to the use of a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length and, based on the numbering according to SEQ ID NO:1, at least one of the positions which correspond to the positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74,
  • 262, 263, 264, 265, 267, 268, 270, 271, 272, 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291, 296, 300, 301, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, has at least one amino acid substitution and/or deletion, for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, in particular preferred for deep cleaning of textiles and for improving the hygiene of textiles.
  • the invention relates to the use of a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length and, based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to the positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77,
  • the dispersin according to the invention is contained in a washing and/or cleaning agent, wherein the agent is substantially free of boron-containing compounds, preferably free of boron-containing compounds; and/or the agent in 1 wt. % solution in deionized water at 20°C has a pH in a range from about 6 to about 11, in particular from about 6.5 to about 10.5, more preferably from about 7 to about 10, particularly preferably from about 8 to about 9.
  • the dispersin or the dispersin-containing washing and/or cleaning agent is used in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
  • an agent for deep fiber cleaning of textiles and/or for improving the hygiene of textiles characterized in that the agent contains a dispersin according to the invention, and to a method for deep fiber cleaning of textiles and/or for improving the hygiene of textiles, characterized in that in at least one method step a dispersin according to the invention or an agent according to the invention is used, preferably in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
  • the invention relates in particular to the removal of microbial deposits that are not visible to the naked eye. Furthermore, the invention relates in particular to the fiber-deep cleaning of textiles. The fiber-deep cleaning can be shown using scanning electron microscope images.
  • At least one as used herein means one or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or more.
  • agent and cleaning agent or “detergent or cleaning agent” as used herein is synonymous with the term “agent” and refers to a composition for cleaning textiles and/or hard surfaces, in particular dishes, as explained in the description.
  • Liquid as used herein includes liquids and gels as well as pasty compositions. It is preferred that the liquid compositions be flowable and pourable at room temperature, but it is also possible that they have a yield point.
  • a substance e.g. a composition or an agent, is solid according to the definition of the invention if it is in the solid state at 25°C and 1013 mbar.
  • a substance e.g. a composition or an agent, is liquid according to the definition of the invention if it is in the liquid state at 25°C and 1013 mbar. Liquid also includes gel form.
  • Variant refers to natural or artificially generated variations of a native enzyme that have a modified amino acid sequence compared to the reference form.
  • the term "textile” as used herein means any textile material, including yarns, yarn precursors, fibers, nonwovens, natural materials, synthetic materials and all other textile materials, fabrics made from these materials and products made from fabrics (e.g. garments and other articles).
  • the textile or fabric may be in the form of knits, wovens, denims, nonwovens, felts, yarns and terry cloth.
  • the textile may be cellulose-based, such as natural cellulose fibers such as cotton, flax/linen, jute, ramie, sisal or coconut fibers, or man-made cellulose fibers (e.g. from wood pulp) such as viscose/rayon, cellulose acetate fibers (tricell), lyocell or mixtures thereof.
  • the textile or fabric may also consist of non-cellulosic fibres, e.g. natural polyamides such as wool, camel, cashmere, mohair, rabbit and silk or synthetic polymers such as nylon, aramid, polyester, acrylic, polypropylene and spandex/elastane or mixtures thereof, as well as mixtures of cellulosic fibres and non-cellulosic fibres.
  • non-cellulosic fibres e.g. natural polyamides such as wool, camel, cashmere, mohair, rabbit and silk or synthetic polymers such as nylon, aramid, polyester, acrylic, polypropylene and spandex/elastane or mixtures thereof, as well as mixtures of cellulosic fibres and non-cellulosic fibres.
  • mixtures are mixtures of cotton and/or rayon/viscose with one or more accompanying materials such as wool, synthetic fibres (e.g.
  • polyamide fibres acrylic fibres, polyester fibres, polyvinyl chloride fibres, polyurethane fibres, polyurea fibres, aramid fibres) and/or cellulosic fibres (e.g. rayon/viscose, ramie, flax/linen, jute, cellulose acetate fibres, lyocell).
  • the fabric may be conventional washable laundry, e.g. soiled household linen. When the term "fabric” or "garment” is used, it is intended to include the broader term "textiles”.
  • the present invention is based on the surprising discovery of the inventors that the dispersin according to the invention reliably removes microbial deposits, bio-deposits and the like from surfaces, in particular household surfaces, as well as dishes and textiles. What is particularly surprising is that this effect not only leads to the removal of microbial deposits that are visible to the naked eye, but also to the removal of deposits that are not visible to the naked eye, i.e. cleaning of the textiles at the fiber level (and not just at the yarn level), i.e. deep cleaning of the fibers.
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length and, based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72, 7 4, 77, 79, 80, 81, 82, 90, 99
  • 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291, 296, 300, 301, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, has at least one amino acid substitution and/or deletion, for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, and for improving the hygiene of textiles.
  • Dispersins belong to the group of hexosaminidases or ß-N-acetylglucosamine minidases (EC 3.2.1.52). These are polypeptides that catalyze the hydrolysis of N-acetyl-D-hexosamine or N-acetylglucosamine polymers.
  • Dispersin B is a ß-hexosaminidase that specifically hydrolyzes ß-1,6-glycosidic bonds of acetylglucosamine polymers that occur, for example, in biofilm, EPS (extracellular polymer structures), cell debris, bio-coatings and other so-called biosoils (ie soiling of biological origin).
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity and comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72 , 74, 77, 79, 80, 81,
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72 , 74, 77, 79, 80, 81,
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 22, 23, 25, 30, 49, 56, 59, 62, 63, 68, 72, 74, 77, 82, 90, 99, 100, 114, 123, 124, 125, 135, 138, 171, 173, 174, 175, 178, 179
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 3, 15, 17, 49, 59, 140, 163, 186, 207, 215, 218, 225, 227, 232, 235, 237, 252, 260, 267, 272, 279, 281 , 288, 308, 309 and 312, at least one Amino acid substitution and/or
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70%, and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 3, 15, 49, 59, 163, 186, 225, 227, 232, 235, 252, 260, 272, 279, 281, 308, 309 and 312, having at least one amino acid substitution and/or deletion selected from the group consisting of Q3I, H15Y, A49W,
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, has at least one and increasingly preferably two, three, four, five, six, seven, eight or nine amino acid substitutions, wherein the Dispersin has an amino acid substitution combination selected from the group consisting of Q3I-A49W, Q3I-N59E, Q3I-S163P, Q3I-S186R, Q3I-Q215K, Q3I-S225G, Q3I
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96% or 96.5% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, at least ten and increasingly preferably eleven, twelve, 13, 14, 15, 16, 17, 18 or more amino acid substitutions, wherein the dispersin has an amino acid substitution combination selected from the group consisting of Q3F-A49W-N59E-S163P-S186R-S225G-N227T-N252P-F276A-Y281 P- K308E-K309E-K312E
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94% or 95% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, has at least 15 and increasingly preferably 16, 17, 18 or 19 amino acid substitutions, wherein the dispersin has an amino acid substitution combination which consists of the Q3F-T17W- A49W-N59E-S163P-S186R-S225G-N227T-G235W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-T17W-
  • a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93% or 94% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, has at least 18 amino acid substitutions, wherein the dispersin has an amino acid substitution combination which consists of the Q3F-H15Y-V140I-S163P-S186R-Q215K- S225G-N227T-E232D-G235W-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q,
  • ß-1,6-N-acetylglucosamnidase activity is synonymous with “hexosaminidase activity” and/or “dispersin activity” and is determined as follows: To determine dispersin activity, 35 ⁇ l of dispersin assay solution (45 mM citrate buffer pH 5 with 0.5 mg/ml p-nitrophenyl-N-acetyl-ß-D-glucosaminide) is added to a microtiter plate containing 5 ⁇ l of sample solution per well. The microtiter plate is incubated for 3 hours at room temperature. After incubation, 40 ⁇ l of stop solution (0.4 M Na2CO3) is added and the absorbance is measured at 405 nm. The activity values obtained are corrected by subtracting the absorbance measurement obtained for a reference without dispersin in order to eliminate background noise. From this, the residual activity (RA) for the respective dispersin variant can be calculated in comparison to a reference dispersin.
  • dispersin assay solution 45 mM
  • the enzymes mentioned here are preferably mature enzymes, i.e. the catalytically active molecule without signal and/or propeptide(s). Unless otherwise stated, the sequences given also refer to mature (processed) enzymes.
  • the respective enzyme is a free enzyme.
  • the enzyme can act directly with all components of the agent and, if the agent is a liquid agent, that the enzyme is in direct contact with the solvent of the agent (eg water).
  • an agent can contain enzymes which form an interaction complex with other molecules or which contain a "coating".
  • a single or multiple enzyme molecule(s) can be separated from the other components of the agent by a structure surrounding them.
  • a structure surrounding structure can be created by, but is not limited to, vesicles, such as a micelle or a liposome.
  • the surrounding structure can also be a virus particle, a bacterial cell or a eukaryotic cell.
  • an agent can contain cells of Bacillus pumilus or Bacillus subtilus which express the proteases according to the invention, or cell culture supernatants of such cells.
  • an enzyme has the specified substitution(s) (or deletion or insertion) means that it contains one (of the specified) substitution(s) (or deletion or insertion) at the respective position, i.e. at least the specified positions are not otherwise mutated or deleted, for example by fragmentation of the enzyme.
  • the enzymes described herein have the sequence of the respective reference sequence with the exception of the explicitly mentioned substitutions, i.e. are 100% identical to the respective reference sequence apart from the substituted positions.
  • nucleic acid or amino acid sequences is determined by comparing sequences. This sequence comparison is based on the BLAST algorithm, which is established and commonly used in the state of the art (see, for example, Altschul et al., Basic local alignment search tool, J. Mol. Biol., 1990, 215: 403-410, and Altschul et al., Gapped BLAST and PSI-BLAST: a new generation of protein database search programs, Nucleic Acids Res., 1997, 25: 3389-3402) and is carried out in principle by assigning similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences to one another. A tabular assignment of the relevant positions is referred to as an alignment.
  • Sequence comparisons are created using computer programs. Frequently used programs include the Clustal series (see e.g. Chenna et al., Multiple sequence alignment with the Clustal series of programs, Nucleic Acid Res., 2003, 31 : 3497-3500), T-Coffee (see e.g. Notredame et al., T-Coffee: A novel method for multiple sequence alignments, J. Mol. Biol., 2000, 302: 205-217) or programs based on these programs or algorithms.
  • sequence comparisons are possible using the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the specified standard parameters, whose AlignX module for sequence comparisons is based on ClustalW, or Clone Manager 10 (use of the BLOSUM 62 scoring matrix for sequence alignment at the amino acid level). Unless otherwise stated, the sequence identity stated here is determined using the BLAST algorithm.
  • Such a comparison also allows a statement to be made about the similarity of the sequences being compared. This is usually expressed as percent identity, i.e. the proportion of identical nucleotides or amino acid residues in the same or in an alignment corresponding Positions are given.
  • the broader term homology includes conserved amino acid exchanges in amino acid sequences, i.e. amino acids with similar chemical activity, since these usually exert similar chemical activities within the protein. Therefore, the similarity of the compared sequences can also be given as percent homology or percent similarity.
  • Identity and/or homology statements can be made for entire polypeptides or genes or just for individual regions. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by similarities in the sequences. Such regions often have identical functions.
  • nucleic acid or amino acid sequence can be small and contain only a few nucleotides or amino acids. Such small regions often perform essential functions for the overall activity of the protein. It can therefore be useful to relate sequence similarities only to individual, possibly small regions. Unless otherwise stated, identity or homology statements in the present application refer to the total length of the nucleic acid or amino acid sequence specified in each case.
  • an amino acid position corresponds to a numerically designated position in SEQ ID NO:1 therefore means that the corresponding position is assigned to the numerically designated position in SEQ ID NO:1 in an alignment as defined above.
  • amino acid exchanges amino acid exchanges
  • 130D/V thus means that position 130 is mutated to D or V.
  • additional amino acids are named after the sequence position.
  • deletions the missing amino acid is replaced by a symbol, for example an asterisk or a dash, or an A is given in front of the corresponding position.
  • P9T describes the substitution of proline at position 9 by threonine
  • P9TH the insertion of histidine after the amino acid threonine at position 9
  • P9* or AP9 the deletion of proline at position 9.
  • a person skilled in the art can use methods that are generally known today, such as chemical synthesis or the polymerase chain reaction (PCR) in conjunction with standard molecular biological and/or protein chemical methods, to produce the corresponding nucleic acids, including complete genes, based on known DNA and/or amino acid sequences.
  • PCR polymerase chain reaction
  • Such methods are known, for example, from Sambrook, J., Fritsch, E.F. and Maniatis, T. 2001. Molecular cloning: a laboratory manual, 3rd Edition Cold Spring Laboratory Press.
  • cleaning performance is defined as the ability of an agent to partially or completely remove existing soiling, in particular the By “cleaning performance” is meant the brightening performance of one or more stains on textiles.
  • cleaning performance within the scope of the present invention also includes the ability to remove microbial deposits, bio-deposits and the like from textiles, dishes and other surfaces, in particular household surfaces. In particular, this also includes the deep cleaning of textiles ("deep clean”).
  • the cleaning performance according to the invention also includes in particular the prevention and/or reduction and/or removal of microbial deposits on textiles, dishes and surfaces, in particular household surfaces, particularly preferably the deep cleaning of textiles and/or the improvement of the hygiene of textiles.
  • both an agent which comprises enzymes or the washing/cleaning liquor formed by this agent and the respective enzyme itself have a respective cleaning performance.
  • the cleaning performance of the enzyme thus contributes to the cleaning performance of the agent or the washing/cleaning liquor formed by the agent.
  • the cleaning performance is preferably determined as stated below.
  • washing or cleaning liquor refers to the solution containing the washing or cleaning agent that acts on the textiles or fabrics or surfaces, in particular dishes or household surfaces, and thus comes into contact with the dirt present on the textiles or fabrics or surfaces.
  • the washing/cleaning liquor is usually created when the washing/cleaning process begins and the agent is diluted with water, for example in a washing machine or dishwasher or in another suitable container.
  • the cleaning performance of textiles or fabrics can be determined in a washing system that contains a detergent in a dosage of between 2.0 and 8.0 grams per liter of washing liquor and the enzyme to be tested.
  • Enzymes to be compared are used at the same concentration (based on active protein). Using the enzymes with the same activity ensures that even if there is a discrepancy in the ratio of active substance to total protein (the values of the specific activity), the respective enzymatic properties, e.g. the cleaning performance on certain stains, are compared. In general, a low specific activity can be compensated by adding a larger amount of protein.
  • the enzymes to be tested can also be used in the same amount of substance or weight if the enzymes to be tested have a different affinity for the test substrate in an activity test.
  • the term "same amount of substance” in this context refers to using the same mole of the enzymes to be tested.
  • the term “equal amount by weight” refers to the use of equal weight of the enzymes to be investigated.
  • the concentration of the enzyme in the detergent intended for this washing system is 0.0001 to 0.1 wt.%, in particular 0.001 to 0.1 wt.%, more preferably 0.01 to 0.06 wt.% and particularly preferably 0.001 to 0.02 wt.%, based on active protein.
  • the protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method (Gornall et al., J. Biol. Chem. 1948, 177: 751-766).
  • the active protein concentration can be determined by titrating the active centers using a suitable irreversible inhibitor and determining the residual activity (cf. Bender et al., J. Am. Chem. Soc. 1966, 88, 24: 5890-5913).
  • a liquid reference detergent for such a washing system can, for example, be composed as follows (all information in percent by weight (wt. %)): 4.4% alkylbenzenesulfonic acid, 5.6% other anionic surfactants, 2.4% C12-18 Na salts of fatty acids (soaps), 4.4% non-ionic surfactants, 0.2% phosphonates, 1.4% citric acid, 0.95% NaOH, 0.01% defoamers, 2% glycerin, 0.08% preservatives, 1% ethanol, remainder demineralized water.
  • the dosage of the liquid detergent is preferably between 3.0 and 6.0 grams per liter of washing liquor, for example 3.0, 3.2, 3.5, 3.7, 4.0, 4.5, 4.7, 4.9 or 5.9 grams per liter of washing liquor. Washing is preferably carried out in a pH value range between pH 7 and pH 10.5, preferably between pH 8 and pH 9.
  • the cleaning performance is determined by measuring the degree of cleaning of the washed textiles compared to soiling on textiles. For example, the washing process can take place for 60 minutes at a temperature of 40°C and the water can have a water hardness between 15.5°dH and 16.5°dH (German hardness).
  • the degree of whiteness i.e. the lightening of the soiling, as a measure of the cleaning performance is determined using optical measuring methods, preferably photometric.
  • One suitable device for this is the Minolta CM508d spectrometer.
  • the devices used for the measurement are usually calibrated beforehand with a white standard, preferably a supplied white standard.
  • Preferred embodiments of uses and agents according to the invention achieve such advantageous cleaning performance even at low temperatures, preferably in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
  • the dispersin according to the invention can be used in a washing and cleaning agent.
  • washing and cleaning agents according to the invention include all conceivable types of washing or cleaning agents, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or for hand washing or cleaning.
  • detergents for textiles, carpets or natural fibers for which the term detergent is used.
  • dishwashing detergents for dishwashers machine dishwashing detergents
  • manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term cleaning agent is used.
  • washing and cleaning agents within the scope of the invention also include washing aids which are added to the actual washing agent during manual or machine textile washing in order to achieve an additional effect.
  • washing and cleaning agents within the scope of the invention also include textile pre- and post-treatment agents, i.e. agents with which the item of laundry is brought into contact before the actual washing, for example to dissolve stubborn dirt, and also agents which, in a step following the actual textile washing, give the laundry other desirable properties such as a pleasant feel, freedom from creasing or low static charge.
  • the latter agents include, among others, fabric softeners. This also includes agents for use in (semi-)automated washing or cleaning systems such as robot mops or wet vacuum cleaners.
  • washing and/or cleaning agents according to the invention which can be in the form of powdered or granular solids, in compacted or re-compacted particle form, as homogeneous solutions or suspensions, can contain, in addition to the enzymes according to the invention, all known ingredients that are customary in such agents, with at least one further ingredient preferably being present in the agent.
  • the agents according to the invention can in particular contain surfactants, builders, complexing agents, polymers, glass corrosion inhibitors, corrosion inhibitors, bleaching agents such as peroxygen compounds, bleach activators or bleach catalysts, water-miscible organic solvents, enzyme stabilizers, sequestering agents, electrolytes, pH regulators and/or other auxiliary substances such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators and dyes and fragrances.
  • Advantageous ingredients of agents according to the invention are disclosed in the international patent application WO 2009/121725, beginning on page 5, penultimate paragraph, and ending on page 13 after the second paragraph. Express reference is made to this disclosure and the disclosure content therein is incorporated into the present patent application.
  • An agent according to the invention advantageously contains the enzymes according to the invention in an amount of from 2 pg to 20 mg, preferably from 5 pg to 17.5 mg, particularly preferably from 20 pg to 15 mg and very particularly preferably from 50 pg to 10 mg per g of the agent.
  • An agent according to the invention contains the enzymes according to the invention increasingly preferably in an amount of from 1 x 10 -8 to 5% by weight, from 0.0001 to 1% by weight, from 0.0005 to 0.5% by weight, from 0.001 to 0.1% by weight, in each case based on active protein and based on the total weight of the agent.
  • a washing and/or cleaning agent according to the invention contains the dispersin in an amount of 0.01 to 5% by weight, preferably 0.1 to 4% by weight, particularly preferably 0.15 to 2.5% by weight, based on the total weight of the agent.
  • a washing and/or cleaning agent according to the invention contains the at least three further enzymes selected from the group consisting of amylase, protease, lipase, Cellulase, mannanase, pectate lyase and mixtures thereof, in total in an amount of 0.01 to 10 wt.%, preferably 0.1 to 8 wt.%, particularly preferably 0.2 to 6 wt.%, based on the total weight of the agent.
  • the enzymes contained in the agent and/or other ingredients of the agent can be coated with a substance that is impermeable to the enzyme at room temperature or in the absence of water, which substance becomes permeable to the enzyme under the conditions of use of the agent.
  • Such an embodiment of the invention is thus characterized in that the enzyme is coated with a substance that is impermeable to the enzyme at room temperature or in the absence of water.
  • the agent itself can also be packaged in a container, preferably an air-permeable container, from which it is released shortly before use or during the washing process.
  • Further embodiments of the invention include all solid, powdery, liquid, gel-like or pasty dosage forms of agents according to the invention, which may optionally also consist of several phases and may be in compressed or non-compressed form.
  • the agent may be in the form of 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 agent also include extrudates, granules, tablets or pouches.
  • the agent may also be liquid, gel-like or pasty, for example in the form of a non-aqueous liquid detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or a water-containing paste.
  • Liquid agents are generally preferred.
  • the agent may be in the form of a one-component system. Such agents consist of one phase. Alternatively, an agent may also consist of several phases. Such a remedy is therefore divided into several components.
  • the agent according to the invention is a textile detergent.
  • the agent according to the invention is a liquid textile detergent.
  • the agent according to the invention is a pre-portioned detergent, in particular a detergent portion unit comprising a detergent preparation according to the invention and a water-soluble film which completely encloses the detergent preparation.
  • the water-soluble film in which the detergent preparation is packaged can comprise one or more structurally different water-soluble polymer(s).
  • Polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and their copolymers are particularly suitable as water-soluble polymer(s).
  • Water-soluble films are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 g/mol, preferably from 20,000 to 500,000 g/mol, particularly preferably from 30,000 to 100,000 g/mol and in particular from 40,000 to 80,000 g/mol.
  • Suitable water-soluble Films for use are sold by MonoSol LLC, for example under the names M8630, M8720, M8310, C8400 or M8900. Also suitable are films called Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.
  • the detergents according to the invention when in liquid form, they preferably contain more than 40% by weight, preferably 50 to 90% by weight and particularly preferably 60 to 80% by weight of water based on their total weight.
  • the agents according to the invention can contain one or more surfactants, with particular emphasis being placed on anionic surfactants, nonionic surfactants and mixtures thereof, but cationic, zwitterionic and/or amphoteric surfactants can also be included.
  • the agents preferably contain 5 to 70% by weight of surfactant, preferably 35 to 60% by weight and more preferably 40 to 55% by weight of surfactant.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Soaps which can be used are preferably the alkali salts of saturated or unsaturated C s fatty acids. Such fatty acids can also be used in a form which is not completely neutralized.
  • the useful surfactants of the sulfate type include the salts of the sulfuric acid half esters of C s fatty alcohols and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the usable surfactants of the sulfonate type include, for example, Cg-14-alkylbenzenesulfonates, alkanesulfonates which are obtained from Cs-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, Ci2-18-olefinsulfonates which are formed by reacting corresponding monoolefins with sulfur trioxide, mixtures of alkene and hydroxyalkanesulfonates, disulfonates such as those obtained from Cs-monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, and ⁇ -sulfofatty acid esters (estersulfonates) which are formed by sulfonating fatty acid methyl or ethyl esters, e.g. ⁇ -sulfonated methyl esters of
  • the agent preferably contains 2 to 55% by weight, preferably 3 to 35% by weight, of anionic surfactant.
  • the agent most preferably contains 3 to 25% by weight of alkylbenzenesulfonate.
  • the agent can preferably contain other anionic surfactants, in particular alkyl ether sulfates, and nonionic surfactants, in particular fatty alcohol alkoxylates. These can then make up the rest of the surfactants.
  • Suitable alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula in which R' and R" are independently H or alkyl and together contain 6 to 19, preferably 7 to 15 and in particular 9 to 13 C atoms.
  • a particularly preferred representative is sodium dodecylbenzylsulfonate.
  • Preferred alk(en)yl sulfates are the alkali metal and especially the sodium salts of the sulfuric acid half esters of the C12-18 fatty alcohols, e.g. from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-20 oxo alcohols and those half esters of secondary alcohols of these chain lengths.
  • alk(en)yl sulfates of the chain length mentioned which contain a synthetic, petrochemically based straight-chain alkyl radical, which have a degradation behavior similar to that of the corresponding compounds based on oleochemical raw materials.
  • the C12-16 alkyl sulfates and C12-15 alkyl sulfates as well as C-18 alkyl sulfates are preferred.
  • sulfuric acid monoesters of straight-chain or branched C7-2i-alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-n-alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci2-18-fatty alcohols with 1 to 4 EO.
  • Suitable alkyl ether sulfates are, for example, compounds of the formula
  • R 1 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, with the representatives with an even number of C atoms being preferred.
  • Particularly preferred radicals R 1 are derived from C s fatty alcohols, e.g.
  • AO is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
  • EO ethylene oxide
  • PO propylene oxide
  • the index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X + stands for a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and among these Na + or K + , with Na + being extremely preferred. Further cations X + can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and mixtures thereof.
  • the stated degree of ethoxylation represents a statistical average, which can be a whole or a fractional number for a specific product.
  • the stated degrees of alkoxylation represent statistical averages, which for a specific Product can be a whole or a fractional number.
  • Preferred alkoxylates/ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • agents also contain soap(s).
  • Preferred agents are therefore characterized by the fact that they contain soap(s).
  • Suitable are saturated 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, e.g. coconut, palm kernel or tallow fatty acids.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and/or propoxylation products of alkyl glycosides or linear or branched alcohols each having 8 to about 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl moiety, and of alkylphenols having 5 to 12 C atoms in the alkyl radical are usable.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 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 can contain linear and methyl-branched radicals in the mixture, as is usually the case in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C6-n alcohol with 7 EO, C8-s alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C8-s alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages which can be a whole or a fractional number for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
  • alkyl polyglycosides Another class of non-ionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • RO(G) Z in which R is a linear or branched, in particular 2-methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1 and 4, preferably between 1 and 2 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglycosides are preferably used, i.e. alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • Non-ionic surfactants of the amine oxide type e.g. N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides may also be suitable.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of that.
  • Suitable amphoteric surfactants are, for example, betaines of the formula
  • R'" is an alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C10-18-alkyldimethylcarboxymethylbetaine and Cn-17-alkylamidopropyldimethylcarboxymethylbetaine.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula
  • R vi to R ix are four identical or different, in particular two long-chain and two short-chain, alkyl radicals and X- is an anion, in particular a halide ion, e.g. didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof.
  • Suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • Another preferred component of agents according to the invention are complexing agents.
  • Particularly preferred complexing agents are phosphonates, provided their use is permitted by regulations.
  • the complexing phosphonates include a range of different compounds, such as diethylenetriaminepenta(methylenephosphonic acid) (DTPMP).
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues are preferably used as aminoalkanephosphonates. They are preferably used in the form of neutral sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP. As The preferred builder is HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the phosphonates mentioned, particularly if the agents also contain bleach.
  • a preferred agent in the context of this application contains one or more phosphonate(s) from the group aminotrimethylenephosphonic acid (ATMP) and/or its salts; ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and/or its salts;
  • DTPMP Diethylenetriaminepenta(methylenephosphonic acid) and/or salts thereof; 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and/or salts thereof; 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and/or salts thereof; hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) and/or salts thereof; nitrilotri(methylenephosphonic acid) (NTMP) and/or salts thereof.
  • the agents according to the invention can contain two or more different phosphonates.
  • Preferred agents according to the invention are characterized in that the agent contains at least one complexing agent from the group of phosphonates, preferably 1-hydroxyethane-1,1-diphosphonate, wherein the weight proportion of the phosphonate in the total weight of the agent is preferably 0.1 and 8.0 wt.%, preferably 0.2 and 5.0 wt.%, more preferably 0.3 and 3.0 wt.% and particularly preferably 0.5-2.0 wt.%.
  • the washing and/or cleaning agents according to the invention are essentially free of phosphonate-containing compounds.
  • "Essentially free of phosphonate-containing compounds” in this context means that the corresponding agents contain less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight and particularly preferably less than 0.1% by weight of phosphonate-containing compounds, based on the total weight of the agent. In particularly preferred embodiments, these agents are free of phosphonate-containing compounds.
  • the agents according to the invention preferably also contain builders, preferably at least one water-soluble and/or water-insoluble, organic and/or inorganic builder.
  • the builders include in particular silicates, carbonates and organic cobuilders.
  • Organic cobuilders include, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below. Organic cobuilder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight. Useful organic builders are, for example, polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to be carboxylic acids which have more than one acid function.
  • Examples of these are citric acid, adipic acid, succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids and carboxymethylinulins, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, glutaminediacetic acid, nitrilotriacetic acid (NTA), iminodisuccinate such as ethylenediamine-N,N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), lysinetetra(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxy
  • Such organic builder substances can, if desired, be contained in amounts of up to 50% by weight, in particular up to 25% by weight, preferably from 10 to 20% by weight and particularly preferably from 1 to 5% by weight.
  • the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are particularly suitable here.
  • Citric acid or salts of citric acid are particularly preferably used as the builder substance.
  • MGDA methylglycine disidic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • EDDS ethylenediamine disuccinate
  • carboxymethylinulin and polyaspartate methylglycine disidic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • EDDS ethylenediamine disuccinate
  • Citric acid/citrate can each be used in the form of their hydrates, for example citric acid can be used in the form of the monohydrate, citrate in the form of the trisodium citrate dihydrate.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, e.g. those with a relative molecular mass of 500 to 70,000 g/mol.
  • the molar masses given for polymeric polycarboxylates in the sense of this application are weight-average molar masses Mw of the respective acid form, which were generally determined by means of gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which, due to its structural similarity to the polymers examined, provides realistic molar weight values. These figures differ significantly from the molar weight figures for which polystyrene sulfonic acids are used as a standard.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular weights of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, may be preferred. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have proven particularly suitable.
  • Their relative molecular weight, based on free acids is generally 2000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol and in particular 30,000 to 40,000 g/mol.
  • a solid agent according to the invention preferably contains at least one water-soluble and/or water-insoluble, organic and/or inorganic builder.
  • the water-soluble organic builder substances include the above-mentioned organic framework substances.
  • the agents of the invention can also contain inorganic water-soluble builders.
  • Suitable water-soluble inorganic builder materials are in particular alkali silicates, alkali carbonates, alkali hydrogen carbonates, alkali phosphates and/or sesquicarbonates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Small amounts of calcium carbonates can also be contained in solid textile detergents. Suitable examples are water-soluble crystalline and/or amorphous alkali silicates.
  • the alkali silicates that can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO2 of less than 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are sodium silicates, in particular amorphous sodium silicates, with a molar ratio Na2O:SiO2 of 1:2 to 1:2.8.
  • Crystalline silicates which can be present alone or in a mixture with amorphous silicates are preferably crystalline layered silicates of the general formula Na2Si x O2x+i • y H2O, in which x, the so-called modulus, is a number from 1.9 to 22, in particular 1.9 to 4, and y is a number from 0 to 33, and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na2Si2 ⁇ 5 • y H2O are preferred.
  • Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali silicates, can also be used in agents according to the invention.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment of agents according to the invention.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.
  • Crystalline layered silicates of the above formula (I) are sold by Clariant GmbH under the trade name Na-SKS, e.g. Na-SKS-1 (Na2Si22O45 • x H2O, Kenyaite), Na-SKS-2 (Na2Sii4O29 • x H2O, Magadiite), Na- SKS-3 (Na2SisOi7 • x H2O) or Na-SKS-4 (Na2Si4Ü9 • x H2O, macatite).
  • Na-SKS e.g. Na-SKS-1 (Na2Si22O45 • x H2O, Kenyaite), Na-SKS-2 (Na2Sii4O29 • x H2O, Magadiite), Na- SKS-3 (Na2SisOi7 • x H2O) or Na-SKS-4 (Na2Si4Ü9 • x H2O, macatite).
  • Na-SKS-5 (a-Na 2 Si 2 O 5 ), Na-SKS-7 (ß-Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 • 3 H2O), Na-SKS-10 (NaHSi 2 O 5 • 3 H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na2Si2C>5) are particularly suitable.
  • a granular compound of crystalline layered silicate and citrate, of crystalline layered silicate and the above-mentioned (co-)polymeric polycarboxylic acid, or of alkali silicate and alkali carbonate is used, as is commercially available under the name Nabion® 15, for example.
  • Such water-soluble inorganic builder materials are preferably contained in the inventive agents in amounts of 1 to 20% by weight, in particular 5 to 15% by weight.
  • Other important water-soluble inorganic builder substances are carbonates (and hydrocarbonates), in particular sodium carbonate, and phosphonic acids/phosphonates.
  • the agents according to the invention are preferably free of phosphate builders, i.e. they contain less than 1% by weight, preferably no deliberately added phosphate builder.
  • the agents can also contain water-insoluble builder substances.
  • Water-insoluble inorganic builder materials used are in particular crystalline or amorphous water-dispersible alkali aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, in particular from 3 to 20% by weight and particularly preferably from 1 to 15% by weight.
  • preference is given to crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, zeolite P, zeolite MAP and optionally zeolite X, alone or in mixtures, e.g.
  • zeolites A and X in the form of a co-crystallizate of zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta S.p.A.). Amounts close to the upper limit mentioned are preferably used in solid, particulate agents. Suitable aluminosilicates in particular do not contain any particles with a grain size of more than 30 pm and preferably consist of at least 80% by weight of particles with a size of less than 10 pm. Their calcium binding capacity, which can be determined according to DE 2412837 A1, is generally in the range of 100 to 200 mg CaO per gram.
  • the agent may contain cleaning-active polymers.
  • the weight proportion of the cleaning-active polymers in the total weight of the agent according to the invention is preferably 0.1 to 20 wt. %, preferably 1.0 to 15 wt. %, and more preferably 2.0 to 12 wt. %.
  • Peroxygen compounds suitable for use in agents according to the invention are, in particular, organic peracids or peracidic salts 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, including perborate, percarbonate, persilicate and/or persulfate such as caroate, as well as hydrogen peroxide inclusion compounds such as H2G2-urea adducts. Hydrogen peroxide can also be produced with the aid of an enzymatic system, ie an oxidase and its substrate.
  • solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be used in principle in can be coated in a known manner.
  • the peroxygen compounds can be added to the washing solution as such or in the form of agents containing them, which in principle can contain all the usual washing, cleaning or disinfectant ingredients.
  • Alkali percarbonate or alkali perborate monohydrate is particularly preferably used. If an agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5 to 30% by weight, more preferably from 0.1 to 20% by weight.
  • Compounds which, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid, can be used as bleach activators in the agents.
  • Substances which carry O- and/or N-acyl groups of the stated number of C atoms and/or optionally substituted benzoyl groups are suitable.
  • acylated 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 or carboxylates or the sulfonic or carboxylic acids thereof, in particular nonanoyl or isononanoyloxybenzenesulfonate or laroyloxybenzenesulfonate (NOBS or iso-NOBS or LOBS), 4-(2-decanoyloxyethoxycarbonyloxy)benzenesulfonate (DECOBS) or decanoy
  • N-benzoylcaprolactam nitriles from which perimidic acids are formed, in particular aminoacetonitrile derivatives with a quaternized nitrogen atom, and/or oxygen-transferring sulfonimines and/or acylhydrazones.
  • the hydrophilically substituted acyl acetals and the acyl lactams are also preferred.
  • Combinations of conventional bleach activators can also be used.
  • Such bleach activators can be present in the usual amount range, preferably in amounts of 0.5 to 10% by weight, in particular 1 to 8% by weight, based on the total agent, particularly in the presence of the above-mentioned hydrogen peroxide-producing bleaching agents, but are preferably completely absent when percarboxylic acid is used as the sole bleaching agent.
  • solid agents can also contain sulfonimines and/or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts.
  • Suitable greying inhibitors or soil release agents are cellulose ethers such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Sodium carboxymethylcellulose, Hydroxypropylmethylcellulose and mixtures thereof and optionally mixtures thereof with methylcellulose are used.
  • the soil-release active ingredients commonly used include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
  • the proportion of graying inhibitors and/or soil-release active ingredients in agents according to the invention is generally not more than 2% by weight and is preferably 0.5 to 1.5% by weight, particularly preferably 0.5 to 2% by weight.
  • Optical brighteners particularly for textiles made from cellulose fibers (e.g. cotton), can include derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable examples are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilbene-2,2'-disulfonic acid or similarly structured compounds which have a diethanolamino group, a methylamino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type can also be present, e.g.
  • Brighteners of the 1,3-diaryl-2-pyrazoline type e.g. 1-(p-sulfoamoylphenyl)-3-(p-chlorophenyl)-2-pyrazoline and similarly structured compounds, are particularly suitable for polyamide fibers.
  • the content of optical brighteners or brightener mixtures in the agent is generally not more than 1% by weight, preferably 0.05 to 0.5% by weight. In a preferred embodiment of the invention, the agent is free of such active ingredients.
  • the usual foam regulators that can be used in the agents according to the invention include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanized or otherwise hydrophobized.
  • the polysiloxanes can consist of linear compounds as well as cross-linked polysiloxane resins and mixtures thereof.
  • Other defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, whose melting point is above 40°C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, e.g. sodium behenate, and alkali salts of phosphoric acid mono- and/or dialkyl esters, in which the alkyl chains each have 12 to 22 C atoms.
  • sodium monoalkyl phosphate and/or dialkyl phosphate with Ci6-18 alkyl groups is preferably used.
  • the proportion of foam regulators may preferably be 0.2 to 2 wt.%, particularly preferably not more than 1 wt.%.
  • the agents according to the invention can contain system- and environmentally compatible acids, in particular 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 alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides, preferably sodium hydroxide.
  • Such pH regulators are preferably contained in the agents according to the invention in amounts of no more than 10% by weight, in particular from 0.5 to 6% by weight, particularly preferably from 0.3 to 2% by weight.
  • the agents according to the invention can contain an organic solvent as a further component.
  • organic solvents have a beneficial effect on the Enzyme stability and the cleaning performance of these agents.
  • Preferred organic solvents come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are selected from ethanol, n- or i-propanol, butanol, glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, 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 methyl ether, dipropylene glycol ethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol
  • the weight proportion of these organic solvents in the total weight of agents according to the invention is preferably 0.1 to 10 wt. %, preferably 0.2 to 8.0 wt. %, and more preferably 0.5 to 5.0 wt. %.
  • a particularly preferred organic solvent that is particularly effective in terms of stabilizing the agents is glycerin and 1,2-propylene glycol.
  • Liquid agents preferably comprise at least one polyol, preferably from the group glycerin and 1,2-propylene glycol, based on the total weight of the agent, preferably 0.1 to 10 wt. %, preferably 0.2 to 8.0 wt. %, and more preferably 0.5 to 5.0 wt. %.
  • organic solvents are organic amines and alkanolamines.
  • the agents according to the invention preferably contain these amines in amounts of 0.1 to 10 wt. %, preferably 0.2 to 8.0 wt. %, and more preferably 0.5 to 5.0 wt. %, in each case based on their total weight.
  • a particularly preferred alkanolamine is ethanolamine.
  • Detergents and/or cleaning agents according to the invention can contain exclusively the enzymes according to the invention. Alternatively, they can also contain further hydrolytic enzymes or other enzymes in a concentration suitable for the effectiveness of the agent. A further embodiment of the invention thus represents agents which further comprise one or more further enzymes.
  • All enzymes which can preferably be used as further enzymes are those which can display a catalytic activity in the agent according to the invention, in particular a protease, lipase, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, ß-glucosidase, pectinase, carrageenase, perhydrolase, oxidase, oxidoreductase, and mixtures thereof.
  • Further enzymes are advantageously contained in the agent in an amount of 1 x 10 8 to 5 percent by weight, based on active protein.
  • Each additional enzyme is increasingly preferably present in agents according to the invention in an amount of 1 x 10 -7 to 3% by weight, from 0.00001 to 1% by weight, from 0.00005 to 0.5% by weight, from 0.0001 to 0.1% by weight and particularly preferably from 0.0001 to 0.05% by weight, based on active protein.
  • the enzymes particularly preferably exhibit synergistic cleaning performance against certain soilings or stains, ie the enzymes contained in the agent composition support each other in their cleaning performance.
  • proteases are the subtilisins BPN' from Bacillus amyloliquefaciens and Carlsberg from Bacillus licheniformis, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, subtilisin DY and the subtilases, but no longer the subtilisins in the narrower sense Thermitase, Proteinase K and the proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from the company Novozymes.
  • Subtilisins 147 and 309 are sold under the trade names Esperase® and Savinase® respectively by the company Novozymes.
  • Protease variants are derived from the protease from Bacillus lentus DSM 5483, described in e.g. WO 95/23221, WO 92/21760, WO 2013/060621 and EP 3660151.
  • Other useful proteases are e.g.
  • proteases from Bacillus gibsonii and Bacillus pumilus which are disclosed in WO 2008/086916, WO 2007/131656, WO 2017/215925, WO 2021/175696 and WO 2021/175697, are also particularly preferably used.
  • amylases are the a-amylases from Bacillus licheniformis, Bacillus amyloliquefaciens or Bacillus stearothermophilus and in particular their further developments that have been improved for use in washing and/or cleaning agents.
  • the enzyme from Bacillus licheniformis is available from Novozymes under the name Termamyl® and from Danisco/DuPont under the name Purastar® ST. Further developments of this a-amylase are available under the trade names Duramyl® and Termamyl® ultra (both from Novozymes), Purastar® OxAm (Danisco/DuPont) and Keistase® (Daiwa Seiko Inc.).
  • the a-amylase from Bacillus amyloliquefaciens is sold by the company Novozymes under the name BAN®, and variants derived from the a-amylase from Bacillus stearothermophilus under the names BSG® and Novamyl®, also by the company Novozymes.
  • Other products that are worth mentioning for this purpose are the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948). Fusion products of all of the molecules mentioned can also be used.
  • a-amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are also suitable.
  • Other commercial products that can be used advantageously are, for example, Amylase-LT® and Stainzyme® or Stainzyme® ultra or Stainzyme® plus as well as AmplifyTM 12L or Amplify PrimeTM 100L, the latter also from the company Novozymes, as well as the PREFERENZ S® series from the company Danisco/DuPont, including, for example, PREFERENZ S100®, PREFERENZ S1000® or PREFERENZ S210®.
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein-engineered mutants are included. Suitable cellulases are cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum, which are disclosed in US 4435307, US 5648263, US 5691178, US 5776757 and WO 89/09259.
  • cellulases are the alkaline or neutral cellulases with color-care properties.
  • Examples of such cellulases are cellulases described in EP 0495257, EP 0531372, WO 96/11262, WO 96/29397, WO 98/08940.
  • Other examples are cellulase variants as described in WO 94/07998, EP 0531315, EP 3212777, EP 3502243, EP 3653705, EP 3653706, US 5457046, US 5686593, US 5763254, WO 95/24471, WO 98/12307 and WO 99/01544 and WO 2019/122520.
  • cellulases with endo-1,4-glucanase activity are described in WO 2002/099091, e.g. those having a sequence of at least 97% identity to the amino acid sequence of positions 1 to 773 of SEQ ID NO:2 of WO 2002/099091.
  • Another example may comprise a GH44 xyloglucanase, e.g. a xyloglucanase enzyme having a sequence of at least 60% identity to positions 40 to 559 of SEQ ID NO:2 of WO 2001/062903.
  • Other examples of cellulases include the GH45 cellulases described in WO 96/29397.
  • CelluzymeTM Commercially available cellulases include CelluzymeTM, CarezymeTM, Carezyme PremiumTM, CellucleanTM (e.g. CellucleanTM 5000L and CellulcleanTM 4000T), Celluclean ClassicTM, CellusoftTM, Endolase®, Renozyme® and WhitezymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), KAC-500(B)TM (Kao Corporation), RevitalenzTM 1000, RevitalenzTM 2000 and RevitalenzTM 3000 (DuPont), as well as Ecostone® and Biotouch® (AB Enzymes).
  • CelluzymeTM e.g. CellucleanTM 5000L and CellulcleanTM 4000T
  • Celluclean ClassicTM CellusoftTM, Endolase®, Renozyme® and WhitezymeTM
  • Novozymes A/S Novozymes A/S
  • ClazinaseTM and Puradax HATM Genen
  • Suitable lipases are, for example, those from Thermomyces, e.g. from T. lanuginosus (formerly Humicola lanuginosa) as described in EP 0258068 and EP 0305216, lipase from strains of Pseudomonas (some of them now renamed Burkholderia), e.g. P. alcaligenes or P. pseudoalcaligenes, P. cepacia, P. sp. strain SD705, P.
  • Preferred lipases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed therefrom, in particular those with one or more of the following amino acid substitutions starting from the lipase mentioned in positions D96L, T213R and/or N233R, particularly preferably T213R and N233R.
  • the preferred commercial lipase products include LipolaseTM, LipexTM, LipolexTM and LipocleanTM (Novozymes A/S), Lumafast (Genencor/DuPont) and Lipomax (Gist-Brocades).
  • Suitable mannanases are, for example, the Bacillus subtilis endo-ß-mannanase, Bacillus sp. I633 Endo-ß-mannanase, Bacillus sp. AAI12 Endo-ß-mannanase, Bacillus sp.
  • Endo-ß-mannanase Bacillus agaradhaerens NCIMB 40482 Endo-ß-mannanase, Bacillus halodurans Endo-ß-mannanase, Bacillus clausii Endo-ß-mannanase, Bacillus licheniformis Endo-ß-mannanase, Humicola insolens Endo-ß-mannanase and Caldocellulosiruptor sp. endo-ß-mannanase (see e.g. US 6060299, WO 99/64573, US 6566114 and WO 99/64619).
  • Pectate lyases suitable for washing and cleaning agents are described, for example, in WO 2003/095638 or WO 2015/121133.
  • suitable pectinolytic enzymes are also the enzymes and enzyme preparations available under the trade names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from the company Novozymes, under the trade names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® from the company AB Enzymes and under the trade name Pyrolase® from the company Diversa Corp.
  • the enzymes to be used can also be formulated together with accompanying substances, for example from fermentation.
  • the enzymes are preferably used as enzyme liquid formulation(s).
  • the enzymes are generally not provided in the form of pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other additives.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer that is impermeable to water, air and/or chemicals.
  • active ingredients such as stabilizers, emulsifiers, pigments, bleaching agents or dyes, can be applied in superimposed layers.
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable in storage due to the coating.
  • the enzymes can also be incorporated into water-soluble films, such as those used in the packaging of detergents and cleaning agents in unit dosage form. Such a film enables the release of the enzymes after contact with water.
  • water-soluble refers to a film structure that is preferably completely water-soluble.
  • a film consists of (fully or partially hydrolyzed) polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • the agents according to the invention can comprise one or more reversible enzyme inhibitors/stabilizers.
  • the agents according to the invention can contain the reversible enzyme inhibitors/stabilizers in a concentration of 0.1 to 2% by weight, preferably 0.3 to 1.5% by weight, based on the total weight of the agent. If several inhibitors/stabilizers are included, these details refer to the total concentration.
  • polyols such as glycerin or 1,2-ethylene glycol, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters or derivatives, in particular phenylboronic acid derivatives or 4-formylphenylboronic acid (4-FPBA), antioxidants, special peptide compounds and combinations thereof.
  • polyols such as glycerin or 1,2-ethylene glycol, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters or derivatives, in particular phenylboronic acid derivatives or 4-formylphenylboronic acid (4-FPBA), antioxidants, special peptide compounds and combinations thereof.
  • phenylboronic acid derivative is understood to mean a compound with the formula (III).
  • the compound of the formula (III) has the following structural formula: where R is hydrogen, a hydroxyl, a C 1-6 alkyl, a substituted C 1-6 alkyl, a C 1-6 alkenyl or a substituted C 1-6 alkenyl group.
  • R is hydrogen, a hydroxyl, a C 1-6 alkyl, a substituted C 1-6 alkyl, a C 1-6 alkenyl or a substituted C 1-6 alkenyl group.
  • the radical R in the phenylboronic acid derivative is a C 1-6 alkyl group and more preferably -CH3, -CH3CH2 or -CH3CH2CH2. More preferably, the radical R in the phenylboronic acid derivative is hydrogen.
  • the phenylboronic acid derivative is particularly preferably 4-formylphenylboronic acid (4-FPBA).
  • the inhibitor/stabilizer compound used can be boric acid.
  • the washing and/or cleaning agent according to the invention is essentially free of boron-containing compounds.
  • "Essentially free of boron-containing compounds" in this context means that the agents according to the invention contain less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight and particularly preferably less than 0.1% by weight, of boron-containing compounds, based on the total weight of the agent.
  • the agents according to the invention are free of boron-containing compounds, i.e. they contain in particular no boric acid and/or phenylboronic acid derivatives.
  • the enzyme and the inhibitor/stabilizer compound can be pre-formulated in an enzyme composition.
  • the enzyme protein only forms a fraction of the total weight of conventional enzyme preparations.
  • Preferably used enzyme preparations contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein.
  • the inhibitor/stabilizer compound can be present in an amount of 0.05 to 35% by weight, preferably from 0.05 to 10% by weight, based on the total weight in the enzyme composition.
  • This enzyme composition which is also a component of the present invention, can then be used in agents according to the invention in amounts which lead to the final concentrations in the agent indicated above.
  • a further subject matter of the invention is an agent for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, as well as for improving the hygiene of textiles, characterized in that the agent contains a dispersin, wherein the dispersin has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical and, with respect to the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3,
  • a preferred embodiment relates to an agent for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, as well as for improving the hygiene of textiles, characterized in that the agent contains a dispersin, wherein the dispersin has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical and, with respect to the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15,
  • a further subject matter of the invention relates to a method for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, and for improving the hygiene of textiles, characterized in that in at least one method step a dispersin according to the invention, as described herein, and/or an agent according to the invention, as described herein, is used, wherein the method is preferably carried out in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
  • Processes for cleaning textiles are generally characterized by the fact that various cleaning-active substances are applied to the item to be cleaned in several process steps and washed off after the exposure time, or that the item to be cleaned is treated in some other way with a detergent or a solution or dilution of this agent.
  • This also includes processes using (semi-)automated washing or cleaning systems such as robot mops or wet vacuum cleaners.
  • This subject matter of the invention also includes a machine dishwashing process.
  • the dosing of the agent according to the invention into the cleaning solution can be carried out in such a process, for example, by means of the dosing chamber in the door or by means of an additional dosing container in the interior of the dishwasher.
  • the agent can also be applied directly to the soiled dishes or to one of the interior walls of the dishwasher, e.g. the inside of the door.
  • the process according to the invention is carried out in the interior of a commercially available dishwasher.
  • the cleaning program in a dishwasher can usually be selected and set by the consumer before the dishwashing process is carried out.
  • the cleaning program of the dishwasher used in the process according to the invention comprises at least one pre-wash cycle and a cleaning cycle.
  • cleaning programs are preferred which include further cleaning or rinsing cycles, e.g. a final rinse cycle.
  • the method according to the invention is particularly preferably part of a cleaning program comprising a pre-rinse cycle, a cleaning cycle and a final rinse cycle.
  • the method according to the invention is preferably used in conjunction with cleaning programs in which the washing liquor is heated during the cleaning cycle.
  • the cleaning cycle, during which the agent according to the invention is metered into the interior of the dishwasher is characterized in that during its course the temperature of the cleaning liquor rises to values above 30°C, preferably above 40°C and in particular above 50°C.
  • Alternative embodiments of this subject matter of the invention also represent processes for treating textile raw materials or for textile care, in which an agent according to the invention is active in at least one process step.
  • processes for textile raw materials, fibers or textiles with natural components are preferred, and very particularly for those with wool or silk.
  • Figure 1 shows scanning electron microscope images of fibers after washing (magnification: 50 pm).
  • Figure 1 A shows a picture of fibers after washing twice with a non-inventive detergent (V1; without dispersin).
  • Figure 1B shows a photo of fibers after washing twenty times with a non-inventive detergent (V1; without dispersin).
  • Figure 1C shows a photo of fibers after washing twice with a detergent according to the invention (E1; with dispersin).
  • Figure 1D shows a photo of fibers after washing twenty times with a detergent according to the invention (E1; with dispersin).
  • the dispersin according to the invention can be used in various washing and cleaning agents and realize its effect.

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Abstract

The invention relates to detergents and cleaning agents, in particular enzyme-containing detergents and cleaning agents, and relates to the use of a dispersin or of a dispersin-containing agent to prevent and/or reduce and/or remove microbially induced deposits on textiles, crockery and other surfaces, in particular household surfaces, particularly preferably to deep clean textiles down to the fibres, and to enhance textile hygiene. The invention also relates to a corresponding agent and to a method.

Description

WASCH- UND REINIGUNGSMITTEL MIT DISPERSIN WASHING AND CLEANING PRODUCTS WITH DISPERSIN
BESCHREIBUNG DESCRIPTION
Die Erfindung liegt auf dem Gebiet der Wasch- und Reinigungsmittel, insbesondere enzymhaltigen Wasch- und Reinigungsmittel, und betrifft die Verwendung eines Dispersin bzw. eines dispersinhaltigen Mittels zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt ein vorportioniertes Textilwaschmittel, umfassend mindestens ein Dispersin und mindestens einen Duftstoff. Ebenfalls Bestandteil der Erfindung sind die entsprechenden Wasch- und/oder Reinigungsverfahren und die Verwendung der hierin beschriebenen Mittel zur Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien. Des Weiteren betrifft die Erfindung entsprechende Mittel und Verfahren. The invention is in the field of washing and cleaning agents, in particular enzyme-containing washing and cleaning agents, and relates to the use of a dispersin or an agent containing a dispersin for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably a pre-portioned textile detergent comprising at least one dispersin and at least one fragrance. Also part of the invention are the corresponding washing and/or cleaning methods and the use of the agents described herein for cleaning textiles and for improving the hygiene of textiles. The invention also relates to corresponding agents and methods.
Der Einsatz von Enzymen in Waschmitteln ist seit Jahrzehnten im Stand der Technik etabliert. Sie dienen dazu, das Leistungsspektrum der betreffenden Mittel entsprechend ihren speziellen Aktivitäten zu erweitern. Hierzu gehören insbesondere hydrolytische Enzyme wie Proteasen, Amylasen, Lipasen und Cellulasen. Die ersten drei genannten hydrolysieren Proteine, Stärke und Fette und tragen somit unmittelbar zur Schmutzentfernung bei. Cellulasen werden in Textilwaschmitteln insbesondere wegen ihrer Gewebewirkung eingesetzt. Eine weitere Gruppe von Waschmittelenzymen sind oxidative Enzyme, insbesondere Oxidasen, die ggf. im Zusammenspiel mit anderen Komponenten vorzugsweise dazu dienen, Anschmutzungen zu bleichen und/oder die bleichenden Agentien in situ zu erzeugen. Neben diesen Enzymen, die einer fortwährenden Optimierung unterworfen sind, werden laufend weitere Enzyme für den Einsatz in Waschmitteln bereitgestellt, um insbesondere spezielle Anschmutzungen optimal angehen zu können, wie z.B. Pektinasen, Pektatlysasen, Xanthanasen, ß-Glucanasen, Mannanasen, Dispersine und dergleichen, zur Hydrolyse insbesondere spezieller pflanzlicher Polymere. Generell sind nur ausgewählte Enzyme für den Einsatz in flüssigen Tensid-haltigen Zubereitungen überhaupt geeignet. Viele Enzyme zeigen in derartigen Zubereitungen keine ausreichende katalytische Leistung. Für die Anwendung von Enzymen in Reinigungsmitteln ist daher eine hohe katalytische Aktivität unter Bedingungen wie sie sich während eines Waschgangs darstellen und eine hohe Lagerstabilität besonders wünschenswert. The use of enzymes in detergents has been established in the state of the art for decades. They serve to expand the performance spectrum of the agents in question according to their special activities. These include in particular hydrolytic enzymes such as proteases, amylases, lipases and cellulases. The first three mentioned hydrolyze proteins, starch and fats and thus contribute directly to the removal of dirt. Cellulases are used in textile detergents in particular because of their effect on fabrics. Another group of detergent enzymes are oxidative enzymes, in particular oxidases, which, if necessary in conjunction with other components, preferably serve to bleach soiling and/or to generate the bleaching agents in situ. In addition to these enzymes, which are subject to continuous optimization, other enzymes are constantly being made available for use in detergents in order to be able to optimally tackle special types of soiling, such as pectinases, pectate lysases, xanthanases, ß-glucanases, mannanases, dispersins and the like, in particular for the hydrolysis of special plant polymers. In general, only selected enzymes are suitable for use in liquid surfactant-containing preparations. Many enzymes do not show sufficient catalytic performance in such preparations. For the use of enzymes in cleaning agents, a high catalytic activity under conditions such as those encountered during a wash cycle and a high storage stability are therefore particularly desirable.
An die Konfektions- und Angebotsformen von Wasch- und Reinigungsmittel werden sich kontinuierlich ändernde Anforderungen gestellt. Ein Hauptaugenmerk liegt dabei seit geraumer Zeit auf der bequemen Dosierung von Wasch- und Reinigungsmitteln durch den Verbraucher und der Vereinfachung der zur Durchführung eines Wasch- oder Reinigungsverfahren notwendigen Arbeitsschritte. Eine technische Lösung bieten vorportionierte Wasch- oder Reinigungsmittel, beispielsweise Folienbeutel mit einer oder mehreren Aufnahmekammern für feste und/oder flüssige Wasch- und Reinigungsmittel. Ein für die Herstellung dieser Folienbeutel relevanter Trend, ist die Miniaturisierung dieser Folienbeutel. Hintergrund dieser Entwicklung sind neben einer höheren Verbraucherakzeptanz aufgrund vereinfachter Handhabung insbesondere Nachhaltigkeitsaspekte, beispielsweise in Bezug auf Transportvolumina und -kosten und die Menge der eingesetzten Verpackungsmittel. Die Aufkonzentration moderner Wasch- und Reinigungsmittel setzt eine fortschreitende Optimierung bestehender Rezepturen und die Entwicklung neuer, leistungsfähigerer Rezepturen voraus. Ein Ziel dieser Entwicklungen, bei denen in der Regel auf bekannte wasch- und reinigungsaktive Wirkstoffe zurückgegriffen wird, ist es, bei gleichbleibender oder verringerter Dosiermenge eine Wasch- oder Reinigungsleistungssteigerung der Rezepturen zu erreichen. The packaging and supply of detergents and cleaning agents are subject to constantly changing requirements. For some time now, the main focus has been on the convenient dosing of detergents and cleaning agents by the consumer and the simplification of the work steps required to carry out a washing or cleaning process. A technical solution is pre-portioned detergents or cleaning agents, for example foil bags with one or more receiving chambers for solid and/or liquid detergents and cleaning agents. A trend relevant to the production of these foil bags is the Miniaturization of these film bags. The background to this development is not only greater consumer acceptance due to simplified handling, but also sustainability aspects, for example in relation to transport volumes and costs and the amount of packaging used. The concentration of modern washing and cleaning agents requires a progressive optimization of existing recipes and the development of new, more effective recipes. One goal of these developments, which usually rely on known washing and cleaning active ingredients, is to achieve an increase in the washing or cleaning performance of the recipes while maintaining or reducing the dosage.
Das wichtigste Kriterium beim Reinigen von Textilien und/oder harten Oberflächen ist die Reinigungsleistung an verschiedensten Anschmutzungen. Auch wenn die Reinigungsleistung der heutzutage eingesetzten Wasch- und Reinigungsmittel generell hoch ist, stellt sich, auch aufgrund des generellen Trends vermehrt Niedrigtemperatur-Programme zu verwenden sowie durch den Trend zur Kompaktierung der Rezepturen (insbesondere bei vorportionierten Verwendungsformen), allerdings das Problem, dass viele der üblichen Wasch- und Reinigungsmittelrezepturen eine unzureichende Reinigungsleistung, insbesondere an hartnäckigen Anschmutzungen, aufweisen. Eine solche unzureichende Reinigungsleistung führen beim Verbraucher zu Unzufriedenheit und dazu, dass solche Anschmutzungen vom Verbraucher vorbehandelt werden, was wiederum den Wasser- und Energieverbrauch erhöht. The most important criterion when cleaning textiles and/or hard surfaces is the cleaning performance on a wide range of soiling. Even though the cleaning performance of the detergents and cleaning agents used today is generally high, the problem is that many of the usual detergent and cleaning agent formulations have insufficient cleaning performance, especially on stubborn soiling, due to the general trend towards using more low-temperature programs and the trend towards compacting the formulations (particularly in pre-portioned forms of use). Such insufficient cleaning performance leads to dissatisfaction among consumers and to consumers pre-treating such soiling, which in turn increases water and energy consumption.
Mit dem Begriff "Schlechtgeruch", wie hierin verwendet, ist ein Geruch gemeint, der auf Oberflächen, insbesondere Haushaltsoberflächen, Geschirr, Textilien und gereinigten Gegenständen, insbesondere gereinigte Textilien und gereinigtes Geschirr, nicht erwünscht ist. Der gereinigte Gegenstand sollte frisch und sauber riechen, ohne dass ihm ein Schlechtgeruch anhaftet. Verschiedenste Ursachen können auf Oberflächen, insbesondere Haushaltsoberflächen, sowie auf gewaschenen Textilien und/oder gereinigten harten Oberflächen, insbesondere Geschirr, einen unangenehmen Geruch, sog. Schlechtgeruch, verursachen. Der Begriff "Haushaltsoberfläche", wie hierin verwendet, meint z.B. Oberflächen in Wasch- oder Geschirrspülmaschinen, Pumpensümpfen, Vorrats be hä Item, Wasserreservoir, Waschtrommel, Spülkammern, Wasch- oder Spülbecken, Toilettenbecken, Spülkasten, WC-Rand, Siphons, Wasserrohren und/oder -leitungen, Wasserzu- und/oder -abläufen. Schlechtgeruch ist insbesondere bei Textilien und Waschmaschinen als Problem bekannt. Aber auch in der Geschirrspülmaschine findet sich Schlechtgeruch. Betroffen sind alle Bauteile, die mit verschmutzten Gegenständen und/oder Wasser, insbesondere gebrauchtem Wasser, und/oder Wasch-/Reinigungslauge in Berührung kommen, wie z.B. Oberflächen in Wasch- oder Geschirrspülmaschinen, Pumpensümpfen, Vorrats be hä Item, Wasserreservoir, Waschtrommel, Spülkammern, Wasch- oder Spülbecken, Siphons, Wasserrohren und/oder -leitungen, Wasserzu- und/oder -abläufen. Eine, wenn nicht die häufigste, Ursache hierfür sind organischer Natur, wie z.B. Sebum, Körperschmutz (bodysoils; z.B. Körperöle, abgestorbene Hautschuppen und Schweiß), Zellrückstände, Nahrungsmittelreste, Körperausscheidungen, Biobeläge und extrazelluläre polymere Substanzen (EPS; z.B. extrazelluläre polymere Saccharide). Hierbei hervorzuheben sind insbesondere die mikrobiell bedingten Biobeläge, d.h. mikrobiell bedingter Schlechtgeruch in Folge von mikrobiell bedingten Biobelägen. Ein weiteres Beispiel für unangenehme Gerüche ist Schweiß oder Körpergeruch, der an einem Gegenstand anhaftet, der mit Menschen oder Tieren in Berührung gekommen ist. Schlechtgeruch findet sich nicht nur in der Waschmaschine, sondern auch auf der frisch gewaschenen, noch feuchten Wäsche, sowie auch auf der trockenen Wäsche, sowie auf zahlreichen weiteren Oberflächen, insbesondere Haushaltsoberflächen und Geschirr. Dazu zählt auch das sog. Re-Blooming, also Wiederaufblühen des Schlechtgeruchs, beim Tragen der Wäsche durch Körperwärme und/oder -feuchtigkeit. Ablagerungen, Biobeläge, Biosoils, Bodysoils und dergleichen führen jedoch nicht nur zu Schlechtgeruch, sondern können auch als Anschmutzungen auf Textilien und/oder Oberflächen, insbesondere Haushaltsoberflächen und Geschirr, Sichtbarwerden, z.B. in Form von Belägen, Schmier, Ankrustungen, Vergilbungen, Achselflecken und Vergrauungen. Biobeläge und dergleichen ermöglichen durch ihre typischerweise adhäsive Textur auch das Anhaften weiterer Schlechtgeruchs- und/oder Schmutzpartikel. Schlechtgeruch kann jedoch auch schon vorhanden sein, bevor die mikrobiell bedingten Ablagerungen zu sichtbaren Verschmutzungen führen. The term "bad smell" as used herein means a smell that is not desired on surfaces, in particular household surfaces, dishes, textiles and cleaned objects, in particular cleaned textiles and cleaned dishes. The cleaned object should smell fresh and clean without a bad smell clinging to it. A wide variety of causes can cause an unpleasant smell, so-called bad smell, on surfaces, in particular household surfaces, as well as on washed textiles and/or cleaned hard surfaces, in particular dishes. The term "household surface" as used herein means, for example, surfaces in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, wash basins or sinks, toilet bowls, cisterns, toilet rims, siphons, water pipes and/or lines, water inlets and/or outlets. Bad smells are known to be a problem, especially with textiles and washing machines. But bad smells can also be found in dishwashers. All components that come into contact with dirty objects and/or water, especially used water and/or washing/cleaning solutions, such as surfaces in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, wash or sink basins, siphons, water pipes and/or lines, water inlets and/or outlets are affected. One, if not the most common, cause of this is of an organic nature, such as sebum, body dirt (bodysoils; e.g. body oils, dead skin cells and sweat), cell residues, food residues, body excretions, bio-deposits and extracellular polymeric substances (EPS; e.g. extracellular polymeric saccharides). Of particular note here are microbial bio-deposits, i.e. microbial bad smells as a result of from microbial biodeposits. Another example of unpleasant odors is sweat or body odor that clings to an object that has come into contact with people or animals. Bad odors are not only found in the washing machine, but also on freshly washed, still damp laundry, as well as on dry laundry, and on numerous other surfaces, particularly household surfaces and dishes. This also includes so-called re-blooming, i.e. the re-blooming of the bad odor when the laundry is worn due to body heat and/or moisture. Deposits, biodeposits, biosoils, bodysoils and the like do not only lead to bad odors, but can also become visible as soiling on textiles and/or surfaces, particularly household surfaces and dishes, e.g. in the form of deposits, grease, encrustations, yellowing, armpit stains and graying. Due to their typically adhesive texture, biodeposits and the like also allow other bad odor and/or dirt particles to adhere. However, bad smells can also be present before the microbial deposits lead to visible contamination.
Der Begriff "Biobelag" wie hierin verwendet, meint nicht nur Biofilme im engeren Sinne, wie mikrobiell bedingte Ablagerungen, Biofilme oder dergleichen, die von jeglichen Mikroorganismen gebildet werden können, deren Zellen aneinander und/oder an einer Oberfläche anhaften, z.B. an Textilien, Geschirr oder einer harten Oberfläche oder einer anderen Art von Oberfläche, sondern auch allgemeiner jegliche Biobeläge, Bio-Soils, biologisch-bedingten Beläge oder dergleichen inkl., aber nicht ausschließlich, Abbau- und Abscheidungsprodukten von Mikroorganismen, die an einer Oberfläche anhaften, z.B. an Textilien, Geschirr oder einer harten Oberfläche oder einer anderen Art von Oberfläche. Diese anhaftenden Zellen sind häufig in eine selbstproduzierte Matrix aus extrazellulärer polymerer Substanz (EPS) eingebettet. Biofilm-EPS ist ein polymeres Konglomerat, das im Allgemeinen aus extrazellulärer DNA, Proteinen und Polysacchariden besteht. Biofilme können sich auf lebenden oder nicht lebenden Oberflächen bilden. Die mikrobiellen Zellen, die in einem Biofilm wachsen, unterscheiden sich physiologisch von den planktonischen Zellen desselben Organismus, bei denen es sich im Gegensatz dazu um Einzelzellen handelt, die in einem flüssigen Medium schwimmen oder schwimmen können. Bakterienzellen, die in einem Biofilm leben, haben in der Regel deutlich andere Eigenschaften als planktonische Bakterienzellen derselben Art, da die dichte und geschützte Umgebung des Films es ihnen ermöglicht, auf verschiedene Weise zu kooperieren und zu interagieren. Ein Vorteil dieses Milieus für die Mikroorganismen ist die erhöhte Resistenz gegenüber Waschmitteln und Antibiotika, da die dichte extrazelluläre Matrix und die äußere Zellschicht das Innere der Gemeinschaft schützen. Zu den Biofilm produzierenden Bakterien auf Textilien gehören z.B. die folgenden Arten: Acinetobacter sp., Aeromicrobium sp., Brevundimonas sp., Microbacterium sp., Micrococcus luteus, Pseudomonas sp., Staphylococcus epidermidis und Stenotrophomonas sp. Auf harten Oberflächen finden sich biofilmbildende Bakterien z.B. unter den folgenden Arten: Acinetobacter sp., Aeromicrobium sp., Brevundimonas sp., Microbacterium sp., Micrococcus luteus, Pseudomonas sp, Staphylococcus epidermidis, Staphylococcus aureus und Stenotrophomonas sp. In EP 3892708, WO 2021/122117, WO 2021/122118, WO 2021/122120, WO 2021/122121 und WO 2022/008387 sind dispersin- sowie enzymhaltige Wasch- und Reinigungsmittel beschrieben. Es wurde zudem beschrieben, dass Dispersin z.B. Biofilm und EPS abbauen kann. The term "bio-soil" as used herein does not only mean biofilms in the narrow sense, such as microbial deposits, biofilms or the like, which can be formed by any microorganisms whose cells adhere to each other and/or to a surface, e.g. to textiles, tableware or a hard surface or another type of surface, but also more generally any bio-soils, bio-soils, biological deposits or the like including, but not limited to, degradation and deposition products of microorganisms that adhere to a surface, e.g. to textiles, tableware or a hard surface or another type of surface. These adherent cells are often embedded in a self-produced matrix of extracellular polymeric substance (EPS). Biofilm EPS is a polymeric conglomerate that generally consists of extracellular DNA, proteins and polysaccharides. Biofilms can form on living or non-living surfaces. The microbial cells growing in a biofilm are physiologically different from the planktonic cells of the same organism, which, in contrast, are solitary cells that float or can swim in a liquid medium. Bacterial cells living in a biofilm usually have significantly different properties than planktonic bacterial cells of the same species, because the dense and protected environment of the film allows them to cooperate and interact in different ways. An advantage of this environment for the microorganisms is increased resistance to detergents and antibiotics, because the dense extracellular matrix and outer cell layer protect the interior of the community. Biofilm-producing bacteria on textiles include, for example, the following species: Acinetobacter sp., Aeromicrobium sp., Brevundimonas sp., Microbacterium sp., Micrococcus luteus, Pseudomonas sp., Staphylococcus epidermidis and Stenotrophomonas sp. Biofilm-forming bacteria found on hard surfaces include the following species: Acinetobacter sp., Aeromicrobium sp., Brevundimonas sp., Microbacterium sp., Micrococcus luteus, Pseudomonas sp, Staphylococcus epidermidis, Staphylococcus aureus and Stenotrophomonas sp. EP 3892708, WO 2021/122117, WO 2021/122118, WO 2021/122120, WO 2021/122121 and WO 2022/008387 describe washing and cleaning agents containing dispersin and enzymes. It has also been described that dispersin can degrade biofilm and EPS, for example.
Angesammelte organische Verschmutzungen sind oft schwer zu entfernen, und handelsübliche Wasch- und Reinigungsmittel reduzieren den Schlechtgeruch nicht ausreichend. Stattdessen wird der Schlechtgeruch durch die Verwendung verschiedener Duftstoffe überdeckt, was von den Verbrauchern oft als Reinigungseffekt empfunden wird, obwohl die Ursachen der Schlechtgerüche nicht wirklich beseitigt werden. Dies hat zur Folge, dass sich im Laufe der Zeit immer mehr organisches Material und damit immer mehr Schlechtgeruch ansammelt und immer mehr Duftstoffe zugesetzt werden müssen, damit die Textilien nicht immer schlechter riechen. Viele Duftstoffe haben jedoch Nebenwirkungen wie z.B. allergene Eigenschaften, die sich in Form von Hautausschlägen äußern können. Außerdem sind viele dieser Stoffe als Naturchemikalien umweltschädlich, wenn sie ins Abwasser gelangen. In den letzten Jahren werden Duftstoffe zunehmend in Form von Duftstoffmikrokapseln verwendet, obwohl bekannt ist, dass Mikrokapseln als Mikroplastik gelten und daher potenziell umweltschädlich sind. Außerdem sind Duftstoffe teuer und tragen zu den Gesamtkosten der Wasch- und Reinigungsmittel bei. Accumulated organic soiling is often difficult to remove and commercial detergents and cleaning agents do not sufficiently reduce the bad smell. Instead, the bad smell is masked by the use of various fragrances, which is often perceived by consumers as a cleaning effect, although the causes of the bad smell are not actually eliminated. As a result, more and more organic material and thus more and more bad smell accumulates over time and more and more fragrances have to be added to prevent the textiles from smelling worse and worse. However, many fragrances have side effects such as allergenic properties that can manifest themselves in the form of skin rashes. In addition, many of these substances are harmful to the environment as they are natural chemicals if they enter wastewater. In recent years, fragrances have been increasingly used in the form of fragrance microcapsules, although it is known that microcapsules are considered microplastics and are therefore potentially harmful to the environment. In addition, fragrances are expensive and add to the overall cost of detergents and cleaning agents.
Es besteht daher Bedarf, die Reinigungsleistung von enzymhaltigen Wasch- und Reinigungsmitteln, insbesondere von vorportionierten Textilwaschmitteln, weiter zu verbessern, insbesondere im Hinblick auf die Beseitigung von (mit dem bloßen Auge sichtbaren und nicht sichtbaren) mikrobiell bedingten Ablagerungen, Biobelägen und dergleichen von Oberflächen, insbesondere Haushaltsoberflächen, Geschirr und Textilien. There is therefore a need to further improve the cleaning performance of enzyme-containing detergents and cleaning agents, in particular of pre-portioned textile detergents, in particular with regard to the removal of microbial deposits (visible and invisible to the naked eye), bio-deposits and the like from surfaces, in particular household surfaces, dishes and textiles.
Überraschenderweise wurde nun festgestellt, dass das erfindungsgemäße Dispersin mikrobiell bedingte Ablagerungen, Biobeläge und dergleichen zuverlässig von Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, entfernt. Besonders überraschend ist dabei, dass dieser Effekt nicht nur zu einer Entfernung von mikrobiell bedingten Ablagerungen, die mit dem bloßen Auge sichtbar sind, führt, sondern auch zu einer Entfernung von nicht mit dem bloßen Auge sichtbaren Ablagerungen, d.h. eine Reinigung der Textilien auf Faserebene (und nicht nur auf Garnebene), also einer fasertiefen Reinigung ("Deep Cleaning"). Der Deep Cleaning Effekt kann z.B. mittels Rasterelektronenmikroskop-Aufnahmen auch auf Faserebene dargestellt und untersucht werden. Der Begriff "Deep Cleaning", wie hierin verwendet, meint die Auflösung oder Entfernung von sichtbaren und mit dem Auge nicht sichtbaren Bestandteilen organischer Substanzen, z.B. von Talg, Zellresten, Körperschmutz (Body soil), Sebum, Biobelägen, Biofilmen (umfassend z.B. Polysaccharide, PNAG (Poly-N-Acetyl-Glucosamin)), Körperölen oder anderen in organischen Substanzen enthaltene Komponenten, und zwar nicht nur auf mit dem bloßen Auge sichtbaren Ebene, sondern auch Auflösung oder Entfernung von nicht mit dem bloßen Auge sichtbaren mikrobiell bedingten Ablagerungen, insbesondere Biobelägen und dergleichen zwischen einzelnen Fasern von Textilien. Durch den Deep Clean Effekt werden auch die Folgen von mikrobiell bedingten Ablagerungen, z.B. Schlechtgeruch, reduziert bzw. eliminiert, sowie die Hygiene der damit behandelten Textilien und/oder Oberflächen, verbessert, da die Entfernung von mikrobiell bedingten Ablagerungen, Biobelägen und dergleichen auch daran anhaftende Mikroben, z.B. Bakterien, entfernt. Surprisingly, it has now been found that the dispersin according to the invention reliably removes microbial deposits, bio-deposits and the like from textiles, dishes and other surfaces, especially household surfaces. What is particularly surprising is that this effect not only leads to the removal of microbial deposits that are visible to the naked eye, but also to the removal of deposits that are not visible to the naked eye, i.e. cleaning of the textiles at the fiber level (and not just at the yarn level), i.e. deep cleaning. The deep cleaning effect can also be shown and examined at the fiber level, for example using scanning electron microscope images. The term "deep cleaning" as used herein means the dissolution or removal of visible and invisible components of organic substances, e.g. sebum, cell residues, body soil, sebum, biodeposits, biofilms (including e.g. polysaccharides, PNAG (poly-N-acetyl-glucosamine)), body oils or other components contained in organic substances, not only at the level visible to the naked eye, but also the dissolution or removal of microbial deposits not visible to the naked eye, in particular biodeposits and the like between individual fibers of textiles. The deep clean effect also reduces or eliminates the consequences of microbial deposits, e.g. bad smells, and improves the hygiene of the associated treated textiles and/or surfaces, since the removal of microbial deposits, bio-deposits and the like also removes microbes adhering to them, e.g. bacteria.
Gegenstand der Erfindung ist daher in einem ersten Aspekt die Verwendung eines Dispersin, das ß-1 ,6-N-Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135,The invention therefore relates, in a first aspect, to the use of a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length and, based on the numbering according to SEQ ID NO:1, at least one of the positions which correspond to the positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131, 135,
138, 139, 140, 142, 145, 147, 148, 149, 150, 151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175,138, 139, 140, 142, 145, 147, 148, 149, 150, 151, 152, 163, 164, 167, 168, 170, 171, 173, 174, 175,
177, 178, 179, 181 , 185, 186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218,177, 178, 179, 181, 185, 186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218,
221 , 222, 224, 225, 227, 230, 232, 233, 234, 235, 237, 244, 249, 251 , 252, 253, 254, 256, 260, 261 ,221, 222, 224, 225, 227, 230, 232, 233, 234, 235, 237, 244, 249, 251, 252, 253, 254, 256, 260, 261,
262, 263, 264, 265, 267, 268, 270, 271 , 272, 273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 und 323 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion aufweist, zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt zur fasertiefen Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien. 262, 263, 264, 265, 267, 268, 270, 271, 272, 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291, 296, 300, 301, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, has at least one amino acid substitution and/or deletion, for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, in particular preferred for deep cleaning of textiles and for improving the hygiene of textiles.
In einem weiteren Aspekt betrifft die Erfindung die Verwendung eines Dispersin, das ß-1 ,6-N- Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135,In a further aspect, the invention relates to the use of a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length and, based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to the positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131, 135,
138, 139, 140, 142, 145, 147, 148, 149, 150, 151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175,138, 139, 140, 142, 145, 147, 148, 149, 150, 151, 152, 163, 164, 167, 168, 170, 171, 173, 174, 175,
177, 178, 179, 181 , 185, 186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218,177, 178, 179, 181, 185, 186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218,
221 , 222, 224, 225, 227, 230, 232, 233, 234, 235, 237, 244, 249, 251 , 252, 253, 254, 256, 260, 261 , 262, 263, 264, 265, 267, 268, 270, 271 , 272, 273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 und 323 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion, die aus der aus D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52*, Y52M, G54L, G54M, G54N, S56T, S56W, S57W, E58N, N59A, N59C, N59D, N59E, N59F, N59M, N59R, N59V, N59W, T60V, N62C, N62D, N62H, N62Q, N62W, T63C, T63D, T63L, T63N, T63R, T63V, K67A, K67L, N68L, N68Q, L71 H, L71 N, L71 R, L71V, L71W, S72*, S72C, S72D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77A, D79V, K80*, K80E, K80H, K80L, K80N, K80Q, K80V, K80W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S, K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, V106N, V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K107T, K107V, K107W, N110M, N110R, N110V, D111A, D111 E, D111 M, D111 N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, S117*, S117D, S117H, S117N, S117P, E118*, E118A, E118D, E118G, E118L, E119G, E119W, T120I, T120L, T120M, T120V, T120W, D122*, D122H, D122R, Y123W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y124R, Y124T, Y124V, Y124W, D125C, D125G, D125K, D125Q, D125R, N126V, R127D, R127H, R127K, R127L, R127M, R127Q, R127W, V128C, V128L, V128T, D131V, Q135*, Q135A, Q135D, Q135E, Q135K, Q135M, Q135Y, D138K, D138L, D138M, D138Q, D138R, D138S, D138V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P147A, P147C, P147D, P147F, P147G, P147L, P147M, P147R, P147S, P147T, P147V, K148A, K148D, K148L, K148V, F149L, F149M, F149N, E150D, E150H, E150K, E150L, E150M, E150N, E150R, E150V, E150W, E150Y, G151A, G151C, G151 D, G151 L, G151 N, G151 P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G164H, G164S, G164V, V167D, V167E, V167L, V167P, V167Q, V167R, V167W, H168N, L170A, L170D, L170E, L170F, L170H, L170K, L170M, L170N, L170P, L170Q, L170R, L170S, L170V, L170W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, D171 M, D171 Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D174V, D174W, F175Y, N177M, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181C, S181 D, S181 F, S181G, S181 N, S181 P, S181 Q, S181T, S181V, S181W, E185M, E185R, E185V, E185W, S186D, S186E, S186H, S186I, S186K, S186L, S186M, S186N, S186Q, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K187V, K187W, Y188P, E189L, E189V, E189W, S199C, S199L, S199M, S199Y, E200D, E200F, E200K, E200L, E200M, E200N, E200R, E200W, A203C, A203D, A203E, A203G, A203L, A203M, A203P, A203R, A203S, A203T, A203V, A203W, N204L, N204M, N204V, N204W, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, D207Q, D207S, D207V, D207W, S208A, S208C, S208D, S208G, S208L, S208Q, S208T, S208V, S208W, S210T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G222D, E224A, E224P, N227A, N227Q, N227R, N227S, N227T, N227K, D230*, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N233R, N233W, W234R, G235W, G235A, G235E, G235F, G235H, G235I, G235L, G235M, G235N, G235P, G235S, G235V, S237C, S237G, S237M, S237N, S237W, S237Y, Y244C, Y244E, Y244M, L249H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S251 N, S251 R, S251W, N252P, N252C, G253D, G253W, F254I, F254L, F254M, F254Y, Q256E, Q256R, N260*, N260A, N260C, N260E, N260I, N260K, N260L, N260M, N260Q, N260R, N260V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q262W, Q262Y, M263K, M263L, M263Q, D264*, D264C, D264E, Y265F, N267S, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274R, K274A, K274H, F276A, F276C, F276K, F276N, F276G, F276L, F276M, F276P, F276S, F276V, F27Q\I\I, I278A, I278K, I278N, I278Q, 1278V, S279C, S279D, S279E, S279G, S279N, D280C, D280E, Y281*, Y281A, Y281 C, Y281 H, Y281 K, Y281 N, Y281 P, Y282E, Y282N, H283I, A284I, A284L, A284N, A284P, A284T, A284V, T287N, S288D, S288K, S288N, V290I, K291 L, K291 R, K291V, T296C, E300A, E300D, H301 C, H301 N, H301 R, T303A, T303C, T303G, T303K, T303Q, T303R, T303W, D304C, D304M, L305M, L305N, S306C, K308A, K308D, K308G, K308I, K308L, K308Q, K308S, K308T, K308V, K308Y, K309A, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R und Kombinationen davon bestehenden Gruppe ausgewählt ist, aufweist, zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt zur fasertiefen Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien. 221, 222, 224, 225, 227, 230, 232, 233, 234, 235, 237, 244, 249, 251, 252, 253, 254, 256, 260, 261, 262, 263, 264, 267, 268, 270, 271, 272, 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291, 296, 300, 301, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, at least one amino acid substitution and/or deletion selected from the group consisting of D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52 *, Y52M, G54L, G54M, G54N, S56T, S56W, S57W, E58N, N59A, N59C, N59D, N59E, N59F, N59M, N59R, N59V, N59W, T60V, N62C, N62D, N62H, N62Q, N62W, T63C, T63D, T63L, T63 N, T63R, T63V, K67A, K67L, N68L, N68Q, L71 H, L71 N, L71 R, L71V, L71W, S72*, S72C, S72D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77A, D79V, K80*, K80E, K80H, K80L, K80N, K80Q, K80V, K80W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S , K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, V106N, V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K107T, K107V, K107W, N110M, N110R, N110V, D111A, D111 E, D111 M, D111 N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, 7*, S117D, S117H , S117N, S117P, E118*, E118A, E118D, E118G, E118L, E119G, E119W, T120I, T120L, T120M, T120V, T120W, D122*, D122H, D122R, Y123W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y124R, Y124T, Y124V, Y124W, D125C, D125G, D125K, D125Q, D125R, N126V, R127D, R127H, R127K, R127L, 7M, R127Q, R127W, V128C, V128L, V128T, D131V, Q135*, Q135A, Q135D, Q135E, Q135K, Q135M, Q135Y, D138K, D138L, D138M, D138Q, D138R, D138S, D138V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P147A, P147C, P147D, P147F, P147G, P147L, P147M, P147R, P147S, P147T, P147V, K14 8A, K148D, K148L, K148V, F149L , F149M, F149N, E150D, E150H, E150K, E150L, E150M, E150N, E150R, E150V, E150W, E150Y, G151A, G151C, G151 D, G151 L, G151N, G151P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G164H, G164S, G164V, V167D, V167E, V167L, V167P, V167Q, V167R, V167W, H168N, L17 0A, L170D, L170E, L170F, L170H, L170K, L170M, L170N, L170P, L170Q, L170R, L170S, L170V, L170W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, D171 M, D171 Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D174V, D174W, F175Y, N177M, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181C, S18 1D, S181F, S181G , S181 N, S181 P, S181 Q, S181T, S181V, S181W, E185M, E185R, E185V, E185W, S186D, S186E, S186H, S186I, S186K, S186L, S186M, S186N, S186Q, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K187V, K187W, Y188P, E189L, E189V, E189W, S199C, S199L, S199M, S199Y, E200D 0F, E200K, E200L, E200M, E200N, E200R, E200W, A203C, A203D, A203E, A203G, A203L, A203M, A203P, A203R, A203S, A203T, A203V, A203W, N204L, N204M, N204V, N204W, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, D207Q, D207S, D207V, D207W, S208A, S208C, S208D, S208G, S208L, S208Q, S208T, S20 8V, S208W, S210T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G222D, E224A, E224P, N227A, N227Q, N227R, N227S, N227T, N227K, D230*, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N233R, N233W, W234R, G235W, G235A, G235E, G235F, G235H, G235I, G235L, G235M, G23 5N, G235P, G235S, G235V, S237C , S237G, S237M, S237N, S237W, S237Y, Y244C, Y244E, Y244M, L249H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S251 N, S251 R, S251W, N252P, N252C, G253D, G253W, F254I, F254L, F254M, F254Y, Q256E, Q256R, N260*, N260A, N260C, N260E, N260I, N260K, N260L, N260M, 0Q, N260R, N260V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q262W, Q262Y, M263K, M263L, M263Q, D264*, D264C, D264E, Y265F, N267S, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274R, K274A, K27 4H, F276A, F276C, F276K , F276N, F276G, F276L, F276M, F276P, F276S, F276V, F27Q\I\I, I278A, I278K, I278N, I278Q, 1278V, S279C, S279D, S279E, S279G, S279N, D280C, D280E, Y281*, Y281A, Y281 C, Y281 H, Y281 K, Y281 N, P, Y282E, Y282N, H283I, A284I, A284L, A284N, A284P, A284T, A284V, T287N, S288D, S288K, S288N, V290I, K291 L, K291 R, K291V, T296C, E300A, E300D, H301 C, H301 N, H301 R, T303A, T303C, T303G, T303K, T303Q, T303R, T303W, D304C, D304M, L305M, L305N, S306C, K308A, K308D, K308G, K308I, K30 8L, K308Q, K308S, K308T , K308V, K308Y, K309A, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R and combinations thereof, for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, especially household surfaces, particularly preferred for deep fiber cleaning of textiles, as well as for improving the hygiene of textiles.
In bevorzugten Ausführungsformen ist das erfindungsgemäße Dispersin, wie hierin beschrieben, in einem Wasch- und/oder Reinigungsmittel enthalten, wobei das Mittel im Wesentlichen frei von borhaltigen Verbindungen, vorzugsweise frei von borhaltigen Verbindungen, ist; und/oder das Mittel in 1 Gew.-%iger Lösung in entionisiertem Wasser bei 20°C einen pH-Wert in einem Bereich von etwa 6 bis etwa 11 , insbesondere von etwa 6,5 bis etwa 10,5, weiter bevorzugt von etwa 7 bis etwa 10, besonders bevorzugt von etwa 8 bis etwa 9 aufweist. In preferred embodiments, the dispersin according to the invention, as described herein, is contained in a washing and/or cleaning agent, wherein the agent is substantially free of boron-containing compounds, preferably free of boron-containing compounds; and/or the agent in 1 wt. % solution in deionized water at 20°C has a pH in a range from about 6 to about 11, in particular from about 6.5 to about 10.5, more preferably from about 7 to about 10, particularly preferably from about 8 to about 9.
In weiter bevorzugten Ausführungsformen wird das Dispersin oder das dispersinhaltige Wasch- und/oder Reinigungsmittel in einem Temperaturbereich von etwa 10°C bis etwa 60°C, bevorzugt etwa 15°C bis etwa 40°C, besonders bevorzugt etwa 20°C bis etwa 30°C verwendet. In further preferred embodiments, the dispersin or the dispersin-containing washing and/or cleaning agent is used in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
Weitere Gegenstände der Erfindung betreffen ein Mittel zur fasertiefen Reinigung von Textilien und/oder zur Verbesserung der Hygiene von Textilien, dadurch gekennzeichnet dass das Mittel ein erfindungsgemäßes Dispersin enthält, und ein Verfahren zur fasertiefen Reinigung von Textilien und/oder zur Verbesserung der Hygiene von Textilien, dadurch gekennzeichnet, dass in mindestens einem Verfahrensschritt ein erfindungsgemäßes Dispersin oder ein erfindungsgemäßes Mittel angewendet wird, vorzugsweise in einem Temperaturbereich von etwa 10°C bis etwa 60°C, bevorzugt etwa 15°C bis etwa 40°C, besonders bevorzugt etwa 20°C bis etwa 30°C. Further objects of the invention relate to an agent for deep fiber cleaning of textiles and/or for improving the hygiene of textiles, characterized in that the agent contains a dispersin according to the invention, and to a method for deep fiber cleaning of textiles and/or for improving the hygiene of textiles, characterized in that in at least one method step a dispersin according to the invention or an agent according to the invention is used, preferably in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
Die Erfindung betrifft insbesondere die Entfernung von nicht mit dem bloßen Auge sichtbaren mikrobiell bedingten Ablagerungen. Ferner betrifft die Erfindung insbesondere die fasertiefe Reinigung von Textilien. Die fasertiefe Reinigung ist mittels Rasterelektronenmikroskop-Aufnahmen darstellbar. The invention relates in particular to the removal of microbial deposits that are not visible to the naked eye. Furthermore, the invention relates in particular to the fiber-deep cleaning of textiles. The fiber-deep cleaning can be shown using scanning electron microscope images.
Diese und weitere Aspekte, Merkmale und Vorteile der Erfindung werden für den Fachmann aus dem Studium der folgenden detaillierten Beschreibung und Ansprüche ersichtlich. Dabei kann jedes Merkmal aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Ferner ist es selbstverständlich, dass die hierin enthaltenen Beispiele die Erfindung beschreiben und veranschaulichen sollen, diese aber nicht einschränken und insbesondere die Erfindung nicht auf diese Beispiele beschränkt ist. These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. It should be understood that any feature of one aspect of the invention may be employed in any other aspect of the invention. It is further understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples.
Alle Prozentangaben sind, sofern nicht anders angegeben, Gewichtsprozent (Gew.-%). Numerische Bereiche, die in dem Format "von x bis y" angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden. All percentages are by weight (wt%) unless otherwise stated. Numerical ranges specified in the format "from x to y" include the values specified. If several preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the different endpoints are also included.
"Mindestens eine", wie hierin verwendet, bedeutet eine oder mehrere, d.h. 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14 oder mehr. "At least one" as used herein means one or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or more.
Der Begriff "Wasch- und Reinigungsmittel" bzw. "Wasch- oder Reinigungsmittel", wie hierin verwendet, ist gleichbedeutend mit dem Begriff "Mittel" und bezeichnet eine Zusammensetzung zum Reinigen von Textilien und/oder harten Oberflächen, insbesondere Geschirr, wie in der Beschreibung erläutert. The term "detergent and cleaning agent" or "detergent or cleaning agent" as used herein is synonymous with the term "agent" and refers to a composition for cleaning textiles and/or hard surfaces, in particular dishes, as explained in the description.
"Etwa", "ca." oder "ungefähr", wie hierin in Bezug auf einen Zahlenwert verwendet, beziehen sich auf den entsprechenden Zahlenwert ±10%, vorzugsweise ±5%. "About," "approximately," or "approximately," as used herein in reference to a numerical value, refers to the corresponding numerical value ±10%, preferably ±5%.
"Flüssig", wie hierin verwendet, schließt Flüssigkeiten und Gele sowie auch pastöse Zusammensetzungen ein. Es ist bevorzugt, dass die flüssigen Zusammensetzungen bei Raumtemperatur fließfähig und gießbar sind, es ist aber auch möglich, dass sie eine Fließgrenze aufweisen. "Liquid" as used herein includes liquids and gels as well as pasty compositions. It is preferred that the liquid compositions be flowable and pourable at room temperature, but it is also possible that they have a yield point.
Ein Stoff, z.B. eine Zusammensetzung oder ein Mittel ist gemäß Definition der Erfindung festförmig, wenn sie bei 25°C und 1013 mbar im festen Aggregatzustand vorliegt. A substance, e.g. a composition or an agent, is solid according to the definition of the invention if it is in the solid state at 25°C and 1013 mbar.
Ein Stoff, z.B. eine Zusammensetzung oder ein Mittel ist gemäß Definition der Erfindung flüssig, wenn sie bei 25°C und 1013 mbar im flüssigen Aggregatzustand vorliegt. Dabei umfasst flüssig auch gelförmig. A substance, e.g. a composition or an agent, is liquid according to the definition of the invention if it is in the liquid state at 25°C and 1013 mbar. Liquid also includes gel form.
"Variante", wie hierin verwendet, bezieht sich auf natürliche oder artifiziell erzeugte Variationen eines nativen Enzyms, das eine gegenüber der Referenzform abgewandelte Aminosäuresequenz aufweist. "Variant", as used herein, refers to natural or artificially generated variations of a native enzyme that have a modified amino acid sequence compared to the reference form.
Der Begriff "Textil", wie hierin verwendet, bezeichnet jedes textile Material, einschließlich Garne, Garnvorprodukte, Fasern, Vliesstoffe, natürliche Materialien, synthetische Materialien und alle anderen textilen Materialien, Gewebe aus diesen Materialien und aus Geweben hergestellte Produkte (z.B. Kleidungsstücke und andere Artikel). Das Textil oder Gewebe kann in Form von Gewirken, Geweben, Denims, Vliesstoffen, Filzen, Garnen und Frottee vorliegen. Das Textil kann auf Cellulose basieren, wie z.B. natürliche Cellulosefasern wie Baumwolle, Flachs/Leinen, Jute, Ramie, Sisal oder Kokosfasern, oder künstlich hergestellte Zellulosefasern (z.B. aus Zellstoff) wie Viskose/Rayon, Celluloseacetatfasern (Tricell), Lyocell oder Mischungen davon. Das Textil oder Gewebe kann auch aus Nicht-Cellulosefasern bestehen, z.B. aus natürlichen Polyamiden wie Wolle, Kamel, Kaschmir, Mohair, Kaninchen und Seide oder aus synthetischen Polymeren wie Nylon, Aramid, Polyester, Acryl, Polypropylen und Spandex/Elasthan oder Mischungen daraus sowie aus Mischungen von Cellulosefasern und Nicht-Cellulosefasern. Beispiele für Mischungen sind Mischungen aus Baumwolle und/oder Rayon/Viskose mit einem oder mehreren Begleitmaterialien wie Wolle, synthetischen Fasern (z.B. Polyamidfasern, Acrylfasern, Polyesterfasern, Polyvinylchloridfasern, Polyurethanfasern, Polyharnstofffasern, Aramidfasern) und/oder cellulosehaltigen Fasern (z. B. Rayon/Viskose, Ramie, Flachs/Leinen, Jute, Celluloseacetatfasern, Lyocell). Bei dem Gewebe kann es sich um herkömmliche waschbare Wäsche handeln, z.B. um verschmutzte Haushaltswäsche. Wenn der Begriff "Gewebe" oder "Kleidungsstück" verwendet wird, soll er auch den weiter gefassten Begriff "Textilien" umfassen. The term "textile" as used herein means any textile material, including yarns, yarn precursors, fibers, nonwovens, natural materials, synthetic materials and all other textile materials, fabrics made from these materials and products made from fabrics (e.g. garments and other articles). The textile or fabric may be in the form of knits, wovens, denims, nonwovens, felts, yarns and terry cloth. The textile may be cellulose-based, such as natural cellulose fibers such as cotton, flax/linen, jute, ramie, sisal or coconut fibers, or man-made cellulose fibers (e.g. from wood pulp) such as viscose/rayon, cellulose acetate fibers (tricell), lyocell or mixtures thereof. The textile or fabric may also consist of non-cellulosic fibres, e.g. natural polyamides such as wool, camel, cashmere, mohair, rabbit and silk or synthetic polymers such as nylon, aramid, polyester, acrylic, polypropylene and spandex/elastane or mixtures thereof, as well as mixtures of cellulosic fibres and non-cellulosic fibres. Examples of mixtures are mixtures of cotton and/or rayon/viscose with one or more accompanying materials such as wool, synthetic fibres (e.g. polyamide fibres, acrylic fibres, polyester fibres, polyvinyl chloride fibres, polyurethane fibres, polyurea fibres, aramid fibres) and/or cellulosic fibres (e.g. rayon/viscose, ramie, flax/linen, jute, cellulose acetate fibres, lyocell). The fabric may be conventional washable laundry, e.g. soiled household linen. When the term "fabric" or "garment" is used, it is intended to include the broader term "textiles".
Die vorliegende Erfindung basiert auf der überraschenden Erkenntnis der Erfinder, dass das erfindungsgemäße Dispersin mikrobiell bedingte Ablagerungen, Biobeläge und dergleichen zuverlässig von Oberflächen, insbesondere Haushaltsoberflächen, sowie Geschirr und Textilien entfernt. Besonders überraschend ist dabei, dass dieser Effekt nicht nur zu einer Entfernung von mikrobiell bedingten Ablagerungen, die mit dem bloßen Auge sichtbar sind, führt, sondern auch zu einer Entfernung von nicht mit dem bloßen Auge sichtbaren Ablagerungen, d.h. eine Reinigung der Textilien auf Faserebene (und nicht nur auf Garnebene), also einer fasertiefen Reinigung ("Deep Cleaning"). The present invention is based on the surprising discovery of the inventors that the dispersin according to the invention reliably removes microbial deposits, bio-deposits and the like from surfaces, in particular household surfaces, as well as dishes and textiles. What is particularly surprising is that this effect not only leads to the removal of microbial deposits that are visible to the naked eye, but also to the removal of deposits that are not visible to the naked eye, i.e. cleaning of the textiles at the fiber level (and not just at the yarn level), i.e. deep cleaning of the fibers.
Erfindungsgemäß wird ein Dispersin, das ß-1 ,6-N-Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135, 138, 139, 140, 142, 145, 147, 148, 149, 150,According to the invention, a dispersin which has ß-1,6-N-acetylglucosaminidase activity comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length and, based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72, 7 4, 77, 79, 80, 81, 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111, 113, 114, 116, 117, 118, 119, 120, 122, 123, 125, 126, 127, 128, 131, 135, 138, 139, 140, 142, 145, 147, 148, 149, 150,
151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175, 177, 178, 179, 181 , 185, 186, 187, 188, 189,151, 152, 163, 164, 167, 168, 170, 171, 173, 174, 175, 177, 178, 179, 181, 185, 186, 187, 188, 189,
199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221 , 222, 224, 225, 227, 230, 232, 233, 234,199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221, 222, 224, 225, 227, 230, 232, 233, 234,
235, 237, 244, 249, 251 , 252, 253, 254, 256, 260, 261 , 262, 263, 264, 265, 267, 268, 270, 271 , 272,235, 237, 244, 249, 251, 252, 253, 254, 256, 260, 261, 262, 263, 264, 265, 267, 268, 270, 271, 272,
273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 und 323 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion aufweist, zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt zur fasertiefen Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien, verwendet. 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291, 296, 300, 301, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, has at least one amino acid substitution and/or deletion, for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, and for improving the hygiene of textiles.
Dispersine gehören zur Gruppe der Hexosaminidasen oder ß-N-Acetylglucosamininidasen (EC 3.2.1 .52). Diese sind Polypeptide, welche die Hydrolyse von N-Acetyl-D-hexosamin- oder N- Acetylglucosamin-Polymeren katalysieren. Dispersin B ist eine ß-Hexosaminidase, die spezifisch ß- 1 ,6-glykosidische Bindungen von Acetylglucosamin-Polymeren, die z.B. in Biofilm, EPS (extrazelluläre Polymerstrukturen), Zelltrümmer, Biobeläge und andere sog. Biosoils (d.h. Anschmutzungen biologischen Ursprungs) vorkommen, hydrolysiert. Erfindungsgemäß wird ein Dispersin verwendet, das ß-1 ,6-N-Acetylglucosaminidase-Aktivität aufweist und eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist, und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113,Dispersins belong to the group of hexosaminidases or ß-N-acetylglucosamine minidases (EC 3.2.1.52). These are polypeptides that catalyze the hydrolysis of N-acetyl-D-hexosamine or N-acetylglucosamine polymers. Dispersin B is a ß-hexosaminidase that specifically hydrolyzes ß-1,6-glycosidic bonds of acetylglucosamine polymers that occur, for example, in biofilm, EPS (extracellular polymer structures), cell debris, bio-coatings and other so-called biosoils (ie soiling of biological origin). According to the invention, a dispersin is used which has ß-1,6-N-acetylglucosaminidase activity and comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72 , 74, 77, 79, 80, 81, 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111, 113,
114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135, 138, 139, 140, 142, 145,114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131, 135, 138, 139, 140, 142, 145,
147, 148, 149, 150, 151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175, 177, 178, 179, 181 , 185,147, 148, 149, 150, 151, 152, 163, 164, 167, 168, 170, 171, 173, 174, 175, 177, 178, 179, 181, 185,
186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221 , 222, 224, 225, 227,186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221, 222, 224, 225, 227,
230, 232, 233, 234, 235, 237, 244, 249, 251 , 252, 253, 254, 256, 260, 261 , 262, 263, 264, 265, 267, 268, 270, 271 , 272, 273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 und 323 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion aufweist. 230, 232, 233, 234, 235, 237, 244, 249, 251, 252, 253, 254, 256, 260, 261, 262, 263, 264, 265, 267, 268, 270, 271, 272, 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291, 296, 300, 301, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, has at least one amino acid substitution and/or deletion.
In bevorzugten Ausführungsformen wird ein Dispersin verwendet, das ß-1 ,6-N- Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist, und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135, 138, 139, 140, 142, 145, 147, 148, 149, 150, 151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175, 177, 178, 179, 181 , 185, 186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221 , 222, 224, 225, 227, 230, 232, 233, 234, 235, 237, 244, 249, 251 , 252, 253, 254, 256, 260, 261 , 262, 263, 264, 265, 267, 268, 270, 271 , 272, 273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 und 323 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion, die aus der aus D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52*, Y52M, G54L, G54M, G54N, S56T, S56W, S57W, E58N, N59A, N59C, N59D, N59E, N59F, N59M, N59R, N59V, N59W, T60V, N62C, N62D, N62H, N62Q, N62W, T63C, T63D, T63L, T63N, T63R, T63V, K67A, K67L, N68L, N68Q, L71 H, L71 N, L71 R, L71V, L71W, S72*, S72C, S72D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77A, D79V, K80*, K80E, K80H, K80L, K80N, K80Q, K80V, K80W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S, K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, V106N, V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K107T, K107V, K107W, N110M, N110R, N110V, D111A, D111 E, D111 M, D111 N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, S117*, S117D, S117H, S117N, S117P, E118*, E118A, E118D, E118G, E118L, E119G, E119W, T120I, T120L, T120M, T120V, T120W, D122*, D122H, D122R, Y123W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y124R, Y124T, Y124V, Y124W, D125C, D125G, D125K, D125Q, D125R, N126V, R127D, R127H, R127K, R127L, R127M, R127Q, R127W, V128C, V128L, V128T, D131V, Q135*, Q135A, Q135D, Q135E, Q135K, Q135M, Q135Y, D138K, D138L, D138M, D138Q, D138R, D138S, D138V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P147A, P147C, P147D, P147F, P147G, P147L, P147M, P147R, P147S, P147T, P147V, K148A, K148D, K148L, K148V, F149L, F149M, F149N, E150D, E150H, E150K, E150L, E150M, E150N, E150R, E150V, E150W, E150Y, G151A, G151C, G151 D, G151 L, G151 N, G151 P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G164H, G164S, G164V, V167D, V167E, V167L, V167P, V167Q, V167R, V167W, H168N, L170A, L170D, L170E, L170F, L170H, L170K, L170M, L170N, L170P, L170Q, L170R, L170S, L170V, L170W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, D171 M, D171 Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D174V, D174W, F175Y, N177M, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181C, S181 D, S181 F, S181G, S181 N, S181 P, S181 Q, S181T, S181V, S181W, E185M, E185R, E185V, E185W, S186D, S186E, S186H, S186I, S186K, S186L, S186M, S186N, S186Q, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K187V, K187W, Y188P, E189L, E189V, E189W, S199C, S199L, S199M, S199Y, E200D, E200F, E200K, E200L, E200M, E200N, E200R, E200W, A203C, A203D, A203E, A203G, A203L, A203M, A203P, A203R, A203S, A203T, A203V, A203W, N204L, N204M, N204V, N204W, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, D207Q, D207S, D207V, D207W, S208A, S208C, S208D, S208G, S208L, S208Q, S208T, S208V, S208W, S210T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G222D, E224A, E224P, N227A, N227Q, N227R, N227S, N227T, N227K, D230*, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N233R, N233W, W234R, G235W, G235A, G235E, G235F, G235H, G235I, G235L, G235M, G235N, G235P, G235S, G235V, S237C, S237G, S237M, S237N, S237W, S237Y, Y244C, Y244E, Y244M, L249H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S251 N, S251 R, S251W, N252P, N252C, G253D, G253W, F254I, F254L, F254M, F254Y, Q256E, Q256R, N260*, N260A, N260C, N260E, N260I, N260K, N260L, N260M, N260Q, N260R, N260V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q262W, Q262Y, M263K, M263L, M263Q, D264*, D264C, D264E, Y265F, N267S, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274R, K274A, K274H, F276A, F276C, F276K, F276N, F276G, F276L, F276M, F276P, F276S, F276V, F276W, I278A, I278K, I278N, I278Q, I278V, S279C, S279D, S279E, S279G, S279N, D280C, D280E, Y281*, Y281A, Y281 C, Y281 H, Y281 K, Y281 N, Y281 P, Y282E, Y282N, H283I, A284I, A284L, A284N, A284P, A284T, A284V, T287N, S288D, S288K, S288N, V290I, K291 L, K291 R, K291V, T296C, E300A, E300D, H301 C, H301 N, H301 R, T303A, T303C, T303G, T303K, T303Q, T303R, T303W, D304C, D304M, L305M, L305N, S306C, K308A, K308D, K308G, K308I, K308L, K308Q, K308S, K308T, K308V, K308Y, K309A, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R und Kombinationen davon bestehenden Gruppe ausgewählt ist, aufweist. In preferred embodiments, a dispersin is used which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72 , 74, 77, 79, 80, 81, 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111, 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135, 138, 139, 140, 142, 145, 147, 148, 149, 150, 151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175, 177, 178, 179, 181 , 185, 186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221 , 222, 224, 225, 227, 230, 232, 233, 234, 235, 237, 244, 249, 251, 252, 253, 254, 256, 260, 261, 262, 263, 264, 265, 267, 268, 270, 271, 272, 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291, 296, 300, 301, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, at least one amino acid substitution and/or deletion selected from the group consisting of D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52*, Y52M, G54L, G54 M, G54N, S56T, S56W, S57W, E58N, N59A, N59C, N59D, N59E, N59F, N59M, N59R, N59V, N59W, T60V, N62C, N62D, N62H, N62Q, N62W, T63C, T63D, T63L, T63N, T63R, T63V, K67A, K67L, N68L, N68Q, L71 H, L71 N, L71 R, L71V, L71W, S72*, S72C, S72D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77 A, D79V, K80*, K80E, K80H, K80L, K80N, K80Q, K80V, K80W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S, K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, V106N, V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K10 7T, K107V, K107W, N110M, N110R, N110V, D111A, D111 E, D111 M, D111 N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, S117*, S117D, S117H, S117N, S117P, E118*, E118A, E118D, E118G, E118L, E119G, E119W, T120I, T120L, T120M, T120V, T120W, D122*, D122H, D122R, Y12 3W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y124R, Y124T, Y124V, Y124W, D125C, D125G, D125K, D125Q, D125R, N126V, R127D, R127H, R127L, R127M, R127Q, R127W, V128C, V128L, V128T, D131V, Q135*, Q135A, Q135D, Q135E, Q135K, Q135M, Q135Y, D138K, D138L, D138M, D138Q, D138R, D138S, 8V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P147A, P147C, P147D, P147F, P147G, P147L, P147M, P147R, P147S, P147V, K148A, K148D, K148L, K148V, F149L, F149M, F149N, E150D, E150H, E150K, E150L, E150M, E150N, E150R, E150V, E150W, E150Y, G151A, G151C, G151 D, G15 1L, G151N, G151P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G164H, G164S, G164V, V167D, V167E, V167L, V167P, V167Q, V167R, V167W, L170A, L170D, L170E, L170F, L170H, L170K, L170M, L170N, L170P, L170Q, L170R, L170S, L170V, L170W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, 1M, D171 Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D174V, D174W, F175Y, N177M, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181 D, S181 F, S181G, S181 N, S181 P, S181 Q, S181T, S181V, S181W, E185M, E185R, E185V, E185W, S186D, S186E, S186H, S186I, S186K, S186L, S186M, S18 6N, S186Q, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K187V, K187W, Y188P, E189L, E189V, E189W, S199C, S199L, S199M, S199Y, E200F, E200K, E200L, E200M, E200N, E200R, E200W, A203C, A203D, A203E, A203G, A203L, A203M, A203P, A203R, A203S, A203T, A203V, A203W, N204L, N20 4M, N204V, N204W, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, D207Q, D207S, D207V, D207W, S208A, S208C, S208D, S208G, S208L, S208T, S208V, S208W, S210T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G222D, E224A, E224P, N227A, N227Q, N227R, N227S, N22 7T, N227K, D230*, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N233R, N233W, W234R, G235W, G235A, G235E, G235F, G235H, G235I, G235M, G235N, G235P, G235S, G235V, S237C, S237G, S237M, S237N, S237W, S237Y, Y244C, Y244E, Y244M, L249H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S25 1N. N260Q, N260R, N260V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q262W, Q262Y, M263K, M263L, M263Q, D264*, D264C, D26 4E, Y265F, N267S, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274A, K274H, F276A, F276C, F276K, F276N, F276G, F276L, F276M, F276P, F276S, F276V, F276W, I278A, I278K, I278N, I278Q, I278V, S279C, S279D, S279E, S27 9G, S279N, D280C, D280E, Y281*, Y281A, Y281 C, Y281 H, Y281 K, Y281 N, Y281 P, Y282E, Y282N, H283I, A284I, A284L, A284N, A284P, A284T, A284V, S288D, S288K, S288N, V290I, K291 L, K291 R, K291V, T296C, E300A, E300D, H301 C, H301 N, H301 R, T303A, T303C, T303G, T303K, T303Q, T303R, T303W, D30 4C, D304M, L305M, L305N, S306C, K308A, K308D, K308G, K308I, K308L, K308Q, K308S, K308T, K308V, K308Y, K309A, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R and combinations thereof.
In weiter bevorzugten Ausführungsformen wird ein Dispersin verwendet, das ß-1 ,6-N- Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist, und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 22, 23, 25, 30, 49, 56, 59, 62, 63, 68, 72, 74, 77, 82, 90, 99, 100, 114, 123, 124, 125, 135, 138, 170, 171 , 173, 174, 175, 178, 179, 181 , 185, 186, 187, 188, 189, 199, 203, 204, 205, 207, 210, 215, 218, 227, 232, 235, 237, 244, 252, 256, 260, 262, 263, 264, 265, 267, 270, 272, 273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 288, 290, 291 , 296, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319 und 321 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion, die aus der aus D2V, Q3F, Q3I, S12A, H15Y, T17W, T17E, V18L, K22M, S23I, S23C, S23T, S23L, S23V, S23E, V25R, Y30L, A49W, A49Y, S56T, N59D, N59C, N59E, N59R, N59F, N59W, N59V, N62C, N62D, T63C, N68Q, S72D, S72E, I74L, S77A, I82V, L90F, E99Q, L100S, T114S, T114C, Y123W, Y124I , Y124M, Y124R, Y124V, Y124Q, Y124T, Y124K, D125R, D125C, D125G, D125K, D125Q, Q135M, D138R, D138K, D138Q, L170D, L170K, L170S, L170H, D171 E, D171 K, D171Y, D171 M, D171 Q, D171 L, I173C, D174W, D174H, D174M, D174N, F175Y, Q178K, I179T, S181T, S181 F, S181Q, S181G, S181 N, S181 C, E185R, E185M, E185V, S186K, S186M, S186R, S186H, K187G, Y188P, E189V, S199C, S199L, A203G, A203E, A203V, N204L, N204Y, N204V, L205I, D207N, D207S, D207C, D207G, S210T, Q215R, T218Q, N227T, N227K, E232D, G235W, S237W, Y244M, Y244C, N252P, N252C, Q256E, N260Q, Q262H, M263Q, D264E, Y265F, N267T, N267S, Y270F, H272M, H272P, H272I, H272V, N273W, K274H, F276A, F276N, F276K, F276C, I278V, S279N, S279D, S279G, D280E, D280C, Y281 P, Y282N, H283I, A284T, A284L, A284I, S288K, V290I, K291 R, T296C, T303Q, D304M, D304C, L305M, L305N, S306C, K308D, K308A, K308V, K308Q, K308S, K308Y, K308G, K308L, K308T, K308I, K309C, K309L, K309D, K309Q, K309N, K309T, K309A, K309S, K309M, K309H, K312A, K312Q, K312S, K312W, K312L, K312N, E314L, E314V, E314I, L315I, R319A, N323R und Kombinationen davon bestehenden Gruppe ausgewählt ist, aufweist. In further preferred embodiments, a dispersin is used which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 22, 23, 25, 30, 49, 56, 59, 62, 63, 68, 72, 74, 77, 82, 90, 99, 100, 114, 123, 124, 125, 135, 138, 171, 173, 174, 175, 178, 179, 181, 185, 186, 187, 188, 189, 199, 203, 204, 205, 207, 210, 215, 218, 227, 232, 235, 237, 244, 252, 256, 260, 262, 263, 264, 265, 267, 270, 272, 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 288, 290, 291, 296, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319 and 321, at least one amino acid substitution and/or deletion selected from the group consisting of D2V, Q3F, Q3I, S12A, H15Y, T17W, T17E, V18L, K22M, S23I, S23C, S23T, S23L, S23V, S23E, V25R, Y30L, A49W, A49Y, S56T, N59D, N59C, N59E, N59R, N59F, N59W, N59V, N62C, N62D, T63C, N68Q, S72D, S72E, I74 L, S77A, I82V, L90F, E99Q, L100S, T114S, T114C, Y123W, Y124I, Y124M, Y124R, Y124V, Y124Q, Y124T, Y124K, D125R, D125C, D125G, D125K, D125Q, Q135M, D138R, D138K, D138Q, L170D, L170K, L170S, L170H, D171 E, D171 K, D171Y, D171 M, D171 Q, D171 L, I173C, D174W, D174H, D174M, D174N, F175Y, Q17 8K, I179T, S181T, S181 F, S181Q, S181G, S181 N, S181 C, E185R, E185M, E185V, S186K, S186M, S186R, S186H, K187G, Y188P, E189V, S199C, S199L, A203E, A203V, N204L, N204Y, N204V, L205I, D207N, D207S, D207C, D207G, S210T, Q215R, T218Q, N227T, N227K, E232D, G235W, S237W, Y244M, Y244C, N25 2P, N252C, Q256E, N260Q, Q262H, M263Q, D264E, Y265F, N267T, N267S, Y270F, H272M, H272P, H272I, H272V, N273W, K274H, F276A, F276N, F276C, I278V, S279N, S279D, S279G, D280E, D280C, Y281 P, Y282N, H283I, A284T, A284L, A284I, S288K, V290I, K291 R, T296C, T303Q, D304M, D304C, L305M, L30 5N, S306C, K308D, K308A, K308V, K308Q, K308S, K308Y, K308G, K308L, K308T, K308I, K309C, K309L, K309D, K309Q, K309N, K309T, K309A, K309S, K309H, K312A, K312Q, K312S, K312W, K312L, K312N, E314L, E314V, E314I, L315I, R319A, N323R and combinations thereof.
In weiter bevorzugten Ausführungsformen wird ein Dispersin verwendet, das ß-1 ,6-N- Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist, und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 3, 15, 17, 49, 59, 140, 163, 186, 207, 215, 218, 225, 227, 232, 235, 237, 252, 260, 267, 272, 279, 281 , 288, 308, 309 und 312 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion, die aus der aus Q3F, Q3I, H15Y, T17W, A49W, N59E, V140I, S163P, S186R, D207N, Q215K, T218Q, S225G, N227T, E232D, G235W, S237W, N252P, N260Q, N267T, H272V, H272P, S279D, Y281 P, S288P, K308Q, K309E, K312Q und Kombinationen davon bestehenden Gruppe ausgewählt ist, aufweist. In further preferred embodiments, a dispersin is used which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 3, 15, 17, 49, 59, 140, 163, 186, 207, 215, 218, 225, 227, 232, 235, 237, 252, 260, 267, 272, 279, 281 , 288, 308, 309 and 312, at least one Amino acid substitution and/or deletion selected from the group consisting of Q3F, Q3I, H15Y, T17W, A49W, N59E, V140I, S163P, S186R, D207N, Q215K, T218Q, S225G, N227T, E232D, G235W, S237W, N252P, N260Q, N267T, H272V, H272P, S279D, Y281 P, S288P, K308Q, K309E, K312Q, and combinations thereof.
In besonders bevorzugten Ausführungsformen wird ein Dispersin verwendet, das ß-1 ,6-N- Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist, und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 3, 15, 49, 59, 163, 186, 225, 227, 232, 235, 252, 260, 272, 279, 281 , 308, 309 und 312 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion, die aus der aus Q3I, H15Y, A49W, N59E, S163P, S186R, S225G, N227T, E232D, G235W, N252P, N260Q, H272V, S279D, Y281 P, K308Q, K309E, K312Q und Kombinationen davon bestehenden Gruppe ausgewählt ist, aufweist. In particularly preferred embodiments, a dispersin is used which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70%, and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 3, 15, 49, 59, 163, 186, 225, 227, 232, 235, 252, 260, 272, 279, 281, 308, 309 and 312, having at least one amino acid substitution and/or deletion selected from the group consisting of Q3I, H15Y, A49W, N59E, S163P, S186R, S225G, N227T, E232D, G235W, N252P, N260Q, H272V, S279D, Y281 P, K308Q, K309E, K312Q and combinations thereof.
In bevorzugten Ausführungsformen wird ein Dispersin verwendet, das ß-1 ,6-N- Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist, mindestens eine und zunehmend bevorzugt zwei, drei vier, fünf, sechs, sieben, acht oder neun Aminosäuresubstitutionen aufweist, wobei das Dispersin eine Aminosäuresubstitutionskombination aufweist, die aus der aus Q3I-A49W, Q3I-N59E, Q3I-S163P, Q3I-S186R, Q3I-Q215K, Q3I-S225G, Q3I-N227T, Q3I-N252P, Q3I-N267T, Q3I-F276A, Q3I-Y281 P, Q3I-K308Q, Q3I-K308E, Q3I-K309E, Q3I-K312Q, Q3I-K312E, Q3I-H15Y, Q3I-E232D, Q3I-G235W, Q3I-N260Q, Q3I-H272V, Q3I-S279D, Q3I-H15Y-A49W, Q3I-H15Y-N59E, Q3I-H15Y-S163P, Q3I- H15Y-S186R, Q3I-H15Y-S225G, Q3I-H15Y-N227T, Q3I-H15Y-E232D, Q3I-H15Y-G235W, Q3I-H15Y- N252P, Q3I-H15Y-N260Q, Q3I-H15Y-H272V, Q3I-H15Y-S279D, Q3I-H15Y-Y281 P, Q3I-H15Y- K308Q, Q3I-H15Y-K309E, Q3I-H15Y-K312Q, Q3I-A49W-N59E, Q3I-A49W-S163P, Q3I-A49W- S186R, Q3I-A49W-S225G, Q3I-A49W-N227T, Q3I-A49W-E232D, Q3I-A49W-G235W, Q3I-A49W- N252P, Q3I-A49W-N260Q, Q3I-A49W-H272V, Q3I-A49W-S279D, Q3I-A49W-Y281 P, Q3I-A49W- K308Q, Q3I-A49W-K309E, Q3I-A49W-K312Q, Q3I-N59E-S163P, Q3I-N59E-S186R, Q3I-N59E- S225G, Q3I-N59E-N227T, Q3I-N59E-E232D, Q3I-N59E-G235W, Q3I-N59E-N252P, Q3I-N59E- N260Q, Q3I-N59E-H272V, Q3I-N59E-S279D, Q3I-N59E-Y281 P, Q3I-N59E-K308Q, Q3I-N59E- K309E, Q3I-N59E-K312Q, Q3I-S163P-S186R, Q3I-S163P-S225G, Q3I-S163P-N227T, Q3I-S163P- E232D, Q3I-S163P-G235W, Q3I-S163P-N252P, Q3I-S163P-N260Q, Q3I-S163P-H272V, Q3I-S163P- S279D, Q3I-S163P-Y281 P, Q3I-S163P-K308Q, Q3I-S163P-K309E, Q3I-S163P-K312Q, Q3I-S186R- S225G, Q3I-S186R-N227T, Q3I-S186R-E232D, Q3I-S186R-G235W, Q3I-S186R-N252P, Q3I-S186R- N260Q, Q3I-S186R-H272V, Q3I-S186R-S279D, Q3I-S186R-Y281 P, Q3I-S186R-K308Q, Q3I-S186R- K309E, Q3I-S186R-K312Q, Q3I-S225G-N227T, Q3I-S225G-E232D, Q3I-S225G-G235W, Q3I-S225G- N252P, Q3I-S225G-N260Q, Q3I-S225G-H272V, Q3I-S225G-S279D, Q3I-S225G-Y281 P, Q3I-S225G- K308Q, Q3I-S225G-K309E, Q3I-S225G-K312Q, Q3I-N227T-E232D, Q3I-N227T-G235W, Q3I-N227T- N252P, Q3I-N227T-N260Q, Q3I-N227T-H272V, Q3I-N227T-S279D, Q3I-N227T-Y281 P, Q3I-N227T- K308Q, Q3I-N227T-K309E, Q3I-N227T-K312Q, Q3I-E232D-G235W, Q3I-E232D-N252P, Q3I-E232D- N260Q, Q3I-E232D-H272V, Q3I-E232D-S279D, Q3I-E232D-Y281 P, Q3I-E232D-K308Q, Q3I-E232D- K309E, Q3I-E232D-K312Q, Q3I-G235W-N252P, Q3I-G235W-N260Q, Q3I-G235W-H272V, Q3I- G235W-S279D, Q3I-G235W-Y281 P, Q3I-G235W-K308Q, Q3I-G235W-K309E, Q3I-G235W-K312Q, Q3I-N252P-N260Q, Q3I-N252P-H272V, Q3I-N252P-S279D, Q3I-N252P-Y281 P, Q3I-N252P-K308Q, Q3I-N252P-K309E, Q3I-N252P-K312Q, Q3I-N260Q-H272V, Q3I-N260Q-S279D, Q3I-N260Q-Y281 P, Q3I-N260Q-K308Q, Q3I-N260Q-K309E, Q3I-N260Q-K312Q, Q3I-H272V-S279D, Q3I-H272V-Y281 P, Q3I-H272V-K308Q, Q3I-H272V-K309E, Q3I-H272V-K312Q, Q3I-S279D-Y281 P, Q3I-S279D-K308Q, Q3I-S279D-K309E, Q3I-S279D-K312Q, Q3I-Y281 P-K308Q, Q3I-Y281 P-K309E, Q3I-Y281 P-K312Q, Q3I-K308Q-K309E, Q3I-K308Q-K312Q, Q3I-K309E-K312Q, Q3I-Q225G-N227T-N252P-N260Q- S186R-K308Q-K309E-K312Q, Q3I-S163P-Q225G-N227T-N252P-N260Q-K308Q-K309E-K312Q, Q3F-A49W, Q3F-N59E, Q3F-S163P, Q3F-S186R, Q3F-Q215K, Q3F-S225G, Q3F-N227T, Q3F- N252P, Q3F-N267T, Q3F-F276A, Q3F-Y281 P, Q3F-K308Q, Q3F-K308E, Q3F-K309E, Q3F-K312E, Q3F-K312Q, Q3F-A49W-Q215K-F276A-K308E-K309E-K312E-N227T, Q3F-A49W-Q215K-F276A- K308E-K309E-K312E-N267T, Q3F-A49W-Q215K-F276A-K308E-K309E-N227T-N267T, Q3F-A49W- Q215K-F276A-K308E-K312E-N227T-N267T, Q3F-A49W-Q215K-F276A-K309E-K312E-N227T- N267T, Q3F-A49W-Q215K-K308E-K309E-K312E-N227T-N267T, Q3F-A49W-F276A-K308E-K309E- K312E-N227T-N267T, Q3F-Q215K-F276A-K308E-K309E-K312E-N227T-N267T, Q3F-Q215K-N227T- N252P-N267T-F276A-K308E-K309E-K312E, Q3F-S163P-Q215K-N227T-N252P-N267T-K308E- K309E-K312E, Q3F-A49W-Q215K-F276A-K308E-K309E-K312E-N227T-N267T, H15Y-A49W, H15Y- N59E, H15Y-S163P, H15Y-S186R, H15Y-S225G, H15Y-N227T, H15Y-E232D, H15Y-235W, H15Y- N252P, H15Y-N260Q, H15Y-H272V, H15Y-S279D, H15Y-Y281 P, H15Y-K308Q, H15Y-K309E, H15Y- K312Q, H15Y-A49W-N59E, H15Y-A49W-S163P, H15Y-A49W-S186R, H15Y-A49W-S225G, H15Y- A49W-N227T, H15Y-A49W-E232D, H15Y-A49W-G235W, H15Y-A49W-N252P, H15Y-A49W-N260Q, H15Y-A49W-H272V, H15Y-A49W-S279D, H15Y-A49W-Y281 P, H15Y-A49W-K308Q, H15Y-A49W- K309E, H15Y-A49W-K312Q, H15Y-N59E-S163P, H15Y-N59E-S186R, H15Y-N59E-S225G, H15Y- N59E-N227T, H15Y-N59E-E232D, H15Y-N59E-G235W, H15Y-N59E-N252P, H15Y-N59E-N260Q, H15Y-N59E-H272V, H15Y-N59E-S279D, H15Y-N59E-Y281 P, H15Y-N59E-K308Q, H15Y-N59E- K309E, H15Y-N59E-K312Q, H15Y-S163P-S186R, H15Y-S163P-S225G, H15Y-S163P-N227T, H15Y- S163P-E232D, H15Y-S163P-G235W, H15Y-S163P-N252P, H15Y-S163P-N260Q, H15Y-S163P- H272V, H15Y-S163P-S279D, H15Y-S163P-Y281 P, H15Y-S163P-K308Q, H15Y-S163P-K309E, H15Y-S163P-K312Q, H15Y-S186R-S225G, H15Y-S186R-N227T, H15Y-S186R-E232D, H15Y- S186R-G235W, H15Y-S186R-N252P, H15Y-S186R-N260Q, H15Y-S186R-H272V, H15Y-S186R- S279D, H15Y-S186R-Y281 P, H15Y-S186R-K308Q, H15Y-S186R-K309E, H15Y-S186R-K312Q, H15Y-S225G-N227T, H15Y-S225G-E232D, H15Y-S225G-G235W, H15Y-S225G-N252P, H15Y- S225G-N260Q, H15Y-S225G-H272V, H15Y-S225G-S279D, H15Y-S225G-Y281 P, H15Y-S225G- K308Q, H15Y-S225G-K309E, H15Y-S225G-K312Q, H15Y-N227T-E232D, H15Y-N227T-G235W, H15Y-N227T-N252P, H15Y-N227T-N260Q, H15Y-N227T-H272V, H15Y-N227T-S279D, H15Y- N227T-Y281 P, H15Y-N227T-K308Q, H15Y-N227T-K309E, H15Y-N227T-K312Q, H15Y-E232D- G235W, H15Y-E232D-N252P, H15Y-E232D-N260Q, H15Y-E232D-H272V, H15Y-E232D-S279D, H15Y-E232D-Y281 P, H15Y-E232D-K308Q, H15Y-E232D-K309E, H15Y-E232D-K312Q, H15Y- G235W-N252P, H15Y-G235W-N260Q, H15Y-G235W-H272V, H15Y-G235W-S279D, H15Y-G235W- Y281 P, H15Y-G235W-K308Q, H15Y-G235W-K309E, H15Y-G235W-K312Q, H15Y-N252P-N260Q, H15Y-N252P-H272V, H15Y-N252P-S279D, H15Y-N252P-Y281 P, H15Y-N252P-K308Q, H15Y- N252P-K309E, H15Y-N252P-K312Q, H15Y-N260Q-H272V, H15Y-N260Q-S279D, H15Y-N260Q- Y281 P, H15Y-N260Q-K308Q, H15Y-N260Q-K309E, H15Y-N260Q-K312Q, H15Y-H272V-S279D, H15Y-H272V-Y281 P, H15Y-H272V-K308Q, H15Y-H272V-K309E, H15Y-H272V-K312Q, H15Y- S279D-Y281 P, H15Y-S279D-K308Q, H15Y-S279D-K309E, H15Y-S279D-K312Q, H15Y-Y281 P- K308Q, H15Y-Y281 P-K309E, H15Y-Y281 P-K312Q, H15Y-K308Q-K309E, H15Y-K308Q-K312Q, H15Y-K309E-K312Q, A49W-N59E, A49W-S163P, A49W-S186R, A49W-Q215K, A49W-S225G, A49W-N227T, A49W-N252P, A49W-N267T, A49W-F276A, A49W-Y281 P, A49W-K308Q, A49W- K308E, A49W-K309E, A49W-K312Q, A49W-K312E, A49W-E232D, A49W-G235W, A49W-N260Q, A49W-H272V, A49W-S279D, A49W-N59E-S163P, A49W-N59E-S186R, A49W-N59E-S225G, A49W- N59E-N227T, A49W-N59E-E232D, A49W-N59E-G235W, A49W-N59E-N252P, A49W-N59E-N260Q, A49W-N59E-H272V, A49W-N59E-S279D, A49W-N59E-Y281 P, A49W-N59E-K308Q, A49W-N59E- K309E, A49W-N59E-K312Q, A49W-S163P-S186R, A49W-S163P-S225G, A49W-S163P-N227T, A49W-S163P-E232D, A49W-S163P-G235W, A49W-S163P-N252P, A49W-S163P-N260Q, A49W- S163P-H272V, A49W-S163P-S279D, A49W-S163P-Y281 P, A49W-S163P-K308Q, A49W-S163P- K309E, A49W-S163P-K312Q, A49W-S186R-S225G, A49W-S186R-N227T, A49W-S186R-E232D, A49W-S186R-G235W, A49W-S186R-N252P, A49W-S186R-N260Q, A49W-S186R-H272V, A49W- S186R-S279D, A49W-S186R-Y281 P, A49W-S186R-K308Q, A49W-S186R-K309E, A49W-S186R- K312Q, A49W-S225G-N227T, A49W-S225G-E232D, A49W-S225G-G235W, A49W-S225G-N252P, A49W-S225G-N260Q, A49W-S225G-H272V, A49W-S225G-S279D, A49W-S225G-Y281 P, A49W- S225G-K308Q, A49W-S225G-K309E, A49W-S225G-K312Q, A49W-N227T-E232D, A49W-N227T- G235W, A49W-N227T-N252P, A49W-N227T-N260Q, A49W-N227T-H272V, A49W-N227T-S279D, A49W-N227T-Y281 P, A49W-N227T-K308Q, A49W-N227T-K309E, A49W-N227T-K312Q, A49W- E232D-G235W, A49W-E232D-N252P, A49W-E232D-N260Q, A49W-E232D-H272V, A49W-E232D- S279D, A49W-E232D-Y281 P, A49W-E232D-K308Q, A49W-E232D-K309E, A49W-E232D-K312Q, A49W-G235W-N252P, A49W-G235W-N260Q, A49W-G235W-H272V, A49W-G235W-S279D, A49W- G235W-Y281 P, A49W-G235W-K308Q, A49W-G235W-K309E, A49W-G235W-K312Q, A49W-N252P- N260Q, A49W-N252P-H272V, A49W-N252P-S279D, A49W-N252P-Y281 P, A49W-N252P-K308Q, A49W-N252P-K309E, A49W-N252P-K312Q, A49W-N260Q-H272V, A49W-N260Q-S279D, A49W- N260Q-Y281 P, A49W-N260Q-K308Q, A49W-N260Q-K309E, A49W-N260Q-K312Q, A49W-H272V- S279D, A49W-H272V-Y281 P, A49W-H272V-K308Q, A49W-H272V-K309E, A49W-H272V-K312Q, A49W-S279D-Y281 P, A49W-S279D-K308Q, A49W-S279D-K309E, A49W-S279D-K312Q, A49W- Y281 P-K308Q, A49W-Y281 P-K309E, A49W-Y281 P-K312Q, A49W-K308Q-K309E, A49W-K308Q- K312Q, A49W-K309E-K312Q, A49W-N227T-F276A-K308E, A49W-S186R-N227T-F276A, A49W- S186R-N227T-K308E, A49W-N227T-A269C-Y282C-K308E, A49W-S186R-N227T-F276A-K308E, A49W-Y124R-N227T-F276A-K308E, A49W-Y124R-S186R-N227T-F276A, A49W-Y124R-S186R- N227T-K308E, A49W-A269C-F276A-Y282C-K308E, A49W-N227T-A269C-F276A-Y282C, A49W- F276A-K308E, A49W-N227T-F276A, A49W-Y124R-S186R-N227T-F276A-K308E, A49W-N227T- A269C-F276A-Y282C-K308E, A49W-S186R-N227T-A269C-F276A-Y282C, A49W-S186R-N227T- A269C-Y282C-K308E, A49W-S186R-N227T-A269C-F276A-Y282C-K308E, A49W-Y124R-N227T- A269C-F276A-Y282C-K308E, A49W-Y124R-S186R-N227T-A269C-F276A-Y282C, A49W-Y124R- S186R-N227T-A269C-Y282C-K308E, A49W-Y124R-S186R-N227T-A269C-F276A-Y282C-K308E, A49W-S163P-Q215K-N227T-N252P-N267T-F276A-K309E-K312E, A49W-Q215K-N227T-N252P- N267T-F276A-K308E-K309E-K312E, A49W-S163P-Q225G-N227T-N252P-N260Q-S186R-K309E- K312Q, A49W-Q225G-N227T-N252P-N260Q-S186R-K308Q-K309E-K312Q, N59E-S163P, N59E- S186R, N59E-Q215K, N59E-S225G, N59E-N227T, N59E-N252P, N59E-N267T, N59E-F276A, N59E- Y281 P, N59E-K308Q, N59E-K308E, N59E-K309E, N59E-K312Q, N59E-K312E, N59E-E232D, N59E- G235W, N59E-N260Q, N59E-H272V, N59E-S279D, N59E-S163P-S186R, N59E-S163P-S225G, N59E-S163P-N227T, N59E-S163P-E232D, N59E-S163P-G235W, N59E-S163P-N252P, N59E- S163P-N260Q, N59E-S163P-H272V, N59E-S163P-S279D, N59E-S163P-Y281 P, N59E-S163P- K308Q, N59E-S163P-K309E, N59E-S163P-K312Q, N59E-S186R-S225G, N59E-S186R-N227T, N59E-S186R-E232D, N59E-S186R-G235W, N59E-S186R-N252P, N59E-S186R-N260Q, N59E- S186R-H272V, N59E-S186R-S279D, N59E-S186R-Y281 P, N59E-S186R-K308Q, N59E-S186R- K309E, N59E-S186R-K312Q, N59E-S225G-N227T, N59E-S225G-E232D, N59E-S225G-G235W, N59E-S225G-N252P, N59E-S225G-N260Q, N59E-S225G-H272V, N59E-S225G-S279D, N59E- S225G-Y281 P, N59E-S225G-K308Q, N59E-S225G-K309E, N59E-S225G-K312Q, N59E-N227T- E232D, N59E-N227T-G235W, N59E-N227T-N252P, N59E-N227T-N260Q, N59E-N227T-H272V, N59E-N227T-S279D, N59E-N227T-Y281 P, N59E-N227T-K308Q, N59E-N227T-K309E, N59E-N227T- K312Q, N59E-E232D-G235W, N59E-E232D-N252P, N59E-E232D-N260Q, N59E-E232D-H272V, N59E-E232D-S279D, N59E-E232D-Y281 P, N59E-E232D-K308Q, N59E-E232D-K309E, N59E- E232D-K312Q, N59E-G235W-N252P, N59E-G235W-N260Q, N59E-G235W-H272V, N59E-G235W- S279D, N59E-G235W-Y281 P, N59E-G235W-K308Q, N59E-G235W-K309E, N59E-G235W-K312Q, N59E-N252P-N260Q, N59E-N252P-H272V, N59E-N252P-S279D, N59E-N252P-Y281 P, N59E- N252P-K308Q, N59E-N252P-K309E, N59E-N252P-K312Q, N59E-N260Q-H272V, N59E-N260Q- S279D, N59E-N260Q-Y281 P, N59E-N260Q-K308Q, N59E-N260Q-K309E, N59E-N260Q-K312Q, N59E-H272V-S279D, N59E-H272V-Y281 P, N59E-H272V-K308Q, N59E-H272V-K309E, N59E- H272V-K312Q, N59E-S279D-Y281 P, N59E-S279D-K308Q, N59E-S279D-K309E, N59E-S279D- K312Q, N59E-Y281 P-K308Q, N59E-Y281 P-K309E, N59E-Y281 P-K312Q, N59E-K308Q-K309E, N59E-K308Q-K312Q, N59E-K309E-K312Q, N59E-N227T-N252P-E232D-S225G, N59E-N227T- N252P-E232D-K308Q, N59E-N227T-N252P-E232D-K309E, N59E-N227T-N252P-S225G-K308Q, N59E-N227T-N252P-S225G-K309E, N59E-N227T-N252P-K308Q-K309E, N59E-N227T-E232D- S225G-K308Q, N59E-N227T-E232D-S225G-K309E, N59E-N227T-E232D-K308Q-K309E, N59E- N227T-S225G-K308Q-K309E, N59E-N252P-E232D-S225G-K308Q, N59E-N252P-E232D-S225G- K309E, N59E-N252P-E232D-K308Q-K309E, N59E-N252P-S225G-K308Q-K309E, N59E-E232D- S225G-K308Q-K309E, N59E-N227T-S225G-K308Q-K312Q, N59E-N227T-S225G-K309E-K312Q, N59E-N227T-K308Q-K309E-K312Q, N59E-S225G-K308Q-K309E-K312Q, 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S186R-N227T-A269C-F276A-Y282C-K308E, S186R-N227T- N252P-S186R-K308Q-K309E-K312Q, S186R-N227T-S225G-S186R-K308Q-K309E-K312Q, S163P- N227T-N252P-S186R-K308Q-K309E-K312Q, Q215K-S225G, Q215K-N227T, Q215K-N252P, Q215K- N267T, Q215K-F276A, Q215K-Y281 P, Q215K-K308E, Q215K-K308Q, Q215K-K309E, Q215K- K312Q, Q215K-K312E, Q215K-F276A-K308E, Q215K-F276A-K312E, Q215K-K308E-K312E, Q215K- K309E-K312E, Q215K-N227T-F276A, Q215K-N227T-K308E, Q215K-N227T-K309E, Q215K-N227T- K312E, Q215K-N227T-N252P, Q215K-N227T-N267T, Q215K-N252P-F276A, Q215K-N252P-K309E, Q215K-N252P-K312E, Q215K-N252P-N267T, Q215K-N267T-F276A, Q215K-N267T-K312E, Q215K- N227T-N252P-N267T-F276A, Q215K-N227T-N252P-N267T-K308E, Q215K-N227T-N252P-N267T- K309E, Q215K-N227T-N252P-F276A-K308E, Q215K-N227T-N252P-F276A-K309E, Q215K-N227T- N252P-K308E-K309E, Q215K-N227T-N267T-F276A-K308E, Q215K-N227T-N267T-F276A-K309E, Q215K-N227T-N267T-K308E-K309E, Q215K-N227T-F276A-K308E-K309E, Q215K-N252P-N267T- F276A-K308E, Q215K-N252P-N267T-F276A-K309E, Q215K-N252P-N267T-K308E-K309E, Q215K- N252P-F276A-K308E-K309E, Q215K-N267T-F276A-K308E-K309E, Q215K-N227T-F276A-K308E- K312E, Q215K-N227T-F276A-K309E-K312E, Q215K-N227T-K308E-K309E-K312E, Q215K-F276A- K308E-K309E-K312E, Q215K-N227T-F276A-K308E-K309E-K312E, Q215K-N227T-N252P-F276A- K308E-K309E-K312E, Q215K-N227T-N267T-F276A-K308E-K309E-K312E, Q215K-N227T-N252P- N267T-F276A-K308E-K309E-K312E, S225G-N227T, S225G-N252P, S225G-N267T, S225G-F276A, S225G-Y281 P, S225G-K308E, S225G-K308Q, S225G-K309E, S225G-K312Q, S225G-K312E, S225G-E232D, S225G-G235W, S225G-N260Q, S225G-H272V, S225G-S279D, S225G-N227T- E232D, S225G-N227T-G235W, S225G-N227T-N252P, S225G-N227T-N260Q, S225G-N227T- H272V, S225G-N227T-S279D, S225G-N227T-Y281 P, S225G-N227T-K308Q, S225G-N227T-K309E, S225G-N227T-K312Q, S225G-E232D-G235W, S225G-E232D-N252P, S225G-E232D-N260Q, S225G-E232D-H272V, S225G-E232D-S279D, S225G-E232D-Y281 P, S225G-E232D-K308Q, S225G- E232D-K309E, S225G-E232D-K312Q, S225G-G235W-N252P, S225G-G235W-N260Q, S225G- G235W-H272V, S225G-G235W-S279D, S225G-G235W-Y281 P, S225G-G235W-K308Q, S225G- G235W-K309E, S225G-G235W-K312Q, S225G-N252P-N260Q, S225G-N252P-H272V, S225G- N252P-S279D, S225G-N252P-Y281 P, S225G-N252P-K308Q, S225G-N252P-K309E, S225G-N252P- K312Q, S225G-N260Q-H272V, S225G-N260Q-S279D, S225G-N260Q-Y281 P, S225G-N260Q- K308Q, S225G-N260Q-K309E, S225G-N260Q-K312Q, S225G-H272V-S279D, S225G-H272V- Y281 P, S225G-H272V-K308Q, S225G-H272V-K309E, S225G-H272V-K312Q, S225G-S279D-Y281 P, S225G-S279D-K308Q, S225G-S279D-K309E, S225G-S279D-K312Q, S225G-Y281 P-K308Q, S225G- Y281 P-K309E, S225G-Y281 P-K312Q, S225G-K308Q-K309E, S225G-K308Q-K312Q, S225G-K309E- K312Q, S225G-K308Q-K309E-K312Q, S225G-N227T-N252P-S186R-N260Q-K308E-K309E-K312E, N227T-N252P, N227T-N267T, N227T-F276A, N227T-Y281 P, N227T-K308Q, N227T-K308E, N227T- K309E, N227T-K312Q, N227T-K312E, N227T-E232D, N227T-G235W, N227T-N260Q, N227T- H272V, N227T-S279D, N227T-E232D-G235W, N227T-E232D-N252P, N227T-E232D-N260Q, N227T-E232D-H272V, N227T-E232D-S279D, N227T-E232D-Y281 P, N227T-E232D-K308Q, N227T- E232D-K309E, N227T-E232D-K312Q, N227T-G235W-N252P, N227T-G235W-N260Q, N227T- G235W-H272V, N227T-G235W-S279D, N227T-G235W-Y281 P, N227T-G235W-K308Q, N227T- G235W-K309E, N227T-G235W-K312Q, N227T-N252P-N260Q, N227T-N252P-H272V, N227T- N252P-S279D, N227T-N252P-Y281 P, N227T-N252P-K308Q, N227T-N252P-K309E, N227T-N252P- K312Q, N227T-N260Q-H272V, N227T-N260Q-S279D, N227T-N260Q-Y281 P, N227T-N260Q-K308Q, N227T-N260Q-K309E, N227T-N260Q-K312Q, N227T-H272V-S279D, N227T-H272V-Y281 P, N227T- H272V-K308Q, N227T-H272V-K309E, N227T-H272V-K312Q, N227T-S279D-Y281 P, N227T-S279D- K308Q, N227T-S279D-K309E, N227T-S279D-K312Q, N227T-Y281 P-K308Q, N227T-Y281 P-K309E, N227T-Y281 P-K312Q, N227T-K308Q-K309E, N227T-K308Q-K312Q, N227T-K309E-K312Q, N227T- N252P-K308E, N227T-N252P-K312E, N227T-N252P-N267T, N227T-N267T-F276A, N227T-N267T- K308E, N227T-N267T-K309E, N227T-N267T-K312E, N227T-F276A-K308E, N227T-F276A-K309E, N227T-F276A-K312E, N227T-K308E-K309E, N227T-K308E-K312E, N227T-K309E-K312E, N227T- F276A-K308E-K309E, N227T-F276A-K308E-K312E, N227T-F276A-K309E-K312E, N227T-K308E- K309E-K312E, N227T-S225G-K308Q-K309E, N227T-S225G-K308Q-K312Q, N227T-S225G-K309E- K312Q, N227T-K308Q-K309E-K312Q, N227T-N267T-F276A-K308E, N227T-N267T-F276A-K309E, N227T-N267T-F276A-K312E, N227T-N267T-S225G-K308Q, N227T-N267T-S225G-K309E, N227T- N267T-S225G-K312Q, N227T-N252P-N267T-F276A-K308E, N227T-N252P-N267T-F276A-K309E, N227T-N252P-N267T-K308E-K309E, N227T-N252P-F276A-K308E-K309E, N227T-N267T-F276A- K308E-K309E, N227T-F276A-K308E-K309E-K312E, N227T-N252P-E232D-S225G-K308Q, N227T- N252P-E232D-S225G-K309E, N227T-N252P-E232D-K308Q-K309E, N227T-N252P-S225G-K308Q- K309E, N227T-E232D-S225G-K308Q-K309E, N227T-S225G-K308Q-K309E-K312Q, N227T-N267T- F276A-K308E-K312E, N227T-N267T-F276A-K309E-K312E, N227T-E232D-S225G-K308Q-K312Q, N227T-E232D-S225G-K309E-K312Q, N227T-N267T-F276A-K308E-K309E-K312E, N227T-N252P- F276A-K308E-K309E-K312E, N227T-S225G-S186R-K308Q-K309E-K312Q, N227T-N252P-S186R- K308Q-K309E-K312Q, N227T-N252P-N267T-F276A-K308E-K309E-K312E, N227T-N252P-S225G- S186R-K308Q-K309E-K312Q, E232D-G235W, E232D-N252P, E232D-N260Q, E232D-H272V, E232D-S279D, E232D-Y281 P, E232D-K308Q, E232D-K309E, E232D-K312Q, E232D-G235W- N252P, E232D-G235W-N260Q, E232D-G235W-H272V, E232D-G235W-S279D, E232D-G235W- Y281 P, E232D-G235W-K308Q, E232D-G235W-K309E, E232D-G235W-K312Q, E232D-N252P- N260Q, E232D-N252P-H272V, E232D-N252P-S279D, E232D-N252P-Y281 P, E232D-N252P-K308Q, E232D-N252P-K309E, E232D-N252P-K312Q, E232D-N260Q-H272V, E232D-N260Q-S279D, E232D- N260Q-Y281 P, E232D-N260Q-K308Q, E232D-N260Q-K309E, E232D-N260Q-K312Q, E232D- H272V-S279D, E232D-H272V-Y281 P, E232D-H272V-K308Q, E232D-H272V-K309E, E232D-H272V- K312Q, E232D-S279D-Y281 P, E232D-S279D-K308Q, E232D-S279D-K309E, E232D-S279D-K312Q, E232D-Y281 P-K308Q, E232D-Y281 P-K309E, E232D-Y281 P-K312Q, E232D-K308Q-K309E, E232D- K308Q-K312Q, E232D-K309E-K312Q, G235W-N252P, G235W-N260Q, G235W-H272V, G235W- S279D, G235W-Y281 P, G235W-K308Q, G235W-K309E, G235W-K312Q, G235W-N252P-N260Q, G235W-N252P-H272V, G235W-N252P-S279D, G235W-N252P-Y281 P, G235W-N252P-K308Q, G235W-N252P-K309E, G235W-N252P-K312Q, G235W-N260Q-H272V, G235W-N260Q-S279D, G235W-N260Q-Y281 P, G235W-N260Q-K308Q, G235W-N260Q-K309E, G235W-N260Q-K312Q, G235W-H272V-S279D, G235W-H272V-Y281 P, G235W-H272V-K308Q, G235W-H272V-K309E, G235W-H272V-K312Q, G235W-S279D-Y281 P, G235W-S279D-K308Q, G235W-S279D-K309E, G235W-S279D-K312Q, G235W-Y281 P-K308Q, G235W-Y281 P-K309E, G235W-Y281 P-K312Q, G235W-K308Q-K309E, G235W-K308Q-K312Q, G235W-K309E-K312Q, G235W-N227T-S186R- K308Q-K309E-K312Q, G235W-N227T-N252P-S186R-N260Q-K308Q-K309E-K312Q, N252P-N267T, N252P-F276A, N252P-Y281 P, N252P-K308Q, N252P-K308E, N252P-K309E, N252P-K312Q, N252P- K312E, N252P-N260Q, N252P-H272V, N252P-S279D, N252P-N260Q-H272V, N252P-N260Q- S279D, N252P-N260Q-Y281 P, N252P-N260Q-K308Q, N252P-N260Q-K309E, N252P-N260Q- K312Q, N252P-H272V-S279D, N252P-H272V-Y281 P, N252P-H272V-K308Q, N252P-H272V-K309E, N252P-H272V-K312Q, N252P-S279D-Y281 P, N252P-S279D-K308Q, N252P-S279D-K309E, N252P- S279D-K312Q, N252P-Y281 P-K308Q, N252P-Y281 P-K309E, N252P-Y281 P-K312Q, N252P-K308Q- K309E, N252P-K308Q-K312Q, N252P-K309E-K312Q, N252P-F276A-K308E, N252P-F276A-K309E, N252P-F276A-K312E, N252P-K308E-K309E, N252P-K308E-K312E, N252P-N267T-F276A, N252P- N267T-K308E, N252P-N267T-K309E, N252P-N267T-K312E, N252P-N267T-F276A-K308E-K309E, N252P-E232D-S225G-K308Q-K309E, N260Q-H272V, N260Q-S279D, N260Q-Y281 P, N260Q- K308Q, N260Q-K309E, N260Q-K312Q, N260Q-H272V-S279D, N260Q-H272V-Y281 P, N260Q- H272V-K308Q, N260Q-H272V-K309E, N260Q-H272V-K312Q, N260Q-S279D-Y281 P, N260Q- S279D-K308Q, N260Q-S279D-K309E, N260Q-S279D-K312Q, N260Q-Y281 P-K308Q, N260Q- Y281 P-K309E, N260Q-Y281 P-K312Q, N260Q-K308Q-K309E, N260Q-K308Q-K312Q, N260Q- K309E-K312Q, N267T-F276A, N267T-Y281 P, N267T-K308E, N267T-K309E, N267T-K312Q, N267T- K312E, N267T-F276A-K308E, N267T-F276A-K309E, N267T-F276A-K312E, N267T-K308E-K309E, N267T-K308E-K312E, N267T-K309E-K312E, H272V-S279D, H272V-Y281 P, H272V-K308Q, H272V- K309E, H272V-K312Q, H272V-S279D-Y281 P, H272V-S279D-K308Q, H272V-S279D-K309E, H272V- S279D-K312Q, H272V-Y281 P-K308Q, H272V-Y281 P-K309E, H272V-Y281 P-K312Q, H272V-K308Q- K309E, H272V-K308Q-K312Q, H272V-K309E-K312Q, F276A-Y281 P, F276A-K308Q, F276A-K308E, F276A-K309E, F276A-K312Q, F276A-K312E, F276A-K308E-K309E, F276A-K308E-K312E, F276A- K309E-K312E, F276A-K308E-K309E-K312E, S279D-Y281 P, S279D-K308Q, S279D-K309E, S279D- K312Q, S279D-Y281 P-K308Q, S279D-Y281 P-K309E, S279D-Y281 P-K312Q, S279D-K308Q-K309E, S279D-K308Q-K312Q, S279D-K309E-K312Q, Y281 P-K308Q, Y281 P-K308E, Y281 P-K309E, Y281 P- K312Q, Y281 P-K312E, Y281 P-K308Q-K309E, Y281 P-K308Q-K312Q, Y281 P-K309E-K312Q, K308E- K312Q, K308E-K312E, K308Q-K312Q, K309E-K312Q, K309E-K312E, K308E-K309E, K308Q-K309E, K308Q-K309E-K312Q, K308E-K309E-K312E, K312E-N227T-F276A, K312E-N227T-K308E, K312E- N227T-K309E, K312E-N227T-K312E, K312E-F276A-K308E, K312E-F276A-K309E, K312E-F276A- K312E, K312E-K308E-K309E, K312E-K308E-K312E, K312E-K309E-K312E, K312E-N227T-F276A- K308E, K312E-N227T-F276A-K309E, K312E-N227T-F276A-K312E, K312E-N227T-K308E-K309E, K312E-N227T-K308E-K312E, K312E-N227T-K309E-K312E, K312E-F276A-K308E-K309E, K312E- F276A-K308E-K312E, K312E-F276A-K309E-K312E, K312E-K308E-K309E-K312E, K312Q-N227T- S225G-K308Q, K312Q-N227T-S225G-K309E, K312Q-N227T-S225G-K312Q, K312Q-N227T-K308Q- K309E, K312Q-N227T-K308Q-K312Q, K312Q-N227T-K309E-K312Q, K312Q-S225G-K308Q-K309E, K312Q-S225G-K308Q-K312Q, K312Q-S225G-K309E-K312Q und K312Q-K308Q-K309E-K312Q bestehenden Gruppe ausgewählt ist, bezogen auf die Nummerierung gemäß SEQ ID NO:1. In preferred embodiments, a dispersin is used which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, has at least one and increasingly preferably two, three, four, five, six, seven, eight or nine amino acid substitutions, wherein the Dispersin has an amino acid substitution combination selected from the group consisting of Q3I-A49W, Q3I-N59E, Q3I-S163P, Q3I-S186R, Q3I-Q215K, Q3I-S225G, Q3I-N227T, Q3I-N252P, Q3I-N267T, Q3I-F276A, Q3I-Y281 P, Q3I-K308Q, Q3I-K308E, Q3I-K309E, Q3I-K312Q, Q3I-K312E, Q3I-H15Y, Q3I-E232D, Q3I-G235W, Q3I-N260Q, Q3I-H272V, Q3I-S279D, Q3I-H15Y-A49W, Q3I-H15Y-N59E, Q3I-H15Y-S163P, Q3I-H15Y-S186R, Q3I-H15Y-S225G, Q3I-H15Y-N227T, Q3I-H15Y-E232D, Q3I-H15Y-G235W, 15Y-N252P, Q3I-H15Y-N260Q, Q3I-H15Y-H272V, Q3I-H15Y-S279D, Q3I-H15Y-Y281P, Q3I-H15Y-K308Q, Q3I-H15Y-K309E, Q3I-H15Y-K312Q, Q3I-A49W-N59E, Q3I-A49W-S163P, Q3I-A49W-S186R, Q3I-A49W-S225G, Q3I-A49W-N227T, Q3I-A49W-E232D, Q3I-A49W-G235W, Q3I-A49W-N252P, A49W-N260Q, Q3I-A49W-H272V, Q3I-A49W-S279D, Q3I-A49W-Y281P, Q3I-A49W-K308Q, Q3I-A49W-K309E, Q3I-A49W-K312Q, Q3I-N59E-S163P, Q3I-N59E-S186R, Q3I-N59E-S225G, Q3I-N59E-N227T, Q3I-N59E-E232D, Q3I-N59E-G235W, Q3I-N59E-N252P, Q3I-N59E-N260Q, Q3I-N59E-H272V, Q3I -N59E-S279D, Q3I-N59E-Y281P, Q3I-N59E-K308Q, Q3I-N59E-K309E, Q3I-N59E-K312Q, Q3I-S163P-S186R, Q3I-S163P-S225G, Q3I-S163P-N227T, Q3I-S163P-E232D, Q3I-S163P-G235W, Q3I-S163P-N252P, Q3I-S163P-N260Q, Q3I-S163P-H272V, Q3I-S163P-S279D, Q3I-S163P-Y281P, Q3I-S163P-K 308Q, Q3I-S163P-K309E, Q3I-S163P-K312Q, Q3I-S186R-S225G, Q3I-S186R-N227T, Q3I-S186R-E232D, Q3I-S186R-G235W, Q3I-S186R-N252P, Q3I-S186R- N260Q, Q3I-S186R-H272V, Q3I-S186R-S279D, Q3I-S186R-Y281 P, Q3I-S186R-K308Q, Q3I-S186R- K309E, Q3I-S186R-K312Q, Q3I-S225G-N227T, Q3I-S225G-E232D, Q3I-S225G-G235W, Q3I-S225G-N252P, Q3I-S225G-N260Q, Q3I-S225G-H272V, 225G-S279D, Q3I-S225G-Y281P, Q3I-S225G-K308Q, Q3I-S225G-K309E, Q3I-S225G-K312Q, Q3I-N227T-E232D, Q3I-N227T-G235W, Q3I-N227T- N252P, Q3I-N227T-N260Q, Q3I-N227T-H272V, Q3I-N227T-S279D, Q3I-N227T-Y281P, Q3I-N227T-K308Q, Q3I-N227T-K309E, Q3I-N227T-K312Q, 232D-G235W, Q3I-E232D-N252P, Q3I-E232D-N260Q, Q3I-E232D-H272V, Q3I-E232D-S279D, Q3I-E232D-Y281P, Q3I-E232D-K308Q, Q3I-E232D-K309E, Q3I-E232D-K312Q, Q3I-G235W-N252P, Q3I-G235W-N260Q, Q3I-G235W-H272V, Q3I-G235W-S279D, Q3I-G235W-Y281 P, Q3I-G235W-K308Q, Q3I-G235W-K 309E, Q3I-G235W-K312Q, Q3I-N252P-N260Q, Q3I-N252P-H272V, Q3I-N252P-S279D, Q3I-N252P-Y281P, Q3I-N252P-K308Q, Q3I-N252P-K309E, Q3I-N252P-K312Q, Q3I-N260Q-H272V, Q3I-N260Q-S279D, Q3I-N260Q-Y281P, Q3I-N260Q-K308Q, Q3I-N260Q-K309E, Q3I-N260Q-K312Q, Q3I-H272V-S 279D, Q3I-H272V-Y281P, Q3I-H272V-K308Q, Q3I-H272V-K309E, Q3I-H272V-K312Q, Q3I-S279D-Y281P, Q3I-S279D-K308Q, Q3I-S279D-K309E, Q3I-S279D-K312Q, Q3I-Y281 P-K308Q, Q3I-Y281 P-K309E, Q3I-Y281 P-K312Q, Q3I-K308Q-K309E, Q3I-K308Q-K312Q, Q3I-K309E-K312Q, Q3I-Q225G-N 227T-N252P-N260Q- S186R-K308Q-K309E-K312Q, Q3I-S163P-Q225G-N227T-N252P-N260Q-K308Q-K309E-K312Q, Q3F-A49W, Q3F-N59E, Q3F-S163P, Q3F-S186R, Q3F-Q215K, Q3F-S225G, Q3F-N227T, Q3F-N252P, Q3F-N267T, Q3F-F276A, Q3F-Y281P, Q3F-K308Q, Q3F-K308E, Q3F-K309E, Q3F-K312E, Q3F -K312Q, Q3F-A49W-Q215K-F276A-K308E-K309E-K312E-N227T, Q3F-A49W-Q215K-F276A- K308E-K309E-K312E-N267T, Q3F-A49W-Q215K-F276A-K308E-K309E-N227T-N267T, Q3F-A49W- Q215K-F276A-K308E-K312E-N227T-N267T, N227T- N267T, Q3F-A49W-Q215K-K308E-K309E-K312E-N227T-N267T, Q3F-A49W-F276A-K308E-K309E- K312E-N227T-N267T, Q3F-Q215K-F276A-K308E-K309E-K312E-N227T-N267T, Q3F-Q215K-N227T-N252P-N267T-F276A-K308E-K309E-K312E, Q3F-S163P-Q215K-N227T-N25 2P-N267T-K308E- K309E-K312E, Q3F-A49W-Q215K-F276A-K308E-K309E-K312E-N227T-N267T, H15Y-A49W, H15Y-N59E, H15Y-S163P, H15Y-S186R, H15Y-S225G, H15Y-N227T, H15Y-E232D, H15Y-235W, H15Y-N252P, H15Y-N260Q, H15Y-H272V, H15Y-S279D, H15Y-Y281P, H15Y-K308Q, H15Y-K309E, H15 Y-K312Q, H15Y-A49W-N59E, H15Y-A49W-S163P, H15Y-A49W-S186R, H15Y-A49W-S225G, H15Y-A49W-N227T, H15Y-A49W-E232D, H15Y-A49W-G235W, H15Y-A49W-N252P, H15Y-A49W-N260Q, H15Y-A49W-H272V, H15Y-A49W-S279D, H15Y-A49W-Y281P, H15Y-A49W-K308Q, H15Y-A49W-K309E, H15Y-A49W-K 312Q, H15Y-N59E-S163P, H15Y-N59E-S186R, H15Y-N59E-S225G, H15Y-N59E-N227T, H15Y-N59E-E232D, H15Y-N59E-G235W, H15Y-N59E-N252P, H15Y-N59E-N260Q, H15Y-N59E-H272V, H15Y-N59E-S279D, H15Y-N59E-Y281P, H15Y-N59E-K308Q, H15Y-N59E-K309E, H15Y-N59E-K312Q, S186R, H15Y-S163P-S225G, H15Y-S163P-N227T, H15Y- S163P-E232D, H15Y-S163P-G235W, H15Y-S163P-N252P, H15Y-S163P-N260Q, H15Y-S163P- H272V, H15Y-S163P-S279D, H15Y-S163P-Y281P, H15Y-S163P-K308Q, H15Y-S163P-K309E, H15Y-S163P-K312Q, H15Y-S186R-S225G, H15Y-S186R-N227 T. H15Y-S186R-K308Q, H15Y-S186R-K309E, H15Y-S186R-K312Q, H15Y-S225G-N227T, H15Y-S225G-E232D, H15Y-S225G-G235W, H15Y-S225G-N252P, H15Y - S225G-N260Q, H15Y-S225G-H272V, H15Y-S225G-S279D, H15Y-S225G-Y281P, H15Y-S225G- H15Y-N227T-H272 V, H15Y-N227T-S279D, H15Y-N227T-Y281P, H15Y-N227T-K308Q, H15Y-N227T-K309E, H15Y-N227T-K312Q, H15Y-E232D-G235W, H15Y-E232D-N252P, H15Y-E232D-N260Q, H15Y-E232D-H272V, H15Y-E232D-S279D, H15Y-E232D-Y281P, H15Y-E232D-K308Q, H15Y-E232D-K309E, H15Y -E232D-K312Q, H15Y- G235W-N252P, H15Y-G235W-N260Q, H15Y-G235W-H272V, H15Y-G235W-S279D, H15Y-G235W- Y281 P, H15Y-G235W-K308Q, H15Y-G235W-K309E, H15Y-G235W-K312Q, H15Y-N252P-N260Q, H15Y-N252P-H272V, H15Y-N252P-S279D, H15Y-N252P-Y281P, H15Y-N252P-K308Q, H15Y - N252P-K309E, H15Y-N252P-K312Q, H15Y-N260Q-H272V, H15Y-N260Q-S279D, H15Y-N260Q-Y281 P, H15Y-N260Q-K308Q, H15Y-N260Q-K309E, H15Y-N260Q-K312Q, H15Y-H272V-S279D, H15Y-H272V-Y281P, H15Y-H272V-K308Q, H15Y-H272V-K309E, H15Y-H272V-K312Q, H15Y-S279D-Y281P, H15Y -S279D-K308Q, H15Y-S279D-K309E, H15Y-S279D-K312Q, H15Y-Y281 P-K308Q, H15Y-Y281 P-K309E, H15Y-Y281 P-K312Q, H15Y-K308Q-K309E, H15Y-K308Q-K312Q, H15Y-K309E-K312Q, A49W-N59E, A49W-S163P, A49W-S186R, A49W-Q215K, A49W-S225G, A49W-N227T, A49W-N252P, A49W-N267T, A4 9W-F276A, A49W-Y281P, A49W-K308Q, A49W-K308E, A49W-K309E, A49W-K312Q, A49W-K312E, A49W-E232D, A49W-G235W, A49W-N260Q, A49W-H272V, A49W-S279D, A49W-N59E-S163P, A49W-N59E-S186R, A49W-N59E-S225G, A49W-N59E-N227T, A49W-N59E-E232D, A49W-N59E-G235W, A49W-N59E-N260Q, A49W-N59E-H272V, A49W-N59E-S279D, A49W-N59E-Y281P, A49W-N59E-K308Q, A49W-N59E-K309E, A49W-N59E-K312Q, A49W-S163P-S186R, A49W-S163P-S225G, A49W-S163P-N227T, A49W-S163P-E232D, A49W-S163P-G235W, A49W-S163P-N252P, A49W-S163P-N260Q, A49W - S163P-H272V, A49W-S163P-S279D, A49W-S163P-Y281P, A49W-S163P-K308Q, A49W-S163P-K309E, A49W-S163P-K312Q, A49W-S186R-S225G, A49W-S186R-N227T, A49W-S186R-E232D, A49W-S186R-G235W, A49W-S186R-N252P, A49W-S186R-N260Q, A49W-S186R-H272V, A49W-S186R-S279D, A49W -S186R-Y281P, A49W-S186R-K308Q, A49W-S186R-K309E, A49W-S186R-K312Q, A49W-S225G-N227T, A49W-S225G-E232D, A49W-S225G-G235W, A49W-S225G-N252P, A49W-S225G-N260Q, A49W-S225G-H272V, A49W-S225G-S279D, A49W-S225G-Y281P, A49W-S225G-K308Q, A49W-S225G-K309E, A49W -S225G-K312Q, A49W-N227T-E232D, A49W-N227T-G235W, A49W-N227T-N252P, A49W-N227T-N260Q, A49W-N227T-H272V, A49W-N227T-S279D, A49W-N227T-Y281P, A49W-N227T-K308Q, A49W-N227T-K309E, A49W-N227T-K312Q, A49W-E232D-G235W, A49W-E232D-N252P, A49W-E232D-N260Q, A49W -E232D-H272V, A49W-E232D-S279D, A49W-E232D-Y281P, A49W-E232D-K308Q, A49W-E232D-K309E, A49W-E232D-K312Q, A49W-G235W-N252P, A49W-G235W-N260Q, A49W-G235W-H272V, A49W-G235W-S279D, A49W-G235W-Y281 P, A49W-G235W-K308Q, A49W-G235W-K309E, A49W-G235W-K312Q, A49W -N252P- N260Q, A49W-N252P-H272V, A49W-N252P-S279D, A49W-N252P-Y281P, A49W-N252P-K308Q, A49W-N252P-K309E, A49W-N252P-K312Q, A49W-N260Q-H272V, A49W-N260Q-S279D, A49W-N260Q-Y281P, A49W-N260Q-K308Q, A49W-N260Q-K309E, A49W-N260Q-K312Q, A49W-H272V-S279D, -H272V-Y281P, A49W-H272V-K308Q, A49W-H272V-K309E, A49W-H272V-K312Q, A49W-S279D-Y281P, A49W-S279D-K308Q, A49W-S279D-K309E, A49W-S279D-K312Q, A49W-Y281 P-K308Q, A49W-Y281 P-K309E, A49W-Y281 P-K312Q, A49W-K308Q-K309E, A49W-K308Q- K312Q, A49W-K309E-K312Q, A49W-N227T-F276A-K308E, A49W-S186R-N227T-F276A, A49W-S186R-N227T-K308E, A49W-N227T-A269C-Y282C-K308E, A4 9W-S186R-N227T-F276A-K308E, A49W-Y124R-N227T-F276A-K308E, A49W-Y124R-S186R-N227T-F276A, A49W-Y124R-S186R-N227T-K308E, A49W-A269C-F276A-Y282C-K308E, A49W-N227T-A269C-F276A-Y282C, A49W-F276A-K308E, A49W-N227T-F276A, A49W-Y124R-S186R-N227T-F276A-K3 08E, A49W-N227T- A269C-F276A-Y282C-K308E, A49W-S186R-N227T-A269C-F276A-Y282C, A49W-S186R-N227T- A269C-Y282C-K308E, A49W-S186R-N227T-A269C-F276A-Y282C-K308E, A49W-Y124R-N227T- A269C-F276A-Y282C-K308E, A49W-Y124R-S186R-N227T-A269C-F276A-Y282C, A49W-Y124R- S186R-N227T-A269C-Y282C-K308E, A49W-Y124R-S186R-N227T-A269C-F276A-Y282C-K308E, A49W-S163P-Q215K-N227T-N252P-N267T-F276A-K309E-K312E, A49W-Q215K-N227T-N252P- N267T-F276A-K308E-K309E-K312E, N227T-N252P-N260Q-S186R-K309E- K312Q, A49W-Q225G-N227T-N252P-N260Q-S186R-K308Q-K309E-K312Q, N59E-S163P, N59E-S186R, N59E-Q215K, N59E-S225G, N59E-N227T, N59E-N252P, N59E-N267T, N59E-F276A, N59E-Y281P, N59E-K308Q, N59E-K308E, N59E-K309E, N59E-K312Q, N59E-K312E, N5 9E-E232D, N59E-G235W, N59E-N260Q, N59E-H272V, N59E-S279D, N59E-S163P-S186R, N59E-S163P-S225G, N59E-S163P-N227T, N59E-S163P-E232D, N59E-S163P-G235W, N59E-S163P-N252P, N59E-S163P-N260Q, N59E-S163P-H272V, N59E-S163P-S279D, N59E-S163P-Y281P, N59E-S163P-K308Q, N59E -S163P-K309E, N59E-S163P-K312Q, N59E-S186R-S225G, N59E-S186R-N227T, N59E-S186R-E232D, N59E-S186R-G235W, N59E-S186R-N252P, N59E-S186R-N260Q, N59E-S186R-H272V, N59E-S186R-S279D, N59E-S186R-Y281P, N59E-S186R-K308Q, N59E-S186R-K309E, N59E-S186R-K312Q, N59E -S225G-N227T, N59E-S225G-E232D, N59E-S225G-G235W, N59E-S225G-N252P, N59E-S225G-N260Q, N59E-S225G-H272V, N59E-S225G-S279D, N59E- N59E-N227T-G235W, N59E-N227T-N252P, N59E-N227T-N227 T-N260Q, N59E-N227T-H272V, N59E-N227T-S279D, N59E-N227T-Y281P, N59E-N227T-K308Q, N59E-N227T-K309E, N59E-N227T-K312Q, N59E-E232D-G235W, N59E-E232D-N252P, N59E-E232D-N260Q, N59E-E232D-H272V, N59E-E232D-S279D, N59E-E232D-Y281P, N59E-E232D-K308Q, N59E -E232D-K309E, N59E- E232D-K312Q, N59E-G235W-N252P, N59E-G235W-N260Q, N59E-G235W-H272V, N59E-G235W- S279D, N59E-G235W-Y281 P, N59E-G235W-K308Q, N59E-G235W-K309E, N59E-G235W-K312Q, N59E-N252P-N260Q, N59E-N252P-H272V, N59E-N252P-S279D, N59E-N252P-Y281P, N59E - N252P-K308Q, N59E-N252P-K309E, N59E-N252P-K312Q, N59E-N260Q-H272V, N59E-N260Q-S279D, N59E-N260Q-Y281P, N59E-N260Q-K308Q, N59E-N260Q-K309E, N59E-N260Q-K312Q, N59E-H272V-S279D, N59E-H272V-Y281P, N59E-H272V-K308Q, N59E-H272V-K309E, N59E-H272V-K312Q, N59E -S279D-Y281, N59E-K308Q-K309E, N59E-K308Q-K312Q, N59E-K309E-K312Q, N59E-N227T-N252P-E232D-S225G, N59E-N227T- N252P-E232D-K308Q, N59E-N227T-N25 2P-E232D-K309E, 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S186R-Y281 P-K308Q, S186R-Y281 P-K309E, S186R-Y281 P-K312Q, S186R-K308Q-K309E, S186R-K308Q-K31 2Q, S186R-K309E-K312Q, S186R-F276A-K308E, S186R-N227T-F276A, S186R-N227T-K308E, S186R-N227T-E232D-K308E, S186R-A269C-F276A-Y282C-K308E, S186R-N227T-A269C-F276A-Y282C, S186R-N227T-A269C-Y282C-K308E, S186R-N227T-A269C-F276A-Y282C-K30 8E, S186R-N227T- N252P-S186R-K308Q-K309E-K312Q, S186R-N227T-S225G-S186R-K308Q-K309E-K312Q, S163P- N227T-N252P-S186R-K308Q-K309E-K312Q, Q215K-S225G, Q215K-N227T, Q215K-N252P, Q215K-N267T, Q215K-F276A, Q215K-Y281 P, Q215K-K308E, 5K-K308Q, Q215K-K309E, Q215K-K312Q, Q215K-K312E, Q215K-F276A-K308E, Q215K-F276A-K312E, Q215K-K308E-K312E, Q215K-K309E-K312E, Q215K-N227T-F276A, Q215K-N227T-K308E, Q215K-N227T-K309E, Q215K-N227T-K312E, Q215K-N227T-N252P, Q215K-N227T-N267T, Q215K-N252P-F27 6A, Q215K-N252P-K309E, Q215K-N252P-K312E, Q215K-N252P-N267T, Q215K-N267T-F276A, Q215K-N267T-K312E, Q215K-N227T-N252P-N267T-F276A, Q215K-N227T-N252P-N267T-K308E, Q215K-N227T-N252P-N267T-K309E, Q215K-N227T-N252P-F276A-K308E, Q215K-N227T-N252P-F276A-K309E, 5K-N227T-N252P-K308E-K309E, Q215K-N227T-N267T-F276A-K308E, Q215K-N227T-N267T-F276A-K309E, Q215K-N227T-N267T-K308E-K309E, Q215K-N227T-F276A-K308E-K309E, Q215K-N252P-N267T- F276A-K308E, Q215K-N252P-N267T-F276A-K309E, Q215K-N252P-N267T-K308E-K309E, 5K-N252P-F276A-K308E-K309E, Q215K-N267T-F276A-K308E-K309E, Q215K-N227T-F276A-K308E-K312E, Q215K-N227T-F276A-K309E-K312E, Q215K-N227T-K308E-K309E-K312E, Q215K-F276A- K308E-K309E-K312E, Q215K-N227T-F276A-K308E-K309E-K312E, Q215K-N227T-N252P-F276A- K30 8E-K309E-K312E, Q215K-N227T-N267T-F276A-K308E-K309E-K312E, Q215K-N227T-N252P- N267T-F276A-K308E-K309E-K312E, S225G-N227T, S225G-N252P, S225G-N267T, S225G-F276A, S225G-Y281P, S225G-K308E, S225G-K308Q, S225G-K309E, S225G-K312Q, S225G-K312E, S225G-E232D, S22 5G-G235W, S225G-N260Q, S225G-H272V, S225G-S279D, S225G-N227T-E232D, S225G-N227T-G235W, S225G-N227T-N252P, S225G-N227T-N260Q, S225G-N227T- H272V, S225G-N227T-S279D, S225G-N227T-Y281P, S225G-N227T-K308Q, S225G-N227T-K309E, S225G-N227T-K312Q, S225G-E232D-G235W, S225G-E23 2D-N252P, S225G-E232D-N260Q, S225G-E232D-H272V, S225G-E232D-S279D, S225G-E232D-Y281P, S225G-E232D-K308Q, S225G-E232D-K309E, S225G-E232D-K312Q, S225G-G235W-N252P, S225G-G235W-N260Q, S225G-G235W-H272V, S225G-G235W-S279D, S225G-G235W-Y281P, S225G-G235W-K30 8Q, S225G-G235W-K309E, S225G-G235W-K312Q, S225G-N252P-N260Q, S225G-N252P-H272V, S225G-N252P-S279D, S225G-N252P-Y281P, S225G-N252P-K308Q, S225G-N252P-K309E, S225G-N252P-K312Q, S225G-N260Q-H272V, S225G-N260Q-S279D, S225G-N260Q-Y281P, S225G-N260Q-K30 8Q, S225G-N260Q-K309E, S225G-N260Q-K312Q, S225G-H272V-S279D, S225G-H272V-Y281P, S225G-H272V-K308Q, S225G-H272V-K309E, S225G-H272V-K312Q, S225G-S279D-Y281P, S225G-S279D-K308Q, S225G-S279D-K309E, S225G-S279D-K312Q, S225G-Y281 P-K308Q, S225G-P-K3 09E, S225G-Y281 P-K312Q, S225G-K308Q-K309E, S225G-K308Q-K312Q, S225G-K309E-K312Q, S225G-K308Q-K309E-K312Q, S225G-N227T-N252P-S186R-N260Q-K308E-K309E-K312E, N227T-N252P, N227T-N267T, N227T-F276A, N227T-Y281P, N227T-K308Q, N227T-K308E, 7T-K309E, N227T-K312Q, N227T-K312E, N227T-E232D, N227T-G235W, N227T-N260Q, N227T-H272V, N227T-S279D, N227T-E232D-G235W, N227T-E232D-N252P, N227T-E232D-N260Q, N227T-E232D-H272V, N227T-E232D-S279D, N227T-E232D-Y281P, N227T-E232D-K308Q, N227T-E232D-K30 9E, N227T-E232D-K312Q, N227T-G235W-N252P, N227T-G235W-N260Q, N227T-G235W-H272V, N227T-G235W-S279D, N227T-G235W-Y281P, N227T-G235W-K308Q, N227T-G235W-K309E, N227T-G235W-K312Q, N227T-N252P-N260Q, N227T-N252P-H272V, N227T-N252P-S279D, N227T-N252P-Y28 1P, N227T-N252P-K308Q, N227T-N252P-K309E, N227T-N252P-K312Q, N227T-N260Q-H272V, N227T-N260Q-S279D, N227T-N260Q-Y281P, N227T-N260Q-K308Q, N227T-N260Q-K309E, N227T-N260Q-K312Q, N227T-H272V-S279D, N227T-H272V-Y281P, N227T-H272V-K308Q, N227T-H272V-K30 9E, N227T-H272V-K312Q, N227T-S279D-Y281P, N227T-S279D-K308Q, N227T-S279D-K309E, N227T-S279D-K312Q, N227T-Y281P-K308Q, N227T-Y281 P-K309E, N227T-Y281 P-K312Q, N227T-K308Q-K309E, N227T-K308Q-K312Q, N227T-K309E-K312Q, N227T-N252P-K308E, N227T-N252P-K312E, N227T-N 252P-N267T, N227T-N267T-F276A, N227T-N267T-K308E, N227T-N267T-K309E, N227T-N267T-K312E, N227T-F276A-K308E, N227T-F276A-K309E, N227T-F276A-K312E, N227T-K308E-K309E, N227T-K308E-K312E, N227T-K309E-K312E, N227T-F276A-K308E-K309E, N227T-F276A-K308E-K312E, 7T-F276A-K309E-K312E, N227T-K308E- K309E-K312E, N227T-S225G-K308Q-K309E, N227T-S225G-K308Q-K312Q, N227T-S225G-K309E- K312Q, N227T-K308Q-K309E-K312Q, N227T-N267T-F276A-K308E, N227T-N267T-F276A-K309E, N227T-N267T-F276A-K312E, N227T-N267T-S225G-K308Q, N22 7T-N267T-S225G-K309E, N227T-N267T-S225G-K312Q, N227T-N252P-N267T-F276A-K308E, N227T-N252P-N267T-F276A-K309E, N227T-N252P-N267T-K308E-K309E, N227T-N252P-F276A-K308E-K309E, N227T-N267T-F276A-K308E-K309E, N227T-F276A-K308E-K309E-K312E, 7T-N252P-E232D-S225G-K308Q, N227T-N252P-E232D-S225G-K309E, N227T-N252P-E232D-K308Q-K309E, N227T-N252P-S225G-K308Q-K309E, N227T-E232D-S225G-K308Q-K309E, N227T-S225G-K308Q-K309E-K312Q, N227T-N267T-F276A-K308E-K312E, N227T-N267T-F276A-K309E-K312E, N22 7T-E232D-S225G-K308Q-K312Q, N227T-E232D-S225G-K309E-K312Q, N227T-N267T-F276A-K308E-K309E-K312E, N227T-N252P- N227T-N252P-N267T-F276A-K30 8E-K309E-K312E, N227T-N252P-S225G- S186R-K308Q-K309E-K312Q, E232D-G235W, E232D-N252P, E232D-N260Q, E232D-H272V, E232D-S279D, E232D-Y281P, E232D-K308Q, E232D-K309E, E232D-K312Q, E232D-G235W-N252P, E232D-G235W-N260Q, E232D-G235W-H272V, E232D-G235W-S279D, E23 2D-G235W-Y281P, E232D-G235W-K308Q, E232D-G235W-K309E, E232D-G235W-K312Q, E232D-N252P-N260Q, E232D-N252P-H272V, E232D-N252P-S279D, E232D-N252P-Y281P, E232D-N252P-K308Q, E232D-N252P-K309E, E232D-N252P-K312Q, E232D-N260Q-H272V, E232D-N260Q-S279D, E232D-N260Q-Y28 1P, E232D-N260Q-K308Q, E232D-N260Q-K309E, E232D-N260Q-K312Q, E232D-H272V-S279D, E232D-H272V-Y281P, E232D-H272V-K308Q, E232D-H272V-K309E, E232D-H272V-K312Q, E232D-S279D-Y281P, E232D-S279D-K308Q, E232D-S279D-K309E, E232D-S279D-K312Q, E232D-Y281 08Q, E232D-Y281 P-K309E, E232D-Y281 P-K312Q, E232D-K308Q-K309E, E232D-K308Q-K312Q, E232D-K309E-K312Q, G235W-N252P, G235W-N260Q, G235W-H272V, G235W-S279D, G235W-Y281P, G235W-K308Q, G235W-K309E, G235W-K312Q, G235W-N252P-N260Q, G235W-N252P-H272V, G235W-N252P-S27 9D, G235W-N252P-Y281P, G235W-N252P-K308Q, G235W-N252P-K309E, G235W-N252P-K312Q, G235W-N260Q-H272V, G235W-N260Q-S279D, G235W-N260Q-Y281P, G235W-N260Q-K308Q, G235W-N260Q-K309E, G235W-N260Q-K312Q, G235W-H272V-S279D, G235W-H272V-Y281P, G235W-H272V-K30 8Q P-K308Q, G235W-Y281 P-K309E, G235W-Y281 P-K312Q, G235W-K308Q-K309E, G235W-K308Q-K312Q, G235W-K309E-K312Q, G235W-N227T-S186R-K308Q-K 309E-K312Q, G235W-N227T-N252P-S186R-N260Q-K308Q-K309E-K312Q, N252P-N267T, N252P-F276A, N252P-Y281P, N252P-K308Q, N252P-K308E, N252P-K309E, N252P-K312Q, N252P-K312E, N252P-N260Q, N252P-H272V, N252P-S279D, N252P-N260Q-H272V, N252P-N260Q-S279D, N252P-N260Q-Y28 1P, N252P-N260Q-K308Q, N252P-N260Q-K309E, N252P-N260Q-K312Q, N252P-H272V-S279D, N252P-H272V-Y281P, N252P-H272V-K308Q, N252P-H272V-K309E, N252P-H272V-K312Q, N252P-S279D-Y281P, N252P-S279D-K308Q, N252P-S279D-K309E, N252P-S279D-K312Q, N252P-Y281 08Q, N252P-Y281 P-K309E, N252P-Y281 P-K312Q, N252P-K308Q-K309E, N252P-K308Q-K312Q, N252P-K309E-K312Q, N252P-F276A-K308E, N252P-F276A-K309E, N252P-F276A-K312E, N252P-K308E-K309E, N252P-K308E-K312E, N252P-N267T-F276A, N252P-N267T-K308E, N252P-N267T-K30 9E, N252P-N267T-K312E, N252P-N267T-F276A-K308E-K309E, N252P-E232D-S225G-K308Q-K309E, N260Q-H272V, N260Q-S279D, N260Q-Y281P, K308Q, N260Q-K309E, N260Q-K312Q, N260Q-H272V-S279D, N260Q-H272V-Y281 P, N260Q- H272V-K308Q, N260Q-H272V-K309E, N260Q-H272V-K312Q, N260Q-S279D-Y281 P, N260Q- S279D-K308Q, N260Q-S279D-K309E, N260Q-S279D-K312Q, N260Q-Y281 P-K308Q, N260Q- Y281 P-K309E, N260Q-Y281 P-K312Q, N260Q-K308Q-K309E, N260Q-K308Q-K312Q, N260Q-K309E-K312Q, N267T-F276A, N267T-Y281 P, N267T-K308E, N267T-K309E, N267T-K312Q, N267T-K31 2E, N267T-F276A-K308E, N267T-F276A-K309E, N267T-F276A-K312E, N267T-K308E-K309E, N267T-K308E-K312E, N267T-K309E-K312E, H272V-Y281P, H272V-K308Q, H272V-K309E, H272V-K312Q, H272V-S279D-Y281P, H272V-S279D-K308Q, H272V-S279D-K309E, H272V- S279D-K312Q, H272V-Y281 P-K308Q, H272V-Y281 P-K309E, H272V-Y281 P-K312Q, H272V-K308Q-K309E, H272V-K308Q-K312Q, H272V-K309E-K312Q, F27 6A-Y281P, F276A-K308Q, F276A-K308E, F276A-K309E, F276A-K312Q, F276A-K312E, F276A-K308E-K309E, F276A-K308E-K312E, F276A- K309E-K312E, F276A-K308E-K309E-K312E, S279D-Y281P, S279D-K308Q, S279D-K309E, S279D-K312Q, S279D-Y281 P-K308Q, S279D-Y281 P-K309E, S27 9D-Y281 P-K312Q, S279D-K308Q-K309E, S279D-K308Q-K312Q, S279D-K309E-K312Q, Y281 P-K308Q, Y281 P-K308E, Y281 P-K309E, Y281 P-K312Q, Y281 P-K312E, Y281 P-K308Q-K309E, Y281 P-K308Q-K312Q, Y281 P-K309E-K312Q, K308E-K312Q, K308E-K312E, K308Q-K312Q, K309E-K312Q, K309E-K312E, K 308E-K309E, K308Q-K309E, K308Q-K309E-K312Q, K308E-K309E-K312E, K312E-N227T-F276A, K312E-N227T-K308E, K312E-N227T-K309E, K312E-N227T-K312E, K312E-F276A-K308E, K312E-F276A-K309E, K312E-F276A-K312E, K312E-K308E-K309E, K312E-K308E-K312E, K312E-K309E-K31 2E, K312E-N227T-F276A- K308E, K312E-N227T-F276A-K309E, K312E-N227T-F276A-K312E, K312E-N227T-K308E-K309E, K312E-N227T-K309E-K312E, K312E-F276A-K308E-K309E, K312E-F276A-K308E-K312E, K312E-F276A-K309E-K312E, K312E-K308E-K309E-K312E, 2Q-N227T- S225G-K308Q, K312Q-N227T-S225G-K309E, K312Q-N227T-S225G-K312Q, K312Q-N227T-K308Q- K309E, K312Q-N227T-K308Q-K312Q, K312Q-N227T-K309E-K312Q, K312Q-S225G-K308Q-K309E, K312Q-S225G-K308Q-K312Q, K312Q-S225G-K309E-K312Q and K312Q-K308Q-K309E-K312Q, based on the numbering according to SEQ ID NO:1.
In weiter bevorzugten Ausführungsformen wird ein Dispersin verwendet, das ß-1 ,6-N- Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96% oder 96,5% identisch ist, mindestens zehn und zunehmend bevorzugt elf, zwölf, 13, 14, 15, 16, 17, 18 oder mehr Aminosäuresubstitutionen aufweist, wobei das Dispersin eine Aminosäuresubstitutionskombination aufweist, die aus der aus Q3F-A49W-N59E-S163P-S186R-S225G-N227T-N252P-F276A-Y281 P- K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-N227T-E232D-N252P-F276A-S279G-K308E- K309E-K312E, Q3F-T17W-A49W-N59E-S163P-S186R-S225G-N227T-G235W-N252P-H272P- Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-N252P-F276A- S279G-K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P- F276A-S279G-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K-N227T-E232D-N252P-N267T- F276A-S279G-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K-S225G-N227T-N252P-N267T- F276A-S279G-K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-N227T-E232D-N252P-F276A- S279G-Y281 P-K308E-K309E-K312E, Q3F-T17W-A49W-N59E-S163P-S186R-D207N-T218Q-S225G- N227T-G235W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R- S225G-N227T-N252P-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-A49W-N59E-S163P- S186R-S225G-N227T-E232D-N252P-H272V-F276A-S279G-K308E-K309E-K312E, Q3F-H15Y- V140I-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N260Q-N267T-H272V-S279D- Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-S163P-S186R-Q215K-S225G-N227T-E232D-N252P- N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-A49W-N59E-S163P- S186R-T218Q-S225G-N227T-G235W-S237W-N252P-H272P-K308Q-K309E-K312Q, Q3F-H15Y- T17W-A49W-N59E-S163P-S186R-D207N-T218Q-S225G-N227T-G235W-S237W-N252P-H272P- Y281 P-K308Q-K309E-K312Q, Q3F-S163P-S186R-Q215K-N227T-E232D-N252P-N267T-H272V- F276A-S279G-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K-N227T-E232D-N252P-N267T- F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-Q215K-N227T-E232D-N252P-N267T- F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-H15Y-T17W-A49W-N59E-S163P-S186R-T218Q- S225G-N227T-G235W-S237W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-S163P-Q215K- S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-K308E-K309E-K312E, Q3F-A49W- N59E-S163P-S186R-N227T-E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K-S225G-N227T-N252P-N267T-F276A-S279G-Y281 P-K308E-K309E- K312E, Q3F-S163P-Q215K-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E- K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-F276A-S279G-In further preferred embodiments, a dispersin is used which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96% or 96.5% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, at least ten and increasingly preferably eleven, twelve, 13, 14, 15, 16, 17, 18 or more amino acid substitutions, wherein the dispersin has an amino acid substitution combination selected from the group consisting of Q3F-A49W-N59E-S163P-S186R-S225G-N227T-N252P-F276A-Y281 P- K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-N227T-E232D-N252P-F276A-S279G-K308E- K309E-K312E, Q3F-T17W-A49W-N59E-S163P-S186R-S225G-N227T-G235W-N252P-H272P- Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-N252P-F276A- S279G-K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S22 5G-N227T-E232D-N252P- F276A-S279G-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K-N227T-E232D-N252P-N267T- F276A-S279G-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K-S225G-N227T-N252P-N267T- F276A-S279G-K308E-K309E-K312E, Q3F-A49W-N59E-S16 3P-S186R-N227T-E232D-N252P-F276A- S279G-Y281 P-K308E-K309E-K312E, Q3F-T17W-A49W-N59E-S163P-S186R-D207N-T218Q-S225G- N227T-G235W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R- S225G-N227T-N252P-F276A-S279G-Y281 P-K308E-K309E- K312E, Q3F-A49W-N59E-S163P- S186R-S225G-N227T-E232D-N252P-H272V-F276A-S279G-K308E-K309E-K312E, Q3F-H15Y- V140I-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N260Q-N267T-H272V-S279D- Y281 P-K308Q-K309E-K312Q, Q215K-S225G-N227T-E232D-N252P- N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-A49W-N59E-S163P-S186R-T218Q-S225G-N227T-G235W-S237W-N252P-H27 2P-K308Q-K309E-K312Q, Q3F-H15Y- T17W-A49W-N59E-S163P-S186R-D207N-T218Q-S225G-N227T-G235W-S237W-N252P-H272P- Y281 P-K308Q-K309E-K312Q, Q3F-S163P-S186R-Q215K-N227T-E232D-N252P-N267T-H272V- F276A-S279G-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K -N227T-E232D-N252P-N267T- F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-Q215K-N227T-E232D-N252P-N267T- F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-H15Y-T17W-A49W-N59E-S163P-S186R-T218Q- S225G-N227T-G235W-S237W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q 3F-S163P-Q215K- S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-K308E-K309E-K312E, Q3F-A49W- N59E-S163P-S186R-N227T-E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, F276A-S279G-Y281 P-K308E-K309E- K312E, Q3F-S163P-Q215K-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E- K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-F276A-S279G-
Y281 P-K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-N252P-H272V-F276A- S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K-S225G-N227T-E232D-N252P- N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-S163P-S186R-Q215K-N227T- E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S186R- Q215K-S225G-N227T-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F- T17W-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N267T-H272V-F276A-S279G- Y281 P-K308E-K309E-K312Q, Q3F-S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T- H272V-F276A-S279G-Y281 P-K308E-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-S225G- N227T-E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S186R- Q215K-S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N260Q-N267T- H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-S163P-Q215K-S225G-N227T-E232D-N252P- N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-H15Y-S163P-S186R-Q215K- S225G-N227T-E232D-G235W-N252P-N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272P-F276A- S279D-Y281 P-K308E-K309E-K312Q, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T- E232D-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-S163P- S186R-Q215K-S225G-N227T-E232D-N252P-N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E- K312Q, Q3F-H15Y-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N267T-H272V- F276A-S279G-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G- N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y- A49W-N59E-V140I-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N260Q-N267T- H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-A49W-N59E-S163P-S186R-S225G-N227T-Y281 P- K308Q-K309E-K312Q, Q3I-A49W-N59E-S163P-S186R-S225G-E232D-Y281 P-K308Q-K309E- K312Q, Q3I-A49W-N59E-S163P-S186R-S225G-G235W-Y281 P-K308Q-K309E-K312Q, Q3I-A49W- N59E-S163P-S186R-S225G-N252P-Y281 P-K308Q-K309E-K312Q, Q3I-A49W-N59E-S163P-S186R- S225G-N260Q-Y281 P-K308Q-K309E-K312Q, Q3I-A49W-N59E-S163P-S186R-S225G-N227T- H272V-Y281 P-K308Q-K309E, Q3I-A49W-N59E-S163P-S186R-S225G-N227T-S279D-Y281 P-K308Q- K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-N260Q-N267T-H272V- S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D- N252P-N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P- S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312E, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D- Y281 P-K308E-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R- S225G-N227T-E232D-Y281 P-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T- G235W-K308Q-K309E-K312Q, H15Y-A49W-S163P-S186R-S225G-N227T-Y281 P-S288P-K308Q- K309E-K312Q, H 15Y-A49W-S163P-S186R-S225G-N227T-N252P-Y281 P-K308Q-K309E-K312Q, H15Y-A49W-S163P-S186R-S225G-N227T-H272P-Y281 P-K308Q-K309E-K312Q, H15Y-A49W- S163P-S186R-S225G-N227T-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P- S186R-S225G-N227T-E232D-Y281 P-K308Q-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G- N227T-E232D-G235W-N252P-N260Q-H272P-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-A49W- N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308Q- K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-N260Q-H272V- Y281 P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272V-S279D-Y281 P-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G- N227T-E232D-N252P-N260Q-H272P-S279D-Y281 P-S288P-K308Q-K309E-K312Q, H15Y-A49W- N59E-S163P-S186R-S225G-N227T-E232D-N252P-N260Q-H272P-S279D-Y281 P-K308Q-K309E- K312Q, H15Y-T17W-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q- H272V-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-T17W-A49W-N59E-S163P-S186R-S225G- N227T-E232D-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q, A49W-N59E-S163P- S186R-S225G-N227T-E232D-N252P-F276A-S279G-K308E-K309E-K312E, A49W-N59E-S163P- S186R-N227T-E232D-N252P-H272V-F276A-S279G-K308E-K309E-K312E, A49W-N59E-S163P- S186R-N227T-E232D-N252P-F276A-S279G-Y281 P-K308E-K309E-K312E, A49W-N59E-S1 ßSP- SI 86R-S225G-N227T-N252P-F276A-S279G-Y281 P-K308E-K309E-K312E, A49W-N59E-S163P- S186R-S225G-N227T-E232D-N252P-H272V-F276A-S279G-K308E-K309E-K312E, A49W-N59E- S163P-S186R-S225G-N227T-E232D-N252P-F276A-S279G-Y281 P-K308E-K309E-K312E, A49W- N59E-S163P-S186R-N227T-E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, A49W-N59E-S163P-S186R-S225G-N227T-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E- K312E, A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-H272V-F276A-S279G-Y281 P- K308E-K309E-K312E, S163P-S186R-Q215K-N227T-E232D-N252P-N267T-F276A-S279G-Y281 P- K308E-K309E-K312E, S163P-S186R-S225G-N227T-E232D-N252P-N267T-F276A-S279G-Y281 P- K308E-K309E-K312E, S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T-F276A-S279G- Y281 P-K308E-K309E-K312E, S163P-Q215K-S225G-N227T-E232D-N252P-N267T-F276A-S279G- Y281 P-K308E-K309E-K312E, S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T-H272V- F276A-S279G-K308E-K309E-K312E, S163P-Q215K-S225G-N227T-E232D-N252P-N267T-H272V- F276A-S279G-K308E-K309E-K312E, S163P-Q215K-N227T-E232D-N252P-N267T-H272V-F276A- S279G-Y281 P-K308E-K309E-K312E, S163P-S186R-Q215K-S225G-N227T-N252P-N267T-H272V- F276A-S279G-Y281 P-K308E-K309E-K312E, S163P-Q215K-S225G-N227T-N252P-N267T-H272V- F276A-S279G-Y281 P-K308E-K309E-K312E, S163P-Q215K-S225G-N227T-E232D-N252P-N267T- H272V-F276A-S279G-Y281 P-K308E-K309E-K312E und S163P-S186R-Q215K-S225G-N227T- E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E bestehenden Gruppe ausgewählt ist, bezogen auf die Nummerierung gemäß SEQ ID NO:1 . Y281 P-K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-N252P-H272V-F276A- S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S18 6R-Q215K-S225G- N227T-E232D-N252P- N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-S163P-S186R-Q215K-N227T- E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S186R- Q215K-S225G-N227T-N252P-N267T-H272V-F276A-S279G -Y281 P-K308E-K309E- K312E, Q3F- T17W-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N267T-H272V-F276A-S279G- Y281 P-K308E-K309E-K312Q, Q3F-S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T- H272V-F276A-S279G-Y281 P-K308E-K309E-K312Q, N59E-S163P-S186R -S225G- N227T-E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S186R- Q215K-S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T-E 232D-G235W-N252P-N260Q -N267T- H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-S163P-Q215K-S225G-N227T-E232D-N252P- N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-H15Y-S163P-S186R-Q215K- S279D-Y281 P-K308Q- K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272P-F276A- S279D-Y281 P-K308E-K309E-K312Q, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T- E232D-N252P-N260Q-N267T-H272V-S279D-Y281 Q, Q3F-H15Y-S163P - S186R-Q215K-S225G-N227T-E232D-N252P-N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E- K312Q, Q3F-H15Y-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N267T-H272V- F276A-S279G-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-S163 P-S186R-Q215K-S225G - N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y- Q3I-A49W-N5 9E-S163P-S186R-S225G -N227T-Y281 P- K308Q-K309E-K312Q, Q3I-A49W-N59E-S163P-S186R-S225G-E232D-Y281 P-K308Q-K309E- K312Q, Q3I-A49W-N59E-S163P-S186R-S225G-G235W-Y281 P-K308Q-K309E-K312Q, Q3I-A49W-N59E-S163P-S186R-S225G-N252P-Y281 P-K308Q-K309E-K312 Q, Q3I-A49W- N59E-S163P-S186R- S225G-N260Q-Y281 P-K308Q-K309E-K312Q, Q3I-A49W-N59E-S163P-S186R-S225G-N227T- H272V-Y281 P-K308Q-K309E, Q3I-A49W-N59E-S163P-S186R-S225G-N227T-S279D-Y281 P-K308Q- K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G- N227T-E232D- N252P-N260Q-N267T-H272V- S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D- N252P-N260Q-N267T-H272P-S279D-Y281, P-K308Q-K309E-K312Q, 72V-S279D-Y281 P- K308Q-K309E-K312E, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308E-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272V-S279D-Y281 , H15Y-A49W-N59E -S163P-S186R- S225G-N227T-E232D-Y281 P-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T- G235W-K308Q-K309E-K312Q, H15Y-A49W-S163P-S186R-S225G-N227T-Y281 P-S288P-K308Q- K309E-K312Q, H 15Y-A49W-S163P-S186R-S225G-N227T -N252P-Y281 P-K308Q -K309E-K312Q, H15Y-A49W-S163P-S186R-S225G-N227T-H272P-Y281 P-K308Q-K309E-K312Q, H15Y-A49W- S163P-S186R-S225G-N227T-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P- S186R-S225G-N227T-E232D-Y281 P-K308Q-K312Q, H15Y-A 49W-N59E-S163P- S186R-S225G- N227T-E232D-G235W-N252P-N260Q-H272P-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-A49W- N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281, P-K308Q-K309E-K312Q, 227T-E232D-N252P-N260Q -H272V- Y281 P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272V-S279D-Y281 P-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G- N227T-E232D-N252P-N260Q-H272P-S279D-Y281 -K308Q-K309E-K312Q, H15Y-A49W- N59E-S163P-S186R-S225G-N227T-E232D-N252P-N260Q-H272P-S279D-Y281 P-K308Q-K309E- K312Q, H15Y-T17W-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q- H272V-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-T17W-A49W-N59E -S163P-S186R-S225G - N227T-E232D-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q, A49W-N59E-S163P- S186R-S225G-N227T-E232D-N252P-F276A-S279G-K308E-K309E-K312E, A49W-N59E-S163P- S186R-N227T-E232D-N252P-H272V-F276A-S279G-K308E -K309E-K312E, A49W-N59E- S163P- S186R-N227T-E232D-N252P-F276A-S279G-Y281 P-K308E-K309E-K312E, A49W-N59E-S1 ßSP-SI 86R-S225G-N227T-N252P-F276A-S279G-Y281 P-K308E-K309E-K312E, A49W-N59E-S163P- S186R-S225G-N227T-E232D-N252P-H272V-F276A-S279G- K308E-K309E-K312E, A49W -N59E- S163P-S186R-S225G-N227T-E232D-N252P-F276A-S279G-Y281 P-K308E-K309E-K312E, A49W- N59E-S163P-S186R-N227T-E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, F276A-S279G-Y281 P- K308E-K309E- K312E, A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-H272V-F276A-S279G-Y281 P- K308E-K309E-K312E, S163P-S186R-Q215K-N227T-E232D-N252P-N267T-F276A-S279G-Y281 P-K308E-K309E-K312E, S163P-S186R-S225G-N227T-E23 2D-N252P-N267T-F276A-S279G -Y281 P- K308E-K309E-K312E, S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T-F276A-S279G- Y281 P-K308E-K309E-K312E, S163P-Q215K-S225G-N227T-E232D-N252P-N267T-F276A-S279G-Y281 P-K308E-K309E-K312E, S163P-S186R-Q215K-S225G-N 227T-E232D-N252P-N267T -H272V- F276A-S279G-K308E-K309E-K312E, S163P-Q215K-S225G-N227T-E232D-N252P-N267T-H272V- F276A-S279G-K308E-K309E-K312E, S163P-Q215K-N227T-E232D-N252P-N267T-H272V-F276A- S279G-Y281 P-K308E-K309E-K312E, S163P-S186R-Q215K-S225G-N227T-N252P-N267T-H272V- F276A-S279G-Y281 P-K308E-K309E-K312E, S163P-Q21 5K-S225G-N227T-N252P- N267T-H272V- F276A-S279G-Y281 P-K308E-K309E-K312E, S163P-Q215K-S225G-N227T-E232D-N252P-N267T- H272V-F276A-S279G-Y281 P-K308E-K309E-K312E and S163P-S186R-Q215K-S225G-N227T- E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E existing group is selected, based on the numbering according to SEQ ID NO:1 .
In besonders bevorzugten Ausführungsformen wird ein Dispersin verwendet, das ß-1 ,6-N- Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94% oder 95% identisch ist, mindestens 15 und zunehmend bevorzugt 16, 17, 18 oder 19 Aminosäuresubstitutionen aufweist, wobei das Dispersin eine Aminosäuresubstitutionskombination aufweist, die aus der Q3F-T17W- A49W-N59E-S163P-S186R-S225G-N227T-G235W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-T17W-A49W-N59E-S163P-S186R-D207N-T218Q-S225G-N227T-G235W-N252P-H272P- Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P- H272V-F276A-S279G-K308E-K309E-K312E, Q3F-H15Y-V140I-S163P-S186R-Q215K-S225G- N227T-E232D-G235W-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F- H15Y-S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N260Q-N267T-H272V-S279D-Y281 P- K308Q-K309E-K312Q, Q3F-H15Y-T17W-A49W-N59E-S163P-S186R-T218Q-S225G-N227T-G235W- S237W-N252P-H272P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-A49W-N59E-S163P-S186R-D207N- T218Q-S225G-N227T-G235W-S237W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y- T17W-A49W-N59E-S163P-S186R-T218Q-S225G-N227T-G235W-S237W-N252P-H272P-Y281 P- K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-N227T-E232D-N252P-H272V-F276A- S279G-Y281 P-K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D- N252P-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S225G- N227T-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K- S225G-N227T-E232D-N252P-N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E-K312Q, Q3F- S163P-S186R-Q215K-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E- K312E, Q3F-S163P-S186R-Q215K-S225G-N227T-N252P-N267T-H272V-F276A-S279G-Y281 P- K308E-K309E-K312E, Q3F-T17W-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P- N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312Q, Q3F-S163P-S186R-Q215K-S225G- N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312Q, Q3F-A49W- N59E-S163P-S186R-S225G-N227T-E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E- K312E, Q3F-S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G- Y281 P-K308E-K309E-K312E, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T-E232D- G235W-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-S163P-Q215K- S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F- H15Y-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N260Q-N267T-H272P-S279D- Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272P-F276A-S279D-Y281 P-K308E-K309E-K312Q, Q3F-H15Y-T17W-S163P- S186R-Q215K-S225G-N227T-E232D-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E- K312Q, Q3F-H15Y-S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N260Q-N267T-H272P- S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-S163P-S186R-Q215K-S225G-N227T-E232D- G235W-N252P-N267T-H272V-F276A-S279G-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W- S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308Q- K309E-K312Q, Q3F-H15Y-A49W-N59E-V140I-S163P-S186R-Q215K-S225G-N227T-E232D-G235W- N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P- S186R-S225G-N227T-E232D-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-N260Q-N267T-H272P-S279D- Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312E, Q3I-H15Y-A49W-N59E-S163P-S186R- S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308E-K309E-K312Q, Q3I- H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D- Y281 P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272P-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R- S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q, H15Y- A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-N260Q-H272V-Y281 P-K308Q-K309E- K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V- S279D-Y281 P-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P- N260Q-H272P-S279D-Y281 P-S288P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R- S225G-N227T-E232D-N252P-N260Q-H272P-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-T17W- A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P- K308Q-K309E-K312Q, H15Y-T17W-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P- N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q, A49W-N59E-S163P-S186R-S225G-N227T- E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E und S163P-S186R-Q215K- S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E bestehenden Gruppe ausgewählt ist, bezogen auf die Nummerierung gemäß SEQ ID NO:1. In particularly preferred embodiments, a dispersin is used which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94% or 95% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, has at least 15 and increasingly preferably 16, 17, 18 or 19 amino acid substitutions, wherein the dispersin has an amino acid substitution combination which consists of the Q3F-T17W- A49W-N59E-S163P-S186R-S225G-N227T-G235W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-T17W-A49W-N59E-S163P-S186R-D207N-T 218Q-S225G-N227T-G235W-N252P-H272P- Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P- H272V-F276A-S279G-K308E-K309E-K312E, Q3F-H15Y-V140I-S163P-S186R-Q215K-S225G- N227T-E232D-G235W-N252P-N260Q-N267T-H272V-S279D- Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-A49W-N59E-S163P-S186R-T218Q-S225G-N227T-G235W- S237W-N252P-H272P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-A49W-N59E-S16 3P-S186R-D207N- T218Q-S225G-N227T-G235W-S237W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y- T17W-A49W-N59E-S163P-S186R-T218Q-S225G-N227T-G235W-S237W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-N227 T-E232D-N252P-H272V-F276A- S279G-Y281 P-K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D- N252P-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-A49W-N59E-S163P-S186R-S225G- N227T-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S186R-Q 215K- S225G-N227T-E232D-N252P-N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E-K312Q, Q3F- S163P-S186R-Q215K-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-S163P-S186R-Q215K-S225G-N227T-N252P -N267T-H272V-F276A-S279G-Y281 P- K308E-K309E-K312E, Q3F-T17W-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P- N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312Q, Q3F-S163P-S186R-Q215K-S225G- N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312Q, Q3F-A49W- N59E-S163P-S186R-S225G-N227T-E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E- K312E, Q3F-S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F-H15Y-T17W-S163P-S186R-Q21 5K-S225G-N227T-E232D- G235W-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-S163P-Q215K- S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E, Q3F- N252P-N260Q-N267T-H272P-S279D- Y281 P-K308Q-K309E-K312Q, Q3F-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272P-F276A-S279D-Y281 P-K308E-K309E- K312Q, Q3F-H15Y-T17W-S163P- S186R-Q215K-S225G-N227T-E232D-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E- K312Q, Q3F-H15Y-S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N260Q-N267T-H272P- S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-S163P-S186R-Q21 5K-S225G-N227T-E232D- G235W-N252P-N267T-H272V-F276A-S279G-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W- S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-A49W-N59E-V140I-S163P-S1 86R-Q215K-S225G-N227T-E232D-G235W- N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P- S186R-S225G-N227T-E232D-N252P-N260Q-N267T-H272V-S279D-Y281, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E2 32D-N252P-N260Q-N267T-H272P-S279D- Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272V-S279D-Y281, P-K308Q-K309E-K312E, 79D-Y281 P-K308E-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272P-S279D-Y281 P-K308Q-K309E-K312Q, H15Y -A49W-N59E-S163P-S186R- S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q, H15Y- A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-N260Q-H272V-Y281 P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E2 32D-G235W-N252P-N260Q-H272V- S279D-Y281 P-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P- N260Q-H272P-S279D-Y281 P-S288P-K308Q-K309E-K312Q, H15Y-A49W-N59E-S163P-S186R- S225G-N227T-E232D-N252P-N260Q-H272P-S279D-Y281 P -K308Q-K309E-K312Q, H15Y-T17W- A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P- K308Q-K309E-K312Q, H15Y-T17W-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P- N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q, A49W-N59E-S163P-S186R-S225G-N227T- E232D-N252P-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E and S163P-S186R-Q215K- S225G-N227T-E232D-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E-K312E is selected based on the numbering according to SEQ ID NO:1.
In ganz besonders bevorzugten Ausführungsformen wird ein Dispersin verwendet, das ß-1 ,6-N- Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71 %, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93% oder 94% identisch ist, mindestens 18 Aminosäuresubstitutionen aufweist, wobei das Dispersin eine Aminosäuresubstitutionskombination aufweist, die aus der Q3F-H15Y-V140I-S163P-S186R-Q215K- S225G-N227T-E232D-G235W-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-A49W-N59E-S163P-S186R-D207N-T218Q-S225G-N227T-G235W-S237W-N252P- H272P-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-A49W-N59E-S163P-S186R-T218Q-S225G- N227T-G235W-S237W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-T17W-S163P-S186R- Q215K-S225G-N227T-E232D-G235W-N252P-N267T-H272V-F276A-S279G-Y281 P-K308E-K309E- K312Q, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N260Q- N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-S163P-S186R-Q215K-S225G- N227T-E232D-G235W-N252P-N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E-K312Q, Q3F- A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272P-F276A-S279D- Y281 P-K308E-K309E-K312Q, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T-E232D- N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-S163P-S186R- Q215K-S225G-N227T-E232D-G235W-N252P-N267T-H272V-F276A-S279G-Y281 P-K308Q-K309E- K312Q, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T-H272V- F276A-S279G-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-A49W-N59E-V140I-S163P-S186R-Q215K- S225G-N227T-E232D-G235W-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-N260Q-N267T-H272V-S279D- Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P- N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R- S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312E, Q3I- H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D- Y281 P-K308E-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q und H15Y-T17W-A49W-N59E-S163P- S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q bestehenden Gruppe ausgewählt ist, bezogen auf die Nummerierung gemäß SEQ ID NO:1. In very particularly preferred embodiments, a dispersin is used which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93% or 94% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, has at least 18 amino acid substitutions, wherein the dispersin has an amino acid substitution combination which consists of the Q3F-H15Y-V140I-S163P-S186R-Q215K- S225G-N227T-E232D-G235W-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17 W-A49W-N59E-S163P-S186R-D207N-T218Q-S225G-N227T-G235W-S237W-N252P- H272P-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-T17W-A49W-N59E-S163P-S186R-T218Q-S225G- N227T-G235W-S237W-N252P-H272P-Y281 P-K308Q-K309E-K312Q, Q3F-T17W-S163P-S186R- F276A-S279G-Y281 P-K308E-K309E- K312Q, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T-E232D-G235W-N252P-N260Q- N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3F-H15Y-S163P-S186R-Q215K-S225G- Y281 P-K308Q-K309E-K312Q, Q3F- A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272P-F276A-S279D- Y281 P-K308E-K309E-K312Q, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T-E232D- N252P-N260Q-N267T-H272V-S279D-Y281 Q, Q3F-H15Y-S163P-S186R- Q215K-S225G-N227T-E232D-G235W-N252P-N267T-H272V-F276A-S279G-Y281 P-K308Q-K309E- K312Q, Q3F-H15Y-T17W-S163P-S186R-Q215K-S225G-N227T-E232D-N252P-N267T-H272V- F276A-S279G-Y281 P-K308Q-K309E-K312Q, V140I-S163P-S186R-Q215K- S225G-N227T-E232D-G235W-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-N252P-N260Q-N267T-H272V-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S 163P-S186R-S225G-N227T-E232D-N252P- N260Q-N267T-H272P-S279D-Y281 P-K308Q-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R- S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312E 35W-N252P-N260Q-H272V-S279D- Y281 P-K308E-K309E-K312Q, Q3I-H15Y-A49W-N59E-S163P-S186R-S225G-N227T-E232D-G235W- N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q and H15Y-T17W-A49W-N59E-S163P- S186R-S225G-N227T-E232D-G235W-N252P-N260Q-H272V-S279D-Y281 P-K308Q-K309E-K312Q, based on the numbering according to SEQ ID NO:1.
"ß-1 ,6-N-acetylglucosamnidase-Aktivität", wie hierin verwendet, ist gleichbedeutend mit "Hexosaminidase-Aktivität" und/oder "Dispersin-Aktivität" und wird wie folgt bestimmt: Zur Bestimmung der Dispersin-Aktivität werden einer Mikrotiterplatte, die pro Vertiefung 5 pl Probenlösung enthält, 35 pl Dispersin-Assay-Lösung (45 mM Citratpuffer pH 5 mit 0,5 mg/ml p-Nitrophenyl-N-acetyl- ß-D-glucosaminid) hinzugefügt. Die Mikrotiterplatte für 3 Stunden bei Raumtemperatur inkubiert. Nach Inkubation werden 40 pl Stopplösung (0,4 M Na2CO3) hinzugegeben und die Absorption bei 405 nm gemessen. Die erhaltenen Aktivitätswerte werden durch Subtraktion der für eine Referenz ohne Dispersin erhaltenen Absorptionsmessung korrigiert, um Hintergrundrauschen zu eliminieren. Daraus kann die Restaktivität (RA) für die jeweilige Dispersinvariante im Vergleich zu einem Referenzdispersin berechnet werden. "ß-1,6-N-acetylglucosamnidase activity" as used herein is synonymous with "hexosaminidase activity" and/or "dispersin activity" and is determined as follows: To determine dispersin activity, 35 μl of dispersin assay solution (45 mM citrate buffer pH 5 with 0.5 mg/ml p-nitrophenyl-N-acetyl-ß-D-glucosaminide) is added to a microtiter plate containing 5 μl of sample solution per well. The microtiter plate is incubated for 3 hours at room temperature. After incubation, 40 μl of stop solution (0.4 M Na2CO3) is added and the absorbance is measured at 405 nm. The activity values obtained are corrected by subtracting the absorbance measurement obtained for a reference without dispersin in order to eliminate background noise. From this, the residual activity (RA) for the respective dispersin variant can be calculated in comparison to a reference dispersin.
Bei den hierin genannten Enzymen handelt es sich vorzugsweise um reife (mature) Enzyme, d.h. um das katalytisch aktive Molekül ohne Signal- und/oder Propeptid(e). Soweit nicht anders angegeben beziehen sich auch die angegebenen Sequenzen auf jeweils reife (prozessierte) Enzyme. The enzymes mentioned here are preferably mature enzymes, i.e. the catalytically active molecule without signal and/or propeptide(s). Unless otherwise stated, the sequences given also refer to mature (processed) enzymes.
In verschiedenen Ausführungsformen der Erfindung ist das jeweilige Enzym ein frei vorliegendes Enzym. Dies bedeutet, dass das Enzym mit allen Komponenten des Mittels direkt agieren kann und, falls es sich bei dem Mittel um ein Flüssigmittel handelt, dass das Enzym direkt mit dem Lösungsmittel des Mittels (z.B. Wasser) in Kontakt steht. In anderen Ausführungsformen kann ein Mittel Enzyme enthalten, die einen Interaktionskomplex mit anderen Molekülen bilden oder die eine "Umhüllung" enthalten. Hierbei kann ein einzelnes oder mehrere Enzymmolekül(e) durch eine sie umgebende Struktur von den anderen Bestandteilen des Mittels getrennt sein. Eine solche trennende Struktur kann entstehen durch, ist allerdings nicht beschränkt auf, Vesikel, wie etwa eine Micelle oder ein Liposom. Die umgebende Struktur kann aber auch ein Viruspartikel, eine bakterielle Zelle oder eine eukaryotische Zelle sein. In verschiedenen Ausführungsformen kann ein Mittel Zellen von Bacillus pumilus oder Bacillus subtilus, die die erfindungsgemäßen Proteasen exprimieren, oder Zellkulturüberstände solcher Zellen enthalten. In various embodiments of the invention, the respective enzyme is a free enzyme. This means that the enzyme can act directly with all components of the agent and, if the agent is a liquid agent, that the enzyme is in direct contact with the solvent of the agent (eg water). In other embodiments, an agent can contain enzymes which form an interaction complex with other molecules or which contain a "coating". In this case, a single or multiple enzyme molecule(s) can be separated from the other components of the agent by a structure surrounding them. Such a separating structure can be created by, but is not limited to, vesicles, such as a micelle or a liposome. The surrounding structure can also be a virus particle, a bacterial cell or a eukaryotic cell. In various embodiments, an agent can contain cells of Bacillus pumilus or Bacillus subtilus which express the proteases according to the invention, or cell culture supernatants of such cells.
Im Zusammenhang mit der vorliegenden Erfindung bedeutet das Merkmal, dass ein Enzym die angegebene(n) Substitution(en) (oder Deletion oder Insertion) aufweist, dass sie an der jeweiligen Position eine (der angegebenen) Substitution(en) (oder Deletion oder Insertion) enthält, d.h. zumindest die angegebenen Positionen nicht anderweitig mutiert oder, beispielsweise durch Fragmentierung des Enzyms, deletiert sind. In verschiedenen Ausführungsformen weisen die hierin beschriebenen Enzyme mit Ausnahme der explizit erwähnten Substitutionen die Sequenz der jeweiligen Referenzsequenz auf, d.h. sind abgesehen von den substituierten Positionen 100% identisch zu der jeweiligen Referenzsequenz. In the context of the present invention, the feature that an enzyme has the specified substitution(s) (or deletion or insertion) means that it contains one (of the specified) substitution(s) (or deletion or insertion) at the respective position, i.e. at least the specified positions are not otherwise mutated or deleted, for example by fragmentation of the enzyme. In various embodiments, the enzymes described herein have the sequence of the respective reference sequence with the exception of the explicitly mentioned substitutions, i.e. are 100% identical to the respective reference sequence apart from the substituted positions.
Die Bestimmung der Identität von Nukleinsäure- oder Aminosäuresequenzen erfolgt durch einen Sequenzvergleich. Dieser Sequenzvergleich basiert auf dem im Stand der Technik etablierten und üblicherweise genutzten BLAST-Algorithmus (vgl. z.B. Altschul et al., Basic local alignment search tool, J. Mol. Biol., 1990, 215: 403-410, und Altschul et al., Gapped BLAST and PSI-BLAST: a new generation of protein database search programs, Nucleic Acids Res., 1997, 25: 3389-3402) und geschieht prinzipiell dadurch, dass ähnliche Abfolgen von Nukleotiden oder Aminosäuren in den Nukleinsäure- oder Aminosäuresequenzen einander zugeordnet werden. Eine tabellarische Zuordnung der betreffenden Positionen wird als Alignment bezeichnet. Ein weiterer im Stand der Technik verfügbarer Algorithmus ist der FASTA-Algorithmus. Sequenzvergleiche (Alignments), insbesondere multiple Sequenzvergleiche, werden mit Computerprogrammen erstellt. Häufig genutzt werden beispielsweise die Clustal-Serie (vgl. z.B. Chenna et al., Multiple sequence alignment with the Clustal series of programs, Nucleic Acid Res., 2003, 31 : 3497-3500), T-Coffee (vgl. z.B. Notredame et al., T-Coffee: A novel method for multiple sequence alignments, J. Mol. Biol., 2000, 302: 205-217) oder Programme, die auf diesen Programmen bzw. Algorithmen basieren. Ferner möglich sind Sequenzvergleiche (Alignments) mit dem Computer-Programm Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, Kalifornien, USA) mit den vorgegebenen Standardparametern, dessen AlignX-Modul für die Sequenzvergleiche auf ClustalW basiert, oder Clone Manager 10 (Verwendung der Scoring Matrix BLOSUM 62 für Sequenz-Alignment auf Aminosäureebene). Soweit nicht anders angegeben, wird die hierin angegebene Sequenzidentität mit dem BLAST-Algorithmus bestimmt. The identity of nucleic acid or amino acid sequences is determined by comparing sequences. This sequence comparison is based on the BLAST algorithm, which is established and commonly used in the state of the art (see, for example, Altschul et al., Basic local alignment search tool, J. Mol. Biol., 1990, 215: 403-410, and Altschul et al., Gapped BLAST and PSI-BLAST: a new generation of protein database search programs, Nucleic Acids Res., 1997, 25: 3389-3402) and is carried out in principle by assigning similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences to one another. A tabular assignment of the relevant positions is referred to as an alignment. Another algorithm available in the state of the art is the FASTA algorithm. Sequence comparisons (alignments), in particular multiple sequence comparisons, are created using computer programs. Frequently used programs include the Clustal series (see e.g. Chenna et al., Multiple sequence alignment with the Clustal series of programs, Nucleic Acid Res., 2003, 31 : 3497-3500), T-Coffee (see e.g. Notredame et al., T-Coffee: A novel method for multiple sequence alignments, J. Mol. Biol., 2000, 302: 205-217) or programs based on these programs or algorithms. Furthermore, sequence comparisons (alignments) are possible using the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the specified standard parameters, whose AlignX module for sequence comparisons is based on ClustalW, or Clone Manager 10 (use of the BLOSUM 62 scoring matrix for sequence alignment at the amino acid level). Unless otherwise stated, the sequence identity stated here is determined using the BLAST algorithm.
Solch ein Vergleich erlaubt auch eine Aussage über die Ähnlichkeit der verglichenen Sequenzen zueinander. Sie wird üblicherweise in Prozent Identität, das heißt dem Anteil der identischen Nukleotide oder Aminosäurereste an denselben oder in einem Alignment einander entsprechenden Positionen angegeben. Der weiter gefasste Begriff der Homologie bezieht bei Aminosäuresequenzen konservierte Aminosäure-Austausche in die Betrachtung mit ein, also Aminosäuren mit ähnlicher chemischer Aktivität, da diese innerhalb des Proteins meist ähnliche chemische Aktivitäten ausüben. Daher kann die Ähnlichkeit der verglichenen Sequenzen auch Prozent Homologie oder Prozent Ähnlichkeit angegeben sein. Identitäts- und/oder Homologieangaben können über ganze Polypeptide oder Gene oder nur über einzelne Bereiche getroffen werden. Homologe oder identische Bereiche von verschiedenen Nukleinsäure- oder Aminosäuresequenzen sind daher durch Übereinstimmungen in den Sequenzen definiert. Solche Bereiche weisen oftmals identische Funktionen auf. Sie können klein sein und nur wenige Nukleotide oder Aminosäuren umfassen. Oftmals üben solche kleinen Bereiche für die Gesamtaktivität des Proteins essenzielle Funktionen aus. Es kann daher sinnvoll sein, Sequenzübereinstimmungen nur auf einzelne, ggf. kleine Bereiche zu beziehen. Soweit nicht anders angegeben beziehen sich Identitäts- oder Homologieangaben in der vorliegenden Anmeldung aber auf die Gesamtlänge der jeweils angegebenen Nukleinsäure- oder Aminosäuresäuresequenz. Such a comparison also allows a statement to be made about the similarity of the sequences being compared. This is usually expressed as percent identity, i.e. the proportion of identical nucleotides or amino acid residues in the same or in an alignment corresponding Positions are given. The broader term homology includes conserved amino acid exchanges in amino acid sequences, i.e. amino acids with similar chemical activity, since these usually exert similar chemical activities within the protein. Therefore, the similarity of the compared sequences can also be given as percent homology or percent similarity. Identity and/or homology statements can be made for entire polypeptides or genes or just for individual regions. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by similarities in the sequences. Such regions often have identical functions. They can be small and contain only a few nucleotides or amino acids. Such small regions often perform essential functions for the overall activity of the protein. It can therefore be useful to relate sequence similarities only to individual, possibly small regions. Unless otherwise stated, identity or homology statements in the present application refer to the total length of the nucleic acid or amino acid sequence specified in each case.
Im Zusammenhang mit der vorliegenden Erfindung bedeutet die Angabe, dass eine Aminosäureposition einer numerisch bezeichneten Position in SEQ ID NO:1 entspricht daher, dass die entsprechende Position der numerisch bezeichneten Position in SEQ ID NO:1 in einem wie oben definierten Alignment zugeordnet ist. In the context of the present invention, the statement that an amino acid position corresponds to a numerically designated position in SEQ ID NO:1 therefore means that the corresponding position is assigned to the numerically designated position in SEQ ID NO:1 in an alignment as defined above.
Für die Beschreibung von Substitutionen, die genau eine Aminosäureposition betreffen (Aminosäureaustausche), wird hierin folgende Konvention angewendet: zunächst wird die natürlicherweise vorhandene Aminosäure in Form des international gebräuchlichen Einbuchstaben- Codes bezeichnet, dann folgt die zugehörige Sequenzposition und schließlich die eingefügte Aminosäure. Mehrere oder alternative Austausche innerhalb derselben Polypeptidkette werden durch Schrägstriche voneinander getrennt. "130D/V" bedeutet somit, dass die Position 130 zu D oder V mutiert ist. Bei Insertionen sind nach der Sequenzposition zusätzliche Aminosäuren benannt. Bei Deletionen ist die fehlende Aminosäure durch ein Symbol, beispielsweise einen Stern oder einen Strich, ersetzt oder vor der entsprechenden Position ein A angegeben. Beispielsweise beschreibt P9T die Substitution von Prolin an Position 9 durch Threonin, P9TH die Insertion von Histidin nach der Aminosäure Threonin an Position 9 und P9* oder AP9 die Deletion von Prolin an Position 9. Diese Nomenklatur ist dem Fachmann auf dem Gebiet der Enzymtechnologie bekannt. The following convention is used to describe substitutions that affect exactly one amino acid position (amino acid exchanges): first, the naturally occurring amino acid is designated in the form of the internationally used one-letter code, then the corresponding sequence position and finally the inserted amino acid. Multiple or alternative exchanges within the same polypeptide chain are separated from one another by slashes. "130D/V" thus means that position 130 is mutated to D or V. In the case of insertions, additional amino acids are named after the sequence position. In the case of deletions, the missing amino acid is replaced by a symbol, for example an asterisk or a dash, or an A is given in front of the corresponding position. For example, P9T describes the substitution of proline at position 9 by threonine, P9TH the insertion of histidine after the amino acid threonine at position 9 and P9* or AP9 the deletion of proline at position 9. This nomenclature is known to those skilled in the art of enzyme technology.
Einem Fachmann ist es über heutzutage allgemein bekannte Methoden, wie beispielsweise die chemische Synthese oder die Polymerase-Kettenreaktion (PCR) in Verbindung mit molekularbiologischen und/oder proteinchemischen Standardmethoden möglich, anhand bekannter DNA- und/oder Aminosäuresequenzen die entsprechenden Nukleinsäuren bis hin zu vollständigen Genen herzustellen. Derartige Methoden sind beispielsweise aus Sambrook, J., Fritsch, E.F. and Maniatis, T. 2001. Molecular cloning: a laboratory manual, 3. Edition Cold Spring Laboratory Press, bekannt. A person skilled in the art can use methods that are generally known today, such as chemical synthesis or the polymerase chain reaction (PCR) in conjunction with standard molecular biological and/or protein chemical methods, to produce the corresponding nucleic acids, including complete genes, based on known DNA and/or amino acid sequences. Such methods are known, for example, from Sambrook, J., Fritsch, E.F. and Maniatis, T. 2001. Molecular cloning: a laboratory manual, 3rd Edition Cold Spring Laboratory Press.
Unter Reinigungsleistung wird im Rahmen der Erfindung das Vermögen eines Mittels, eine vorhandene Anschmutzung teilweise oder vollständig zu entfernen, insbesondere die Aufhellungsleistung an einer oder mehreren Anschmutzungen auf Textilien, verstanden. Ferner umfasst die Reinigungsleistung im Rahmen der vorliegenden Erfindung auch das Vermögen mikrobiell bedingte Ablagerungen, Biobeläge und der dergleichen von Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, zu entfernen. Insbesondere umfasst ist auch die fasertiefe Reinigung von Textilien ("Deep Clean"). Die erfindungsgemäße Reinigungsleistung umfasst insbesondere auch die Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt die fasertiefe Reinigung von Textilien und/oder die Verbesserung der Hygiene von Textilien. Im Rahmen der Erfindung weisen sowohl ein Mittel, welches Enzyme umfasst, bzw. die durch dieses Mittel gebildete Wasch-/Reinigungsflotte, als auch das jeweilige Enzym selbst eine jeweilige Reinigungsleistung auf. Die Reinigungsleistung des Enzyms trägt somit zur Reinigungsleistung des Mittels bzw. der durch das Mittel gebildeten Wasch-ZReinigungsflotte bei. Die Reinigungsleistung wird bevorzugt ermittelt wie weiter unten angegeben. In the context of the invention, cleaning performance is defined as the ability of an agent to partially or completely remove existing soiling, in particular the By "cleaning performance" is meant the brightening performance of one or more stains on textiles. Furthermore, the cleaning performance within the scope of the present invention also includes the ability to remove microbial deposits, bio-deposits and the like from textiles, dishes and other surfaces, in particular household surfaces. In particular, this also includes the deep cleaning of textiles ("deep clean"). The cleaning performance according to the invention also includes in particular the prevention and/or reduction and/or removal of microbial deposits on textiles, dishes and surfaces, in particular household surfaces, particularly preferably the deep cleaning of textiles and/or the improvement of the hygiene of textiles. Within the scope of the invention, both an agent which comprises enzymes or the washing/cleaning liquor formed by this agent and the respective enzyme itself have a respective cleaning performance. The cleaning performance of the enzyme thus contributes to the cleaning performance of the agent or the washing/cleaning liquor formed by the agent. The cleaning performance is preferably determined as stated below.
Unter wasch- bzw. Reinigungsflotte wird diejenige das Wasch- bzw. Reinigungsmittel enthaltende Gebrauchslösung verstanden, die auf die Textilien oder Gewebe bzw. Oberflächen, insbesondere Geschirr oder Haushaltsoberflächen, einwirkt und damit mit den auf den Textilien oder Geweben bzw. Oberflächen vorhandenen Anschmutzungen in Kontakt kommt. Üblicherweise entsteht die Wasch-ZReinigungsflotte, wenn der Wasch-ZReinigungsvorgang beginnt und das Mittel z.B. in einer Wasch- oder Geschirrspülmaschine oder in einem anderen geeigneten Behältnis mit Wasser verdünnt wird. The term washing or cleaning liquor refers to the solution containing the washing or cleaning agent that acts on the textiles or fabrics or surfaces, in particular dishes or household surfaces, and thus comes into contact with the dirt present on the textiles or fabrics or surfaces. The washing/cleaning liquor is usually created when the washing/cleaning process begins and the agent is diluted with water, for example in a washing machine or dishwasher or in another suitable container.
Die Reinigungsleistung an Textilien oder Geweben kann in einem Waschsystem bestimmt werden, das ein Waschmittel in einer Dosierung zwischen 2,0 und 8,0 Gramm pro Liter Waschflotte sowie das zu untersuchende Enzym enthält. Zu vergleichende Enzyme werden konzentrationsgleich (bezogen auf aktives Protein) eingesetzt. Durch den aktivitätsgleichen Einsatz der Enzyme wird sichergestellt, dass auch bei einem etwaigen Auseinanderklaffen des Verhältnisses von Aktivsubstanz zu Gesamtprotein (die Werte der spezifischen Aktivität) die jeweiligen enzymatischen Eigenschaften, also z.B. die Reinigungsleistung an bestimmten Anschmutzungen, verglichen werden. Generell gilt, dass eine niedrige spezifische Aktivität durch Zugabe einer größeren Proteinmenge ausgeglichen werden kann. Ferner können die zu untersuchenden Enzyme auch in gleicher Stoffmenge oder Gewichtsmenge eingesetzt werden, falls die zu untersuchenden Enzyme in einem Aktivitätstest eine unterschiedliche Affinität an das Testsubstrat aufweisen. Der Ausdruck "gleiche Stoffmenge" bezieht sich in diesem Zusammenhang auf eine molgleiche Verwendung der zu untersuchenden Enzyme. Der Ausdruck "gleiche Gewichtsmenge" bezieht sich auf einen gewichtsgleichen Einsatz der zu untersuchenden Enzyme. The cleaning performance of textiles or fabrics can be determined in a washing system that contains a detergent in a dosage of between 2.0 and 8.0 grams per liter of washing liquor and the enzyme to be tested. Enzymes to be compared are used at the same concentration (based on active protein). Using the enzymes with the same activity ensures that even if there is a discrepancy in the ratio of active substance to total protein (the values of the specific activity), the respective enzymatic properties, e.g. the cleaning performance on certain stains, are compared. In general, a low specific activity can be compensated by adding a larger amount of protein. Furthermore, the enzymes to be tested can also be used in the same amount of substance or weight if the enzymes to be tested have a different affinity for the test substrate in an activity test. The term "same amount of substance" in this context refers to using the same mole of the enzymes to be tested. The term "equal amount by weight" refers to the use of equal weight of the enzymes to be investigated.
Die Konzentration des Enzyms in dem für dieses Waschsystem bestimmten Waschmittel beträgt 0,0001 bis 0,1 Gew.-%, insbesondere 0,001 bis 0,1 Gew.-%, weiter bevorzugt 0,01 bis 0,06 Gew.-% und besonders bevorzugt 0,001 bis 0,02 Gew.-%, bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren (Bicinchoninsäure; 2,2‘-Bichinolyl-4,4‘-dicarbonsäure) oder dem Biuret-Verfahren (Gornall et al., J. Biol. Chem. 1948, 177: 751-766) bestimmt werden. Die Bestimmung der Aktivproteinkonzentration kann diesbezüglich über eine Titration der aktiven Zentren unter Verwendung eines geeigneten irreversiblen Inhibitors und Bestimmung der Restaktivität (vgl. Bender et al., J. Am. Chem. Soc. 1966, 88, 24: 5890-5913) erfolgen. The concentration of the enzyme in the detergent intended for this washing system is 0.0001 to 0.1 wt.%, in particular 0.001 to 0.1 wt.%, more preferably 0.01 to 0.06 wt.% and particularly preferably 0.001 to 0.02 wt.%, based on active protein. The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method (Gornall et al., J. Biol. Chem. 1948, 177: 751-766). The active protein concentration can be determined by titrating the active centers using a suitable irreversible inhibitor and determining the residual activity (cf. Bender et al., J. Am. Chem. Soc. 1966, 88, 24: 5890-5913).
Ein flüssiges Referenzwaschmittel für ein solches Waschsystem kann z.B. wie folgt zusammengesetzt sein (alle Angaben in Gewichts-Prozent (Gew .-%)): 4,4% Alkylbenzolsulfonsäure, 5,6% weitere anionische Tenside, 2,4% C12-18 Na-Salze von Fettsäuren (Seifen), 4,4% nicht-ionische Tenside, 0,2% Phosphonate, 1 ,4% Zitronensäure, 0,95% NaOH, 0,01% Entschäumer, 2% Glycerin, 0,08% Konservierungsstoffe, 1% Ethanol, Rest demineralisiertes Wasser. Bevorzugt beträgt die Dosierung des flüssigen Waschmittels zwischen 3,0 und 6,0 Gramm pro Liter Waschflotte, beispielsweise 3,0, 3,2, 3,5, 3,7, 4,0, 4,5, 4,7, 4,9 oder 5,9 Gramm pro Liter Waschflotte. Bevorzugt wird gewaschen in einem pH-Wertebereich zwischen pH 7 und pH 10,5, bevorzugt zwischen pH 8 und pH 9. A liquid reference detergent for such a washing system can, for example, be composed as follows (all information in percent by weight (wt. %)): 4.4% alkylbenzenesulfonic acid, 5.6% other anionic surfactants, 2.4% C12-18 Na salts of fatty acids (soaps), 4.4% non-ionic surfactants, 0.2% phosphonates, 1.4% citric acid, 0.95% NaOH, 0.01% defoamers, 2% glycerin, 0.08% preservatives, 1% ethanol, remainder demineralized water. The dosage of the liquid detergent is preferably between 3.0 and 6.0 grams per liter of washing liquor, for example 3.0, 3.2, 3.5, 3.7, 4.0, 4.5, 4.7, 4.9 or 5.9 grams per liter of washing liquor. Washing is preferably carried out in a pH value range between pH 7 and pH 10.5, preferably between pH 8 and pH 9.
Die Reinigungsleistung wird gegenüber einer Anschmutzung auf Textil durch Messung des Reinigungsgrades der gewaschenen Textilien bestimmt. Beispielsweise kann der Waschvorgang für 60 Minuten bei einer Temperatur von 40°C erfolgen und das Wasser eine Wasserhärte zwischen 15,5°dH und 16,5°dH (deutsche Härte) aufweisen. The cleaning performance is determined by measuring the degree of cleaning of the washed textiles compared to soiling on textiles. For example, the washing process can take place for 60 minutes at a temperature of 40°C and the water can have a water hardness between 15.5°dH and 16.5°dH (German hardness).
Der Weißegrad, d.h. die Aufhellung der Anschmutzungen, als Maß für die Reinigungsleistung wird mit optischen Messverfahren bestimmt, bevorzugt photo metrisch. Ein hierfür geeignetes Gerät ist beispielsweise das Spektrometer Minolta CM508d. Üblicherweise werden die für die Messung eingesetzten Geräte zuvor mit einem Weißstandard, bevorzugt einem mitgelieferten Weißstandard, kalibriert. The degree of whiteness, i.e. the lightening of the soiling, as a measure of the cleaning performance is determined using optical measuring methods, preferably photometric. One suitable device for this is the Minolta CM508d spectrometer. The devices used for the measurement are usually calibrated beforehand with a white standard, preferably a supplied white standard.
Bevorzugte Ausführungsformen erfindungsgemäßer Verwendungen und Mittel erzielen solche vorteilhaften Reinigungsleistungen auch schon bei niedrigen Temperaturen, vorzugsweise in einem Temperaturbereich von etwa 10°C bis etwa 60°C, bevorzugt etwa 15°C bis etwa 40°C, besonders bevorzugt etwa 20°C bis etwa 30°C. Preferred embodiments of uses and agents according to the invention achieve such advantageous cleaning performance even at low temperatures, preferably in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
In einer bevorzugten Ausführungsform kann das erfindungsgemäße Dispersin, wie hierin beschrieben, in einem Wasch- und Reinigungsmittel eingesetzt werden. Zu solchen erfindungsgemäßen Wasch- und Reinigungsmitteln zählen alle denkbaren Wasch- oder Reinigungsmittelarten, sowohl Konzentrate als auch unverdünnt anzuwendende Mittel, zum Einsatz im kommerziellen Maßstab, in der Waschmaschine oder bei der Handwäsche bzw. -reinigung. Dazu gehören beispielsweise Waschmittel für Textilien, Teppiche, oder Naturfasern, für die die Bezeichnung Waschmittel verwendet wird. Dazu gehören beispielsweise auch Geschirrspülmittel für Geschirrspülmaschinen (maschinelle Geschirrspülmittel) oder manuelle Geschirrspülmittel oder Reiniger für harte Oberflächen wie Metall, Glas, Porzellan, Keramik, Kacheln, Stein, lackierte Oberflächen, Kunststoffe, Holz oder Leder, für die die Bezeichnung Reinigungsmittel verwendet wird, also neben manuellen und maschinellen Geschirrspülmitteln beispielsweise auch Scheuermittel, Glasreiniger, WC-Duftspüler, usw. Zu den Wasch- und Reinigungsmittel im Rahmen der Erfindung zählen ferner Waschhilfsmittel, die bei der manuellen oder maschinellen Textilwäsche zum eigentlichen Waschmittel hinzudosiert werden, um eine weitere Wirkung zu erzielen. Ferner zählen zu Wasch- und Reinigungsmittel im Rahmen der Erfindung auch Textilvor- und Nachbehandlungsmittel, also solche Mittel, mit denen das Wäschestück vor der eigentlichen Wäsche in Kontakt gebracht wird, beispielsweise zum Anlösen hartnäckiger Verschmutzungen, und auch solche Mittel, die in einem der eigentlichen Textilwäsche nachgeschalteten Schritt dem Waschgut weitere wünschenswerte Eigenschaften wie angenehmen Griff, Knitterfreiheit oder geringe statische Aufladung verleihen. Zu letztgenannten Mittel werden u.a. die Weichspüler gerechnet. Mit umfasst sind dabei auch Mittel zur Verwendung in (halb-)automatisierten Wasch- oder Reinigungssystemen wie z.B. Wischrobotor oder Nassstaubsauger. In a preferred embodiment, the dispersin according to the invention, as described herein, can be used in a washing and cleaning agent. Such washing and cleaning agents according to the invention include all conceivable types of washing or cleaning agents, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or for hand washing or cleaning. These include, for example, detergents for textiles, carpets or natural fibers, for which the term detergent is used. These also include, for example, dishwashing detergents for dishwashers (machine dishwashing detergents) or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term cleaning agent is used. i.e., in addition to manual and machine dishwashing detergents, for example, scouring agents, glass cleaners, toilet air fresheners, etc. The washing and cleaning agents within the scope of the invention also include washing aids which are added to the actual washing agent during manual or machine textile washing in order to achieve an additional effect. Furthermore, washing and cleaning agents within the scope of the invention also include textile pre- and post-treatment agents, i.e. agents with which the item of laundry is brought into contact before the actual washing, for example to dissolve stubborn dirt, and also agents which, in a step following the actual textile washing, give the laundry other desirable properties such as a pleasant feel, freedom from creasing or low static charge. The latter agents include, among others, fabric softeners. This also includes agents for use in (semi-)automated washing or cleaning systems such as robot mops or wet vacuum cleaners.
Die erfindungsgemäßen Wasch- und/oder Reinigungsmittel, die als pulverförmige oder granuläre Feststoffe, in verdichteter oder nachverdichteter Teilchenform, als homogene Lösungen oder Suspensionen vorliegen können, können neben den erfindungsgemäßen Enzymen alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten, wobei bevorzugt mindestens ein weiterer Inhaltsstoff in dem Mittel vorhanden ist. Die erfindungsgemäßen Mittel können insbesondere Tenside, Builder, Komplexbildner, Polymere, Glaskorrosionsinhibitoren, Korrosionsinhibitoren, Bleichmittel wie Persauerstoffverbindungen, Bleichaktivatoren oder Bleichkatalysatoren, wassermischbare organische Lösungsmittel, Enzymstabilisatoren, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und/oder weitere Hilfsstoffe wie optische Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, Schaumregulatoren sowie Färb- und Duftstoffe enthalten. Vorteilhafte Inhaltsstoffe erfindungsgemäßer Mittel sind offenbart in der internationalen Patentanmeldung WO 2009/121725, dort beginnend auf Seite 5, vorletzter Absatz, und endend auf Seite 13 nach dem zweiten Absatz. Auf diese Offenbarung wird ausdrücklich Bezug genommen und der dortige Offenbarungsgehalt in die vorliegende Patentanmeldung einbezogen. The washing and/or cleaning agents according to the invention, which can be in the form of powdered or granular solids, in compacted or re-compacted particle form, as homogeneous solutions or suspensions, can contain, in addition to the enzymes according to the invention, all known ingredients that are customary in such agents, with at least one further ingredient preferably being present in the agent. The agents according to the invention can in particular contain surfactants, builders, complexing agents, polymers, glass corrosion inhibitors, corrosion inhibitors, bleaching agents such as peroxygen compounds, bleach activators or bleach catalysts, water-miscible organic solvents, enzyme stabilizers, sequestering agents, electrolytes, pH regulators and/or other auxiliary substances such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators and dyes and fragrances. Advantageous ingredients of agents according to the invention are disclosed in the international patent application WO 2009/121725, beginning on page 5, penultimate paragraph, and ending on page 13 after the second paragraph. Express reference is made to this disclosure and the disclosure content therein is incorporated into the present patent application.
Ein erfindungsgemäßes Mittel enthält die erfindungsgemäßen Enzyme jeweils vorteilhafterweise in einer Menge von 2 pg bis 20 mg, vorzugsweise von 5 pg bis 17,5 mg, besonders bevorzugt von 20 pg bis 15 mg und ganz besonders bevorzugt von 50 pg bis 10 mg pro g des Mittels. An agent according to the invention advantageously contains the enzymes according to the invention in an amount of from 2 pg to 20 mg, preferably from 5 pg to 17.5 mg, particularly preferably from 20 pg to 15 mg and very particularly preferably from 50 pg to 10 mg per g of the agent.
Ein erfindungsgemäßes Mittel enthält die erfindungsgemäßen Enzyme zunehmend bevorzugt in einer Menge von jeweils 1 x 10-8 bis 5 Gew.-%, von 0,0001 bis 1 Gew.-%, von 0,0005 bis 0,5 Gew.-%, von 0,001 bis 0,1 Gew. -%, jeweils bezogen auf aktives Protein und bezogen auf das Gesamtgewicht des Mittels. An agent according to the invention contains the enzymes according to the invention increasingly preferably in an amount of from 1 x 10 -8 to 5% by weight, from 0.0001 to 1% by weight, from 0.0005 to 0.5% by weight, from 0.001 to 0.1% by weight, in each case based on active protein and based on the total weight of the agent.
In bevorzugten Ausführungsformen enthält ein erfindungsgemäßes Wasch- und/oder Reinigungsmittel das Dispersin in einer Menge von 0,01 bis 5 Gew.-%, bevorzugt von 0,1 bis 4 Gew.- %, besonders bevorzugt von 0,15 bis 2,5 Gew.-%, bezogen auf das Gesamtgewicht des Mittels. In preferred embodiments, a washing and/or cleaning agent according to the invention contains the dispersin in an amount of 0.01 to 5% by weight, preferably 0.1 to 4% by weight, particularly preferably 0.15 to 2.5% by weight, based on the total weight of the agent.
In bevorzugten Ausführungsformen enthält ein erfindungsgemäßes Wasch- und/oder Reinigungsmittel die mindestens drei weiteren Enzyme, die aus der aus Amylase, Protease, Lipase, Cellulase, Mannanase, Pektatlyase und Mischungen davon ausgewählt sind, insgesamt in einer Menge von 0,01 bis 10 Gew.-%, bevorzugt von 0,1 bis 8 Gew.-%, besonders bevorzugt von 0,2 bis 6 Gew.-%, bezogen auf das Gesamtgewicht des Mittels. In preferred embodiments, a washing and/or cleaning agent according to the invention contains the at least three further enzymes selected from the group consisting of amylase, protease, lipase, Cellulase, mannanase, pectate lyase and mixtures thereof, in total in an amount of 0.01 to 10 wt.%, preferably 0.1 to 8 wt.%, particularly preferably 0.2 to 6 wt.%, based on the total weight of the agent.
Ferner können die in dem Mittel enthaltenen Enzyme und/oder weitere Inhaltsstoffe des Mittels mit einer bei Raumtemperatur oder bei Abwesenheit von Wasser für das Enzym undurchlässigen Substanz umhüllt sein, welche unter Anwendungsbedingungen des Mittels durchlässig für das Enzym wird. Eine solche Ausführungsform der Erfindung ist somit dadurch gekennzeichnet, dass das Enzyme mit einer bei Raumtemperatur oder bei Abwesenheit von Wasser für das Enzym undurchlässigen Substanz umhüllt ist. Weiterhin kann auch das Mittel selbst in einem Behältnis, vorzugsweise einem luftdurchlässigen Behältnis, verpackt sein, aus dem es kurz vor Gebrauch oder während des Waschvorgangs freigesetzt wird. Furthermore, the enzymes contained in the agent and/or other ingredients of the agent can be coated with a substance that is impermeable to the enzyme at room temperature or in the absence of water, which substance becomes permeable to the enzyme under the conditions of use of the agent. Such an embodiment of the invention is thus characterized in that the enzyme is coated with a substance that is impermeable to the enzyme at room temperature or in the absence of water. Furthermore, the agent itself can also be packaged in a container, preferably an air-permeable container, from which it is released shortly before use or during the washing process.
Weitere Ausführungsformen der umfassen alle festen, pulverförmigen, flüssigen, gelförmigen oder pastösen Darreichungsformen erfindungsgemäßer Mittel, die ggf. auch aus mehreren Phasen bestehen können sowie in komprimierter oder nicht komprimierter Form vorliegen können. Das Mittel kann als rieselfähiges Pulver vorliegen, insbesondere mit einem Schüttgewicht von 300 g/l bis 1200 g/l, insbesondere 500 g/l bis 900 g/l oder 600 g/l bis 850 g/l. Zu den festen Darreichungsformen des Mittels zählen ferner Extrudate, Granulate, Tabletten oder Pouches. Alternativ kann das Mittel auch flüssig, gelförmig oder pastös sein, beispielsweise in Form eines nicht-wässrigen Flüssigwaschmittels oder einer nicht-wässrigen Paste oder in Form eines wässrigen Flüssigwaschmittels oder einer wasserhaltigen Paste. Flüssige Mittel sind generell bevorzugt. Weiterhin kann das Mittel als Einkomponentensystem vorliegen. Solche Mittel bestehen aus einer Phase. Alternativ kann ein Mittel auch aus mehreren Phasen bestehen. Ein solches Mittel ist demnach in mehrere Komponenten aufgeteilt. Further embodiments of the invention include all solid, powdery, liquid, gel-like or pasty dosage forms of agents according to the invention, which may optionally also consist of several phases and may be in compressed or non-compressed form. The agent may be in the form of 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 agent also include extrudates, granules, tablets or pouches. Alternatively, the agent may also be liquid, gel-like or pasty, for example in the form of a non-aqueous liquid detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or a water-containing paste. Liquid agents are generally preferred. Furthermore, the agent may be in the form of a one-component system. Such agents consist of one phase. Alternatively, an agent may also consist of several phases. Such a remedy is therefore divided into several components.
In einer bevorzugten Ausführungsform ist das erfindungsgemäße Mittel ein Textilwaschmittel.In a preferred embodiment, the agent according to the invention is a textile detergent.
In einer weiter bevorzugten Ausführungsform ist das erfindungsgemäße Mittel ein flüssiges Textilwaschmittel. In a further preferred embodiment, the agent according to the invention is a liquid textile detergent.
In einer besonders bevorzugten Ausführungsform ist das erfindungsgemäße Mittel ein vorportioniertes Waschmittel, insbesondere eine Waschmittelportionseinheit umfassend eine erfindungsgemäße Waschmittelzubereitung und einen wasserlöslichen Film, welcher die Waschmittelzubereitung vollständig umschließt. In a particularly preferred embodiment, the agent according to the invention is a pre-portioned detergent, in particular a detergent portion unit comprising a detergent preparation according to the invention and a water-soluble film which completely encloses the detergent preparation.
Der wasserlösliche Film, in welche die Waschmittelzubereitung verpackt ist, kann ein oder mehrere strukturell verschiedene wasserlösliche^) Polymer(e) umfassen. Als wasserlösliche(s) Polymer(e) eignen sich insbesondere Polymere aus der Gruppe (gegebenenfalls acetalisierter) Polyvinylalkohole (PVAL) sowie deren Copolymere. Wasserlösliche Filme basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 10000 bis 1000000 g/mol, vorzugsweise von 20000 bis 500000 g/mol, besonders bevorzugt von 30000 bis 100000 g/mol und insbesondere von 40000 bis 80000 g/mol liegt. Geeignete wasserlösliche Filme zum Einsatz werden u.a. von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8630, M8720, M8310, C8400 oder M8900 vertrieben. Geeignet sind beispielsweise auch Filme mit der Bezeichnung Solublon® PT, Solublon® GA, Solublon® KC oder Solublon® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray. The water-soluble film in which the detergent preparation is packaged can comprise one or more structurally different water-soluble polymer(s). Polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and their copolymers are particularly suitable as water-soluble polymer(s). Water-soluble films are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 g/mol, preferably from 20,000 to 500,000 g/mol, particularly preferably from 30,000 to 100,000 g/mol and in particular from 40,000 to 80,000 g/mol. Suitable water-soluble Films for use are sold by MonoSol LLC, for example under the names M8630, M8720, M8310, C8400 or M8900. Also suitable are films called Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.
Wenn die erfindungsgemäßen Waschmittel in flüssiger Form vorliegen, enthalten sie vorzugsweise bezogen auf ihr Gesamtgewicht mehr als 40 Gew.-%, vorzugsweise 50 bis 90 Gew.-% und besonders bevorzugt 60 bis 80 Gew.-% Wasser. When the detergents according to the invention are in liquid form, they preferably contain more than 40% by weight, preferably 50 to 90% by weight and particularly preferably 60 to 80% by weight of water based on their total weight.
Die erfindungsgemäßen Mittel können ein oder mehrere Tenside enthalten, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kommen, aber auch kationische, zwitterionische und/oder amphotere Tenside können enthalten sein. Die Mittel enthalten vorzugsweise 5 bis 70 Gew.-% Tensid, bevorzugt 35 bis 60 Gew.-% und weiter bevorzugt 40 bis 55 Gew.-% Tensid. The agents according to the invention can contain one or more surfactants, with particular emphasis being placed on anionic surfactants, nonionic surfactants and mixtures thereof, but cationic, zwitterionic and/or amphoteric surfactants can also be included. The agents preferably contain 5 to 70% by weight of surfactant, preferably 35 to 60% by weight and more preferably 40 to 55% by weight of surfactant.
Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sulfonat- Gruppen mit bevorzugt Alkaliionen als Kationen enthalten. Verwendbare Seifen sind bevorzugt die Alkalisalze der gesättigten oder ungesättigten C s-Fettsäuren. Derartige Fettsäuren können auch in nicht vollständig neutralisierter Form eingesetzt werden. Zu den brauchbaren Tensiden des Sulfat- Typs gehören die Salze der Schwefelsäurehalbester von C s-Fettalkoholen und die Sulfatierungsprodukte der genannten nichtionischen Tenside mit niedrigem Ethoxylierungsgrad. Zu den verwendbaren Tensiden vom Sulfonat-Typ gehören z.B. Cg-14-Alkylbenzolsulfonate, Alkansulfonate, die aus C s-Alkanen z.B. durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden, Ci2-18-Olefinsulfonate, die bei der Umsetzung entsprechender Monoolefine mit Schwefeltrioxid entstehen, Gemische aus Alken- und Hydroxyalkansulfonaten, Disulfonaten, wie man sie z.B. aus C s-Monoolefinen mit end- oder innenständigen Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, sowie a-Sulfofettsäureester (Estersulfonate), die bei der Sulfonierung von Fettsäuremethyl- oder -ethylestern entstehen, z.B. a- sulfonierte Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren. Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Soaps which can be used are preferably the alkali salts of saturated or unsaturated C s fatty acids. Such fatty acids can also be used in a form which is not completely neutralized. The useful surfactants of the sulfate type include the salts of the sulfuric acid half esters of C s fatty alcohols and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation. The usable surfactants of the sulfonate type include, for example, Cg-14-alkylbenzenesulfonates, alkanesulfonates which are obtained from Cs-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, Ci2-18-olefinsulfonates which are formed by reacting corresponding monoolefins with sulfur trioxide, mixtures of alkene and hydroxyalkanesulfonates, disulfonates such as those obtained from Cs-monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, and α-sulfofatty acid esters (estersulfonates) which are formed by sulfonating fatty acid methyl or ethyl esters, e.g. α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
Vorzugsweise weist das Mittel 2 bis 55 Gew.-%, vorzugsweise 3 bis 35 Gew.-%, Aniontensid auf. Ganz besonders bevorzugt weist das Mittel 3 bis 25 Gew.-% Alkylbenzolsulfonat auf. Darüber hinaus kann das Mittel vorzugsweise noch weitere anionische Tenside, insbesondere Alkylethersulfate, sowie nichtionische Tenside, insbesondere Fettalkoholalkoxylate, enthalten. Diese können dann den Rest der Tenside ausmachen. The agent preferably contains 2 to 55% by weight, preferably 3 to 35% by weight, of anionic surfactant. The agent most preferably contains 3 to 25% by weight of alkylbenzenesulfonate. In addition, the agent can preferably contain other anionic surfactants, in particular alkyl ether sulfates, and nonionic surfactants, in particular fatty alcohol alkoxylates. These can then make up the rest of the surfactants.
Geeignete Alkylbenzolsulfonate sind vorzugsweise ausgewählt aus linearen oder verzweigten Alkylbenzolsulfonaten der Formel
Figure imgf000036_0001
in der R' und R" unabhängig H oder Alkyl sind und zusammen 6 bis 19, vorzugsweise 7 bis 15 und insbesondere 9 bis 13 C-Atome enthalten. Ein ganz besonders bevorzugter Vertreter ist Natriumdodecylbenzylsulfonat. Suitable alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula
Figure imgf000036_0001
in which R' and R" are independently H or alkyl and together contain 6 to 19, preferably 7 to 15 and in particular 9 to 13 C atoms. A particularly preferred representative is sodium dodecylbenzylsulfonate.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der Ci2-18-Fettalkohole, z.B. aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der Cio-20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die Ci2-16-Alkylsulfate und Ci2-15-Alkylsulfate sowie C- s-Alkylsulfate bevorzugt. Preferred alk(en)yl sulfates are the alkali metal and especially the sodium salts of the sulfuric acid half esters of the C12-18 fatty alcohols, e.g. from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-20 oxo alcohols and those half esters of secondary alcohols of these chain lengths. Also preferred are alk(en)yl sulfates of the chain length mentioned which contain a synthetic, petrochemically based straight-chain alkyl radical, which have a degradation behavior similar to that of the corresponding compounds based on oleochemical raw materials. For washing purposes, the C12-16 alkyl sulfates and C12-15 alkyl sulfates as well as C-18 alkyl sulfates are preferred.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-2i-Alkohole, wie 2-Methyl-verzweigte Cg-n-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder Ci2-18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Also suitable are the sulfuric acid monoesters of straight-chain or branched C7-2i-alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-n-alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci2-18-fatty alcohols with 1 to 4 EO.
Geeignete Alkylethersulfate sind z.B. Verbindungen der Formel Suitable alkyl ether sulfates are, for example, compounds of the formula
R1-O-(AO)n-SO3- X+. R 1 -O-(AO) n -SO 3 - X + .
In dieser Formel steht R1 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest, vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R1 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl-, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R1 sind abgeleitet von C s-Fettalkoholen, z.B. von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von Cio-20-Oxoalkoholen. AO steht für eine Ethylenoxid-(EO) oder Propylenoxid-(PO)-Gruppierung, vorzugsweise für eine Ethylenoxidgruppierung. Der Index n steht für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und insbesondere von 2 bis 10. Ganz besonders bevorzugt steht n für die Zahlen 2, 3, 4, 5, 6, 7 oder 8. X+ steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen X+ können ausgewählt sein aus NHT, % Zn2+, % Mg2+, % Ca2+, % Mn2+ und deren Mischungen. In this formula, R 1 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, with the representatives with an even number of C atoms being preferred. Particularly preferred radicals R 1 are derived from C s fatty alcohols, e.g. from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10-20 oxo alcohols. AO is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X + stands for a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and among these Na + or K + , with Na + being extremely preferred. Further cations X + can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and mixtures thereof.
In verschiedenen Ausführungsformen kann das Alkylethersulfat ausgewählt sein aus Fettalkoholethersulfaten der Formel
Figure imgf000037_0001
mit k = 1 1 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na-Ci2-14- Fettalkoholethersulfate mit 2 EO (k = 1 1-13, n = 2). Der angegebenen Ethoxylierungsgrad stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann. Die angegebenen Alkoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoxylate/Ethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). In various embodiments, the alkyl ether sulfate may be selected from fatty alcohol ether sulfates of the formula
Figure imgf000037_0001
with k = 1 1 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Particularly preferred representatives are Na-Ci2-14 fatty alcohol ether sulfates with 2 EO (k = 1 1-13, n = 2). The stated degree of ethoxylation represents a statistical average, which can be a whole or a fractional number for a specific product. The stated degrees of alkoxylation represent statistical averages, which for a specific Product can be a whole or a fractional number. Preferred alkoxylates/ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
Es hat sich für die Kaltwaschleistung als vorteilhaft erwiesen, wenn die Mittel zusätzlich Seife(n) enthalten. Bevorzugte Mittel sind daher dadurch gekennzeichnet, dass sie Seife(n) enthalten. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische. It has proven to be advantageous for cold washing performance if the agents also contain soap(s). Preferred agents are therefore characterized by the fact that they contain soap(s). Suitable are saturated 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, e.g. coconut, palm kernel or tallow fatty acids.
Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylglykosiden oder linearen oder verzweigten Alkoholen mit jeweils 8 bis etwa 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkylaminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten langkettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomen im Alkylrest brauchbar. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and/or propoxylation products of alkyl glycosides or linear or branched alcohols each having 8 to about 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl moiety, and of alkylphenols having 5 to 12 C atoms in the alkyl radical are usable.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2- Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören z.B. Ci2-14-Alkohole mit 3 EO oder 4 EO, Cg-n-Alkohol mit 7 EO, C s-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C s-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus Ci2-14-Alkohol mit 3 EO und C12-18- Alkohol mit 5 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 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 can contain linear and methyl-branched radicals in the mixture, as is usually the case in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C6-n alcohol with 7 EO, C8-s alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C8-s alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages which can be a whole or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
Eine weitere Klasse von nichtionischen Tensiden, die vorteilhaft eingesetzt werden kann, sind die Alkylpolyglycoside (APG). Einsetzbare Alkylpolyglycoside genügen der allgemeinen FormelAnother class of non-ionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Usable alkyl polyglycosides satisfy the general formula
RO(G)Z, in der R für einen linearen oder verzweigten, insbesondere in 2-Stellung methylverzweigten, gesättigten oder ungesättigten, aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Glycosidierungsgrad z liegt dabei zwischen 1 und 4, vorzugsweise zwischen 1 und 2 und insbesondere zwischen 1 ,1 und 1 ,4. Bevorzugt eingesetzt werden lineare Alkylpolyglycoside, also Alkylpolyglycoside, in denen der Polyglycosylrest ein Glucoserest und der Alkylrest ein n-Alkylrest ist. RO(G) Z , in which R is a linear or branched, in particular 2-methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1 and 4, preferably between 1 and 2 and in particular between 1.1 and 1.4. Linear alkyl polyglycosides are preferably used, i.e. alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
Auch nichtionische Tenside vom Typ der Aminoxide, z.B. N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Non-ionic surfactants of the amine oxide type, e.g. N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides may also be suitable. The amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of that.
Geeignete Amphotenside sind z.B. Betaine der Formel Suitable amphoteric surfactants are, for example, betaines of the formula
(Riii)(Riv)(Rv)N+CH2COO-, in der R'" einen ggf. durch Heteroatome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 25, vorzugsweise 10 bis 21 Kohlenstoffatomen und Riv sowie Rv gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten, insbesondere C10-18- Alkyldimethylcarboxymethylbetain und Cn-17-Alkylamidopropyldimethylcarboxymethylbetain. (R iii )(R iv )(R v )N + CH 2 COO-, in which R'" is an alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C10-18-alkyldimethylcarboxymethylbetaine and Cn-17-alkylamidopropyldimethylcarboxymethylbetaine.
Geeignete kationische Tenside sind u.a. die quartären Ammoniumverbindungen der FormelSuitable cationic surfactants include the quaternary ammonium compounds of the formula
(Rvi)(Rvii)(Rviii)(Rix)N+X-, in der Rvi bis Rix für vier gleich- oder verschiedenartige, insbesondere zwei lang- und zwei kurzkettige, Alkylreste und X- für ein Anion, insbesondere ein Halogenidion, stehen, z.B. Didecyldimethylammoniumchlorid, Alkylbenzyldidecylammoniumchlorid und deren Mischungen. Weitere geeignete kationische Tenside sind die quaternären oberflächenaktiven Verbindungen, insbesondere mit einer Sulfonium-, Phosphonium-, Jodonium- oder Arsoniumgruppe, die auch als antimikrobielle Wirkstoffe bekannt sind. Durch den Einsatz von quaternären oberflächenaktiven Verbindungen mit antimikrobieller Wirkung kann das Mittel mit einer antimikrobiellen Wirkung ausgestaltet werden bzw. dessen ggf. aufgrund anderer Inhaltsstoffe bereits vorhandene antimikrobielle Wirkung verbessert werden. (R vi )(R vii )(R viii )(R ix )N + X-, in which R vi to R ix are four identical or different, in particular two long-chain and two short-chain, alkyl radicals and X- is an anion, in particular a halide ion, e.g. didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof. Other suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with antimicrobial action, the agent can be given an antimicrobial effect or its already existing antimicrobial effect can be improved due to other ingredients.
Ein weiterer bevorzugter Bestandteil erfindungsgemäßer Mittel sind Komplexbildner. Besonders bevorzugte Komplexbildner sind die Phosphonate, sofern ihr Einsatz regulatorisch zulässig ist. Die komplexbildenden Phosphonate umfassen neben der 1-Hydroxyethan-1 ,1-diphosphonsäure eine Reihe unterschiedlicher Verbindungen, wie z.B. Diethylentriaminpenta(methylenphosphonsäure) (DTPMP). In dieser Anmeldung bevorzugt sind insbesondere Hydroxyalkan- bzw. Aminoalkanphosphonate. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1 ,1- diphosphonat (HEDP) von besonderer Bedeutung als Cobuilder. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z.B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz der DTPMP, eingesetzt. Als Builder wird dabei aus der Klasse der Phosphonate bevorzugt HEDP verwendet. Die Aminoalkanphosphonate besitzen zudem ein ausgeprägtes Schwermetallbindevermögen. Dementsprechend kann es, insbesondere wenn die Mittel auch Bleiche enthalten, bevorzugt sein, Aminoalkanphosphonate, insbesondere DTPMP, einzusetzen, oder Mischungen aus den genannten Phosphonaten zu verwenden. Ein im Rahmen dieser Anmeldung bevorzugtes Mittel enthält ein oder mehrere Phosphonat(e) aus der Gruppe Aminotrimethylenphosphonsäure (ATMP) und/oder deren Salze; Ethylendiamintetra(methylenphosphonsäure) (EDTMP) und/oder deren Salze; Another preferred component of agents according to the invention are complexing agents. Particularly preferred complexing agents are phosphonates, provided their use is permitted by regulations. In addition to 1-hydroxyethane-1,1-diphosphonic acid, the complexing phosphonates include a range of different compounds, such as diethylenetriaminepenta(methylenephosphonic acid) (DTPMP). In this application, hydroxyalkane and aminoalkanephosphonates are particularly preferred. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues are preferably used as aminoalkanephosphonates. They are preferably used in the form of neutral sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP. As The preferred builder is HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the phosphonates mentioned, particularly if the agents also contain bleach. A preferred agent in the context of this application contains one or more phosphonate(s) from the group aminotrimethylenephosphonic acid (ATMP) and/or its salts; ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and/or its salts;
Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) und/oder deren Salze; 1-Hydroxyethan-1 ,1- diphosphonsäure (HEDP) und/oder deren Salze; 2-Phosphonobutan-1 ,2,4-tricarbonsäure (PBTC) und/oder deren Salze; Hexamethylendiamintetra(methylenphosphonsäure) (HDTMP) und/oder deren Salze; Nitrilotri(methylenphosphonsäure) (NTMP) und/oder deren Salze. Besonders bevorzugt sind Mittel, welche als Phosphonate 1-Hydroxyethan-1 ,1-diphosphonsäure (HEDP) oder Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) enthalten. Selbstverständlich können die erfindungsgemäßen Mittel zwei oder mehr unterschiedliche Phosphonate enthalten. Diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and/or salts thereof; 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and/or salts thereof; 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and/or salts thereof; hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) and/or salts thereof; nitrilotri(methylenephosphonic acid) (NTMP) and/or salts thereof. Particularly preferred are agents which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates. Of course, the agents according to the invention can contain two or more different phosphonates.
Bevorzugte erfindungsgemäße Mittel sind dadurch gekennzeichnet, dass das Mittel mindestens einen Komplexbildner aus der Gruppe der Phosphonate, vorzugsweise 1-Hydroxyethan-1 ,1- diphosphonat, enthält, wobei der Gewichtsanteil des Phosphonat am Gesamtgewicht des Mittels vorzugsweise 0,1 und 8,0 Gew.-%, bevorzugt 0,2 und 5,0 Gew.-%, weiter bevorzugt 0,3 und 3,0 Gew.-% und besonders bevorzugt 0, 5-2,0 Gew.-% beträgt. Preferred agents according to the invention are characterized in that the agent contains at least one complexing agent from the group of phosphonates, preferably 1-hydroxyethane-1,1-diphosphonate, wherein the weight proportion of the phosphonate in the total weight of the agent is preferably 0.1 and 8.0 wt.%, preferably 0.2 and 5.0 wt.%, more preferably 0.3 and 3.0 wt.% and particularly preferably 0.5-2.0 wt.%.
In weiter bevorzugten Ausführungsformen sind die erfindungsgemäßen Wasch- und/oder Reinigungsmittel im Wesentlichen frei von phosphonathaltigen Verbindungen. "Im Wesentlichen frei von phosphonathaltigen Verbindungen" bedeutet in diesem Zusammenhang, dass die entsprechende Mittel weniger als 2 Gew.-%, vorzugsweise weniger als 1 Gew.-%, weiter bevorzugt weniger als 0,5 Gew.-% und besonders bevorzugt weniger als 0,1 Gew.-%, phosphonathaltige Verbindungen, bezogen auf das Gesamtgewicht des Mittels, enthalten. In besonders bevorzugten Ausführungsformen sind diese Mittel frei von phosphonathaltigen Verbindungen. In further preferred embodiments, the washing and/or cleaning agents according to the invention are essentially free of phosphonate-containing compounds. "Essentially free of phosphonate-containing compounds" in this context means that the corresponding agents contain less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight and particularly preferably less than 0.1% by weight of phosphonate-containing compounds, based on the total weight of the agent. In particularly preferred embodiments, these agents are free of phosphonate-containing compounds.
Die erfindungsgemäßen Mittel enthalten weiterhin vorzugsweise Gerüststoff (Builder), vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den Gerüststoffe zählen dabei insbesondere die Silikate, Carbonate und organische Cobuilder. The agents according to the invention preferably also contain builders, preferably at least one water-soluble and/or water-insoluble, organic and/or inorganic builder. The builders include in particular silicates, carbonates and organic cobuilders.
Als organische Cobuilder sind insbesondere Polycarboxylate/Polycarbonsäuren, polymere Polycarboxylate, Asparaginsäure, Polyacetale, Dextrine, weitere organische Cobuilder sowie Phosphonate zu nennen. Diese Stoffklassen werden nachfolgend beschrieben. Organische Cobuildersubstanzen können gewünschtenfalls in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 bis 8 Gew.-% enthalten sein. Brauchbare organische Gerüstsubstanzen sind z.B. die in Form der freien Säure und/oder ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren und Carboxymethylinuline, monomere und polymere Aminopolycarbonsäuren, insbesondere Glycindiessigsäure, Methylglycindiessigsäure, Glutamindiessigsäure, Nitrilotriessigsäure (NTA), Iminodisuccinat wie Ethylendiamin-N,N'-dibernsteinsäure und Hydroxyiminodisuccinate, Ethylendiamintetraessigsäure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylenphosphonsäure), Ethylendiamintetrakis(methylenphosphonsäure), Lysintetra(methylenphosphosäure) und 1-Hydroxyethan-1 ,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly)carbonsäuren, insbesondere durch Oxidation von Polysacchariden bzw. Dextrinen zugängliche Polycarboxylate, und/oder polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 50 Gew.-%, insbesondere bis zu 25 Gew.-%, vorzugsweise von 10 bis 20 Gew.-% und besonders bevorzugt von 1 bis 5 Gew.-% enthalten sein. Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Mitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen. Mit besonderem Vorzug wird als Gerüstsubstanz die Citronensäure oder Salze der Citronensäure eingesetzt. Weitere besonders bevorzugte Gerüstsubstanzen sind ausgewählt unter Methylglycindiessidsäure (MGDA), Glutaminsäurediacetat (GLDA), Asparaginsäurediacetat (ASDA), Hydroxyethyliminodiacetat (HEIDA), Iminodisuccinat (IDS) und Ethylendiamindisuccinat (EDDS), Carboxymethylinulin und Polyaspartat. In bevorzugten Ausführungsformen wird als wasserlöslicher, organischer Builder Citronensäure und/oder Citrat eingesetzt. Besonders bevorzugt ist der Einsatz von 0,5 bis 25 Gew.-%, vorzugsweise 0,75 bis 12,5 Gew.-%, weiter bevorzugt 1 bis 4 Gew.-% Citronensäure und/oder 0,5 bis 25 Gew.-%, vorzugsweise 0,75 bis 12,5 Gew.-%, weiter bevorzugt 1 bis 4 Gew.-% Citrat, vorzugsweise Alkalicitrat, noch bevorzugter Natriumcitrat. Citronensäure/Citrat können jeweils in Form ihrer Hydrate eingesetzt werden, so kann z.B. Citronensäure in Form des Monohydrats, Citrat in Form des Trinatriumcitratdihydrats eingesetzt werden. Organic cobuilders include, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below. Organic cobuilder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight. Useful organic builders are, for example, polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to be carboxylic acids which have more than one acid function. Examples of these are citric acid, adipic acid, succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids and carboxymethylinulins, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, glutaminediacetic acid, nitrilotriacetic acid (NTA), iminodisuccinate such as ethylenediamine-N,N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), lysinetetra(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides or dextrins, and/or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in polymerized form. Such organic builder substances can, if desired, be contained in amounts of up to 50% by weight, in particular up to 25% by weight, preferably from 10 to 20% by weight and particularly preferably from 1 to 5% by weight. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are particularly suitable here. Citric acid or salts of citric acid are particularly preferably used as the builder substance. Other particularly preferred builder substances are selected from methylglycine disidic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), carboxymethylinulin and polyaspartate. In preferred embodiments, citric acid and/or citrate is used as the water-soluble, organic builder. It is particularly preferred to use 0.5 to 25% by weight, preferably 0.75 to 12.5% by weight, more preferably 1 to 4% by weight of citric acid and/or 0.5 to 25% by weight, preferably 0.75 to 12.5% by weight, more preferably 1 to 4% by weight of citrate, preferably alkali citrate, even more preferably sodium citrate. Citric acid/citrate can each be used in the form of their hydrates, for example citric acid can be used in the form of the monohydrate, citrate in the form of the trisodium citrate dihydrate.
Als Gerüststoffe sind weiter polymere Polycarboxylate geeignet, dies sind z.B. die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, z.B. solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol. Bei den für polymere Polycarboxylate angegebenen Molmassen handelt es sich im Sinne dieser Anmeldung um gewichtsmittlere Molmassen Mw der jeweiligen Säureform, die grundsätzlich mittels Gelpermeationschromatographie (GPC) bestimmt wurden, wobei ein UV-Detektor eingesetzt wurde. Die Messung erfolgte dabei gegen einen externen Polyacrylsäure-Standard, der aufgrund seiner strukturellen Verwandtschaft mit den untersuchten Polymeren realistische Molgewichtswerte liefert. Diese Angaben weichen deutlich von den Molgewichtsangaben ab, bei denen Polystyrolsulfonsäuren als Standard eingesetzt werden. Die gegen Polystyrolsulfonsäuren gemessenen Molmassen sind in der Regel deutlich höher als die in dieser Anmeldung angegebenen Molmassen. Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 2000 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 2000 bis 10000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol, aufweisen, bevorzugt sein. Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im Allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol. Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, e.g. those with a relative molecular mass of 500 to 70,000 g/mol. The molar masses given for polymeric polycarboxylates in the sense of this application are weight-average molar masses Mw of the respective acid form, which were generally determined by means of gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which, due to its structural similarity to the polymers examined, provides realistic molar weight values. These figures differ significantly from the molar weight figures for which polystyrene sulfonic acids are used as a standard. The molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molar masses given in this application. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular weights of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, may be preferred. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid, which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have proven particularly suitable. Their relative molecular weight, based on free acids, is generally 2000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol and in particular 30,000 to 40,000 g/mol.
Ein erfindungsgemäßes festes Mittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasserlöslichen organischen Buildersubstanzen gehören die oben genannten organischen Gerüstsubstanzen. A solid agent according to the invention preferably contains at least one water-soluble and/or water-insoluble, organic and/or inorganic builder. The water-soluble organic builder substances include the above-mentioned organic framework substances.
Zusätzlich zu den vorstehend genannten wasserlöslichen organischen Buildern, können die Mittel der Erfindung weiterhin auch anorganische wasserlösliche Builder enthalten. Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Alkalisilikate, Alkalicarbonate, Alkalihydrogenbarbonate, Alkaliphosphate und/oder Sesquicarbonate, die in Form ihrer alkalischen, neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können, in Betracht. Ggf. können auch geringe Mengen an Calciumcarbonate in festen Textilwaschmitteln enthalten sein. Geeignet sind z.B. wasserlöslichen kristalline und/oder amorphe Alkalisilikate. Die in den erfindungsgemäßen Mitteln als Gerüststoffe brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu SiO2 unter 0,95, insbesondere von 1 :1 ,1 bis 1 :12 auf und können amorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na2O:SiO2 von 1 :2 bis 1 :2,8. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der allgemeinen Formel Na2SixO2x+i • y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1 ,9 bis 22, insbesondere 1 ,9 bis 4 und y eine Zahl von 0 bis 33 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch ö-Natriumdisilikate (Na2Si2Ü5 • y H2O) bevorzugt. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der oben genannten allgemeinen Formel, in der x eine Zahl von 1 ,9 bis 2,1 bedeutet, können in erfindungsgemäßen Mitteln eingesetzt werden. In einer weiteren Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1 ,9 bis 3,5 werden in einer weiteren Ausführungsform erfindungsgemäßer Mittel eingesetzt. In Mitteln, die sowohl amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis von amorphem Alkalisilikat zu kristallinem Alkalisilikat vorzugsweise 1 :2 bis 2:1 und insbesondere 1 :1 bis 2:1 . Kristalline schichtförmige Silikate der oben angegebenen Formel (I) werden von der Fa. Clariant GmbH unter dem Handelsnamen Na-SKS vertrieben, z.B. Na-SKS-1 (Na2Si22O45 • x H2O, Kenyait), Na-SKS-2 (Na2Sii4O29 • x H2O, Magadiit), Na- SKS-3 (Na2SisOi7 • x H2O) oder Na-SKS-4 (Na2Si4Ü9 • x H2O, Makatit). Von diesen eignen sich vor allem Na-SKS-5 (a-Na2Si2O5), Na-SKS-7 (ß-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5 • 3 H2O), Na- SKS-10 (NaHSi2O5 • 3 H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (ö-Na2Si2C>5). In einer Ausgestaltung erfindungsgemäßer Mittel setzt man ein granuläres Compound aus kristallinem Schichtsilikat und Citrat, aus kristallinem Schichtsilikat und oben genannter (co-)polymerer Polycarbonsäure, oder aus Alkalisilikat und Alkalicarbonat ein, wie es z.B. unter dem Namen Nabion® 15 im Handel erhältlich ist. Derartige wasserlösliche anorganischen Buildermaterialien sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen von 1 bis 20 Gew.-%, insbesondere 5 bis 15 Gew.-%, enthalten. Des Weiteren sind als wasserlösliche anorganische Buildersubstanzen noch die Carbonate (und Hyodrogencarbonate), insbesondere Natriumcarbonat, und die Phosphonsäuren/Phosphonate von Bedeutung. In addition to the above-mentioned water-soluble organic builders, the agents of the invention can also contain inorganic water-soluble builders. Suitable water-soluble inorganic builder materials are in particular alkali silicates, alkali carbonates, alkali hydrogen carbonates, alkali phosphates and/or sesquicarbonates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Small amounts of calcium carbonates can also be contained in solid textile detergents. Suitable examples are water-soluble crystalline and/or amorphous alkali silicates. The alkali silicates that can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO2 of less than 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are sodium silicates, in particular amorphous sodium silicates, with a molar ratio Na2O:SiO2 of 1:2 to 1:2.8. Crystalline silicates which can be present alone or in a mixture with amorphous silicates are preferably crystalline layered silicates of the general formula Na2Si x O2x+i • y H2O, in which x, the so-called modulus, is a number from 1.9 to 22, in particular 1.9 to 4, and y is a number from 0 to 33, and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na2Si2θ5 • y H2O) are preferred. Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali silicates, can also be used in agents according to the invention. In a further embodiment of agents according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment of agents according to the invention. In agents which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1. Crystalline layered silicates of the above formula (I) are sold by Clariant GmbH under the trade name Na-SKS, e.g. Na-SKS-1 (Na2Si22O45 • x H2O, Kenyaite), Na-SKS-2 (Na2Sii4O29 • x H2O, Magadiite), Na- SKS-3 (Na2SisOi7 • x H2O) or Na-SKS-4 (Na2Si4Ü9 • x H2O, macatite). Of these, Na-SKS-5 (a-Na 2 Si 2 O 5 ), Na-SKS-7 (ß-Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 • 3 H2O), Na-SKS-10 (NaHSi 2 O 5 • 3 H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 (δ-Na2Si2C>5) are particularly suitable. In one embodiment of the inventive agents, a granular compound of crystalline layered silicate and citrate, of crystalline layered silicate and the above-mentioned (co-)polymeric polycarboxylic acid, or of alkali silicate and alkali carbonate is used, as is commercially available under the name Nabion® 15, for example. Such water-soluble inorganic builder materials are preferably contained in the inventive agents in amounts of 1 to 20% by weight, in particular 5 to 15% by weight. Other important water-soluble inorganic builder substances are carbonates (and hydrocarbonates), in particular sodium carbonate, and phosphonic acids/phosphonates.
Die erfindungsgemäßen Mittel sind vorzugsweise frei von Phosphat-Builder, d.h. enthalten weniger als 1 Gew.-%, bevorzugt keinen bewusst zugegebenen Phosphat-Builder. The agents according to the invention are preferably free of phosphate builders, i.e. they contain less than 1% by weight, preferably no deliberately added phosphate builder.
Die Mittel können ferner auch wasserunlösliche Buildersubstanzen enthalten. Als wasserunlösliche anorganische Buildermaterialien werden insbesondere kristalline oder amorphe wasserdispergierbare Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-%, insbesondere von 3 bis 20 Gew.-% und besonders bevorzugt von 1 bis 15 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, Zeolith P, Zeolith MAP und ggf. Zeolith X, allein oder in Mischungen, z.B. in Form eines Co-Kristallisats aus den Zeolithen A und X (Vegobond® AX, ein Handelsprodukt der Condea Augusta S.p.A.), bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 pm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 pm. Ihr Calciumbindevermögen, das gemäß DE 2412837 A1 bestimmt werden kann, liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm. The agents can also contain water-insoluble builder substances. Water-insoluble inorganic builder materials used are in particular crystalline or amorphous water-dispersible alkali aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, in particular from 3 to 20% by weight and particularly preferably from 1 to 15% by weight. Among these, preference is given to crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, zeolite P, zeolite MAP and optionally zeolite X, alone or in mixtures, e.g. in the form of a co-crystallizate of zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta S.p.A.). Amounts close to the upper limit mentioned are preferably used in solid, particulate agents. Suitable aluminosilicates in particular do not contain any particles with a grain size of more than 30 pm and preferably consist of at least 80% by weight of particles with a size of less than 10 pm. Their calcium binding capacity, which can be determined according to DE 2412837 A1, is generally in the range of 100 to 200 mg CaO per gram.
In Ergänzung zu den zuvor beschriebenen Gerüststoffen können in dem Mittel reinigungsaktive Polymere enthalten sein. Der Gewichtsanteil der reinigungsaktiven Polymere am Gesamtgewicht erfindungsgemäßer Mittel beträgt vorzugsweise 0,1 bis 20 Gew.-%, vorzugsweise 1 ,0 bis 15 Gew.-% und weiter bevorzugt 2,0 bis 12 Gew.-%. In addition to the previously described builders, the agent may contain cleaning-active polymers. The weight proportion of the cleaning-active polymers in the total weight of the agent according to the invention is preferably 0.1 to 20 wt. %, preferably 1.0 to 15 wt. %, and more preferably 2.0 to 12 wt. %.
Als für den Einsatz in erfindungsgemäßen Mitteln geeignete Persauerstoffverbindungen kommen insbesondere organische Persäuren bzw. persaure Salze organischer Säuren, wie Phthalimidopercapronsäure, Perbenzoesäure oder Salze der Diperdodecandisäure, Wasserstoffperoxid und unter den Waschbedingungen Wasserstoffperoxid abgebende anorganische Salze, zu denen Perborat, Percarbonat, Persilikat und/oder Persulfat wie Caroat gehören, sowie Wasserstoffperoxid-Einschlussverbindungen, wie H2G2-Harnstoffaddukte, in Betracht. Wasserstoffperoxid kann dabei auch mit Hilfe eines enzymatischen Systems, d.h. einer Oxidase und ihres Substrates, erzeugt werden. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Die Persauerstoffverbindungen können als solche oder in Form diese enthaltender Mittel, die prinzipiell alle üblichen Wasch-, Reinigungs- oder Desinfektionsmittelbestandteile enthalten können, zu der Waschlauge zugegeben werden. Besonders bevorzugt wird Alkalipercarbonat oder Alkaliperborat-Monohydrat eingesetzt. Falls ein erfindungsgemäßes Mittel Persauerstoffverbindungen enthält, sind diese in Mengen von vorzugsweise bis zu 50 Gew.-%, insbesondere von 5 bis 30 Gew.-%, weiter bevorzugt von 0,1 bis 20 Gew.-% vorhanden. Peroxygen compounds suitable for use in agents according to the invention are, in particular, organic peracids or peracidic salts 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, including perborate, percarbonate, persilicate and/or persulfate such as caroate, as well as hydrogen peroxide inclusion compounds such as H2G2-urea adducts. Hydrogen peroxide can also be produced with the aid of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be used in principle in can be coated in a known manner. The peroxygen compounds can be added to the washing solution as such or in the form of agents containing them, which in principle can contain all the usual washing, cleaning or disinfectant ingredients. Alkali percarbonate or alkali perborate monohydrate is particularly preferably used. If an agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5 to 30% by weight, more preferably from 0.1 to 20% by weight.
Als Bleichaktivatoren können in den Mitteln Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C- Atomen, und/oder ggf. substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder ggf. substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1 ,5-Diacetyl-2,4- dioxohexahydro-1 ,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate oder - carboxylate bzw. die Sulfon- oder Carbonsäuren von diesen, insbesondere Nonanoyl- oder Isononanoyloxybenzolsulfonat oder Laroyloxybenzolsulfonat (NOBS bzw. iso-NOBS bzw. LOBS), 4- (2-Decanoyloxyethoxycarbonyloxy)-benzolsulfonat (DECOBS) oder Decanoyloxybenzoat (DOBA), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und Enolester sowie acetyliertes Sorbitol und Mannitol bzw. deren beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose, acetyliertes, ggf. N-alkyliertes Glucamin und Gluconolacton, N-acylierte Lactame, z.B. N-Benzoylcaprolactam, Nitrile, aus denen sich Perimidsäuren bilden, insbesondere Aminoacetonitrilderivate mit quaterniertem Stickstoffatom, und/oder sauerstoffübertragende Sulfonimine und/oder Acylhydrazone. Die hydrophil substituierten Acylacetale und die Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren können, insbesondere bei Anwesenheit obengenannter Wasserstoffperoxid-Iiefernder Bleichmittel, im üblichen Mengenbereich, vorzugsweise in Mengen von 0,5 bis 10 Gew.-%, insbesondere 1 bis 8 Gew.-%, bezogen auf gesamtes Mittel, enthalten sein, fehlen bei Einsatz von Percarbonsäure als alleinigem Bleichmittel jedoch vorzugsweise ganz. Compounds which, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid, can be used as bleach activators in the agents. Substances which carry O- and/or N-acyl groups of the stated number of C atoms and/or optionally substituted benzoyl groups are suitable. Preference is given to multiply acylated 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 or carboxylates or the sulfonic or carboxylic acids thereof, in particular nonanoyl or isononanoyloxybenzenesulfonate or laroyloxybenzenesulfonate (NOBS or iso-NOBS or LOBS), 4-(2-decanoyloxyethoxycarbonyloxy)benzenesulfonate (DECOBS) or decanoyloxybenzoate (DOBA), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, Ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and enol esters as well as acetylated sorbitol and mannitol or their described mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, acetylated, possibly N-alkylated glucamine and gluconolactone, N-acylated lactams, e.g. N-benzoylcaprolactam, nitriles from which perimidic acids are formed, in particular aminoacetonitrile derivatives with a quaternized nitrogen atom, and/or oxygen-transferring sulfonimines and/or acylhydrazones. The hydrophilically substituted acyl acetals and the acyl lactams are also preferred. Combinations of conventional bleach activators can also be used. Such bleach activators can be present in the usual amount range, preferably in amounts of 0.5 to 10% by weight, in particular 1 to 8% by weight, based on the total agent, particularly in the presence of the above-mentioned hydrogen peroxide-producing bleaching agents, but are preferably completely absent when percarboxylic acid is used as the sole bleaching agent.
Zusätzlich zu den konventionellen Bleichaktivatoren oder an deren Stelle können in festen Mitteln auch Sulfonimine und/oder bleichverstärkende Übergangsmetallsalze bzw. Übergangsmetallkomplexe als sogenannte Bleichkatalysatoren enthalten sein. In addition to the conventional bleach activators or instead of them, solid agents can also contain sulfonimines and/or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts.
Geeignete Vergrauungsinhibitoren bzw. soil-release-Wirkstoffe (soil release polymer) sind Celluloseether, wie Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulosen und Cellulosemischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose und Methylcarboxymethylcellulose. Vorzugsweise werden Natriumcarboxymethylcellulose, Hydroxyporpylmethylcellulose und deren Gemische und ggf. deren Gemische mit Methylcellulose eingesetzt. Zu den üblicherweise eingesetzten Soil-release-Wirkstoffen gehören Copolyester, die Dicarbonsäureeinheiten, Alkylenglykoleinheiten und Polyalkylenglykoleinheiten enthalten. Der Anteil an Vergrauungsinhibitoren und/oder soil-release-Wirkstoffen in erfindungsgemäßen Mitteln liegt im Allgemeinen nicht über 2 Gew.-% und beträgt vorzugsweise 0,5 bis 1 ,5 Gew.-%, besonders bevorzugt 0,5 bis 2 Gew.-%. Suitable greying inhibitors or soil release agents (soil release polymers) are cellulose ethers such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Sodium carboxymethylcellulose, Hydroxypropylmethylcellulose and mixtures thereof and optionally mixtures thereof with methylcellulose are used. The soil-release active ingredients commonly used include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and/or soil-release active ingredients in agents according to the invention is generally not more than 2% by weight and is preferably 0.5 to 1.5% by weight, particularly preferably 0.5 to 2% by weight.
Als optische Aufheller für insbesondere Textilien aus Cellulosefasern (z.B. Baumwolle) können z.B. Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten sein. Geeignet sind z.B. Salze der 4,4’-Bis(2-anilino-4-morpholino-1 ,3,5-triazin-6-yl-amino)-stilben-2,2’-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ des substituierten 4,4’-Distyryl-diphenyl anwesend sein, z.B. 4,4’- Bis-(4-chlor-3-sulfostyryl)-diphenyl. Auch Gemische von Aufhellern können verwendet werden. Für Polyamidfasern eignen sich besonders gut Aufheller vom Typ der 1 ,3-Diaryl-2-pyrazoline, z.B. 1-(p- Sulfoamoylphenyl)-3-(p-chlorphenyl)-2-pyrazolin sowie gleichartig aufgebaute Verbindungen. Der Gehalt des Mittels an optischen Aufhellern bzw. Aufhellergemischen liegt im Allgemeinen nicht über 1 Gew.-%, vorzugsweise 0,05 bis 0,5 Gew.-%. In einer bevorzugten Ausführungsform der Erfindung ist das Mittel frei von derartigen Wirkstoffen. Optical brighteners, particularly for textiles made from cellulose fibers (e.g. cotton), can include derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable examples are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilbene-2,2'-disulfonic acid or similarly structured compounds which have a diethanolamino group, a methylamino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type can also be present, e.g. 4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl. Mixtures of brighteners can also be used. Brighteners of the 1,3-diaryl-2-pyrazoline type, e.g. 1-(p-sulfoamoylphenyl)-3-(p-chlorophenyl)-2-pyrazoline and similarly structured compounds, are particularly suitable for polyamide fibers. The content of optical brighteners or brightener mixtures in the agent is generally not more than 1% by weight, preferably 0.05 to 0.5% by weight. In a preferred embodiment of the invention, the agent is free of such active ingredients.
Zu den in den erfindungsgemäßen Mitteln einsetzbaren üblichen Schaumregulatoren gehören z.B. Polysiloxan-Kieselsäure-Gemische, wobei die darin enthaltene feinteilige Kieselsäure vorzugsweise silaniert oder anderweitig hydrophobiert ist. Die Polysiloxane können sowohl aus linearen Verbindungen wie auch aus vernetzten Polysiloxan-Harzen sowie aus deren Gemischen bestehen. Weitere Entschäumer sind Paraffinkohlenwasserstoffe, insbesondere Mikro paraffine und Paraffinwachse, deren Schmelzpunkt oberhalb 40°C liegt, gesättigte Fettsäuren bzw. Seifen mit insbesondere 20 bis 22 C-Atomen, z.B. Natriumbehenat, und Alkalisalze von Phosphorsäuremono- und/oder -dialkylestern, in denen die Alkylketten jeweils 12 bis 22 C-Atome aufweisen. Unter diesen wird bevorzugt Natriummonoalkylphosphat und/oder -dialkylphosphat mit Ci6-18-Alkylgruppen eingesetzt. Der Anteil der Schaumregulatoren kann vorzugsweise 0,2 bis 2 Gew.-%, besonders bevorzugt nicht mehr als 1 Gew.-% betragen. The usual foam regulators that can be used in the agents according to the invention include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanized or otherwise hydrophobized. The polysiloxanes can consist of linear compounds as well as cross-linked polysiloxane resins and mixtures thereof. Other defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, whose melting point is above 40°C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, e.g. sodium behenate, and alkali salts of phosphoric acid mono- and/or dialkyl esters, in which the alkyl chains each have 12 to 22 C atoms. Among these, sodium monoalkyl phosphate and/or dialkyl phosphate with Ci6-18 alkyl groups is preferably used. The proportion of foam regulators may preferably be 0.2 to 2 wt.%, particularly preferably not more than 1 wt.%.
Zur Einstellung des gewünschten pH-Werts können die erfindungsgemäßen Mittel system- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure oder Alkalihydrogensulfate, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, vorzugsweise Natriumhydroxid, enthalten. Derartige pH- Regulatoren sind in den erfindungsgemäßen Mitteln vorzugsweise nicht über 10 Gew.-%, insbesondere von 0,5 bis 6 Gew.-%, besonders bevorzugt von 0,3 bis 2 Gew.-% enthalten. To set the desired pH value, the agents according to the invention can contain system- and environmentally compatible acids, in particular 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 alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides, preferably sodium hydroxide. Such pH regulators are preferably contained in the agents according to the invention in amounts of no more than 10% by weight, in particular from 0.5 to 6% by weight, particularly preferably from 0.3 to 2% by weight.
Als einen weiteren Bestandteil können die erfindungsgemäßen Mittel ein organisches Lösungsmittel enthalten. Der Zusatz organischer Lösungsmittel wirkt sich vorteilhaft auf die Enzymstabilität und die Reinigungsleistung dieser Mittel aus. Bevorzugte organische Lösungsmittel stammen aus der Gruppe ein- oder mehrwertigen Alkohole, Alkanolamine oder Glykolether. Vorzugsweise werden die Lösungsmittel ausgewählt aus Ethanol, n- oder i-Propanol, Butanol, Glykol, Propandiol, Butandiol, Glycerin, Diglykol, Propyldiglykol, Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Etheylenglykolmono-n- butylether, Diethylenglykolmethylether, Di-ethylenglykolethylether, Propylenglykolmethylether, Propylenglykolethylether, Propylenglykolpropylether, Dipropylenglykolmethylether, Dipropylenglykolethylether, Methoxytriglykol, Ethoxytriglykol, Butoxytriglykol, 1-Butoxyethoxy-2- propanol, 3-Methyl-3-methoxybutanol, Propylenglykol-t-butylether sowie Mischungen dieser Lösungsmittel. Der Gewichtsanteil dieser organischen Lösungsmittel am Gesamtgewicht erfindungsgemäßer Mittel beträgt vorzugsweise 0,1 bis 10 Gew.-%, bevorzugt 0,2 bis 8,0 Gew.-% und weiter bevorzugt 0,5 bis 5,0 Gew.-%. Ein besonders bevorzugtes und in Bezug auf die Stabilisierung der Mittel besonders wirksames organisches Lösungsmittel ist das Glycerin sowie das 1 ,2 Propylenglykol. Flüssige Mittel umfassen vorzugsweise mindestens ein Polyol, vorzugsweise aus der Gruppe Glycerin und 1 ,2-Propylenglycol, bezogen auf das Gesamtgewicht des Mittels, vorzugsweise zu 0,1 bis 10 Gew.-%, bevorzugt 0,2 bis 8,0 Gew.-% und weiter bevorzugt 0,5 bis 5,0 Gew.-%. Weitere bevorzugte organische Lösungsmittel sind die organischen Amine und Alkanolamine. Die erfindungsgemäßen Mittel enthalten diese Amine vorzugsweise in Mengen von 0,1 bis 10 Gew.-%, bevorzugt von 0,2 bis 8,0 Gew.-% und weiter bevorzugt von 0,5 bis 5,0 Gew.-%, jeweils bezogen auf ihr Gesamtgewicht. Ein besonders bevorzugtes Alkanolamin ist das Ethanolamin. The agents according to the invention can contain an organic solvent as a further component. The addition of organic solvents has a beneficial effect on the Enzyme stability and the cleaning performance of these agents. Preferred organic solvents come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanol, glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, 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 methyl ether, dipropylene glycol ethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. The weight proportion of these organic solvents in the total weight of agents according to the invention is preferably 0.1 to 10 wt. %, preferably 0.2 to 8.0 wt. %, and more preferably 0.5 to 5.0 wt. %. A particularly preferred organic solvent that is particularly effective in terms of stabilizing the agents is glycerin and 1,2-propylene glycol. Liquid agents preferably comprise at least one polyol, preferably from the group glycerin and 1,2-propylene glycol, based on the total weight of the agent, preferably 0.1 to 10 wt. %, preferably 0.2 to 8.0 wt. %, and more preferably 0.5 to 5.0 wt. %. Other preferred organic solvents are organic amines and alkanolamines. The agents according to the invention preferably contain these amines in amounts of 0.1 to 10 wt. %, preferably 0.2 to 8.0 wt. %, and more preferably 0.5 to 5.0 wt. %, in each case based on their total weight. A particularly preferred alkanolamine is ethanolamine.
Erfindungsgemäße Wasch- und/oder Reinigungsmittel können ausschließlich die erfindungsgemäßen Enzyme enthalten. Alternativ können sie auch weitere hydrolytische Enzyme oder andere Enzyme in einer für die Wirksamkeit des Mittels zweckmäßigen Konzentration enthalten. Eine weitere Ausführungsform der Erfindung stellen somit Mittel dar, die ferner eines oder mehrere weitere Enzyme umfassen. Als weitere Enzyme bevorzugt einsetzbar sind alle Enzyme, die in dem erfindungsgemäßen Mittel eine katalytische Aktivität entfalten können, insbesondere eine Protease, Lipase, Amylase, Cellulase, Hemicellulase, Mannanase, Tannase, Xylanase, Xanthanase, Xyloglucanase, ß-Glucosidase, Pektinase, Carrageenase, Perhydrolase, Oxidase, Oxidoreduktase, sowie deren Gemische. Weitere Enzyme sind in dem Mittel vorteilhafterweise jeweils in einer Menge von 1 x I O 8 bis 5 Gewichts-Prozent bezogen auf aktives Protein enthalten. Zunehmend bevorzugt ist jedes weitere Enzym in einer Menge von 1 x 10-7 bis 3 Gew.-%, von 0,00001 bis 1 Gew.-%, von 0,00005 bis 0,5 Gew.-%, von 0,0001 bis 0,1 Gew.-% und besonders bevorzugt von 0,0001 bis 0,05 Gew.-% in erfindungsgemäßen Mitteln enthalten, bezogen auf aktives Protein. Besonders bevorzugt zeigen die Enzyme synergistische Reinigungsleistungen gegenüber bestimmten Anschmutzungen oder Flecken, d.h. die in der Mittelzusammensetzung enthaltenen Enzyme unterstützen sich in ihrer Reinigungsleistung gegenseitig. Detergents and/or cleaning agents according to the invention can contain exclusively the enzymes according to the invention. Alternatively, they can also contain further hydrolytic enzymes or other enzymes in a concentration suitable for the effectiveness of the agent. A further embodiment of the invention thus represents agents which further comprise one or more further enzymes. All enzymes which can preferably be used as further enzymes are those which can display a catalytic activity in the agent according to the invention, in particular a protease, lipase, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, ß-glucosidase, pectinase, carrageenase, perhydrolase, oxidase, oxidoreductase, and mixtures thereof. Further enzymes are advantageously contained in the agent in an amount of 1 x 10 8 to 5 percent by weight, based on active protein. Each additional enzyme is increasingly preferably present in agents according to the invention in an amount of 1 x 10 -7 to 3% by weight, from 0.00001 to 1% by weight, from 0.00005 to 0.5% by weight, from 0.0001 to 0.1% by weight and particularly preferably from 0.0001 to 0.05% by weight, based on active protein. The enzymes particularly preferably exhibit synergistic cleaning performance against certain soilings or stains, ie the enzymes contained in the agent composition support each other in their cleaning performance.
Beispiele für Proteasen sind die Subtilisine BPN' aus Bacillus amyloliquefaciens und Carlsberg aus Bacillus licheniformis, die Protease PB92, die Subtilisine 147 und 309, die Protease aus Bacillus lentus, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7. Subtilisin Carlsberg ist in weiterentwickelter Form unter dem Handelsnamen Alcalase® von dem Unternehmen Novozymes erhältlich. Die Subtilisine 147 und 309 werden unter den Handelsnamen Esperase® bzw. Savinase® von dem Unternehmen Novozymes vertrieben. Von der Protease aus Bacillus lentus DSM 5483 leiten sich Protease- Varianten ab, beschrieben in z.B. WO 95/23221 , WO 92/21760 WO 2013/060621 und EP 3660151. Weitere brauchbare Proteasen sind z.B. die unter den Handelsnamen Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase®, Progress Uno 101 L® und Ovozyme® von dem Unternehmen Novozymes, die unter den Handelsnamen, Purafect®, Purafect® OxP, Purafect® Prime, Excellase®, Properase®, Preferenz P100® und Preferenz P300® von dem Unternehmen Danisco/DuPont, das unter dem Handelsnamen Lavergy pro 104 LS® von dem Unternehmen BASF, das unter dem Handelsnamen Protosol® von dem Unternehmen Advanced Biochemicals Ltd., das unter dem Handelsnamen Wuxi® von dem Unternehmen Wuxi Snyder Bioproducts Ltd., die unter den Handelsnamen Proleather® und Protease P® von dem Unternehmen Amano Pharmaceuticals Ltd., und das unter der Bezeichnung Proteinase K-16 von dem Unternehmen Kao Corp, erhältlichen Enzyme. Besonders bevorzugt eingesetzt werden auch die Proteasen aus Bacillus gibsonii und Bacillus pumilus, die offenbart sind in WO 2008/086916, WO 2007/131656, WO 2017/215925, WO 2021/175696 und WO 2021/175697. Examples of proteases are the subtilisins BPN' from Bacillus amyloliquefaciens and Carlsberg from Bacillus licheniformis, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, subtilisin DY and the subtilases, but no longer the subtilisins in the narrower sense Thermitase, Proteinase K and the proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from the company Novozymes. Subtilisins 147 and 309 are sold under the trade names Esperase® and Savinase® respectively by the company Novozymes. Protease variants are derived from the protease from Bacillus lentus DSM 5483, described in e.g. WO 95/23221, WO 92/21760, WO 2013/060621 and EP 3660151. Other useful proteases are e.g. those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase®, Progress Uno 101 L® and Ovozyme® from the company Novozymes, those under the trade names Purafect®, Purafect® OxP, Purafect® Prime, Excellase®, Properase®, Preferenz P100® and Preferenz P300® from the company Danisco/DuPont, those under the trade name Lavergy pro 104 LS® from the company BASF, those under the trade name Protosol® from the company Advanced Biochemicals Ltd., the enzymes available under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., the enzymes available under the trade names Proleather® and Protease P® from Amano Pharmaceuticals Ltd., and the enzymes available under the name Proteinase K-16 from Kao Corp. The proteases from Bacillus gibsonii and Bacillus pumilus, which are disclosed in WO 2008/086916, WO 2007/131656, WO 2017/215925, WO 2021/175696 and WO 2021/175697, are also particularly preferably used.
Beispiele für Amylasen sind die a-Amylasen aus Bacillus licheniformis, Bacillus amyloliquefaciens oder Bacillus stearothermophilus sowie insbesondere auch deren für den Einsatz in Wasch- und/oder Reinigungsmitteln verbesserte Weiterentwicklungen. Das Enzym aus Bacillus licheniformis ist von dem Unternehmen Novozymes unter dem Namen Termamyl® und von dem Unternehmen Danisco/DuPont unter dem Namen Purastar® ST erhältlich. Weiterentwicklungsprodukte dieser a- Amylase sind unter den Handelsnamen Duramyl® und Termamyl® ultra (beide von Novozymes), Purastar® OxAm (Danisco/DuPont) und Keistase® (Daiwa Seiko Inc.) erhältlich. Die a-Amylase von Bacillus amyloliquefaciens wird von dem Unternehmen Novozymes unter dem Namen BAN® vertrieben, und abgeleitete Varianten von der a-Amylase aus Bacillus stearothermophilus unter den Namen BSG® und Novamyl®, ebenfalls von dem Unternehmen Novozymes. Des Weiteren sind für diesen Zweck die a-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin- Glucanotransferase (CGTase) aus Bacillus agaradherens (DSM 9948) hervorzuheben. Ebenso sind Fusionsprodukte aller genannten Moleküle einsetzbar. Darüber hinaus sind die unter den Handelsnamen Fungamyl® von dem Unternehmen Novozymes erhältlichen Weiterentwicklungen der a-Amylase aus Aspergillus niger und A. oryzae geeignet. Weitere vorteilhaft einsetzbare Handelsprodukte sind z.B. die Amylase-LT® und Stainzyme® oder Stainzyme® ultra bzw. Stainzyme® plus sowie Amplify™ 12L oder Amplify Prime™ 100L, letztere ebenfalls von dem Unternehmen Novozymes, sowie die PREFERENZ S® Serie von dem Unternehmen Danisco/DuPont, umfassend z.B. PREFERENZ S100®, PREFERENZ S1000® oder PREFERENZ S210®. Auch durch Punktmutationen erhältliche Varianten dieser Enzyme können erfindungsgemäß eingesetzt werden. Geeignete Cellulasen umfassen solche bakterieller oder pilzlicher Herkunft. Chemisch modifizierte oder proteintechnisch veränderte Mutanten sind eingeschlossen. Geeignete Cellulasen sind Cellulasen aus den Gattungen Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, z. B. die Pilzcellulasen aus Humicola insolens, Myceliophthora thermophila und Fusarium oxysporum, die in US 4435307, US 5648263, US 5691178, US 5776757 und WO 89/09259 offenbart sind. Besonders geeignete Cellulasen sind die alkalischen oder neutralen Cellulasen mit farbpflegenden Eigenschaften. Beispiele für solche Cellulasen sind Cellulasen, die in EP 0495257, EP 0531372, WO 96/11262, WO 96/29397, WO 98/08940 beschrieben sind. Andere Beispiele sind Cellulase- Varianten, wie sie in WO 94/07998, EP 0531315, EP 3212777, EP 3502243, EP 3653705, EP 3653706, US 5457046, US 5686593, US 5763254, WO 95/24471 , WO 98/12307 und WO 99/01544 und WO 2019/122520 beschrieben sind. Beispiele für Cellulasen mit Endo-1 ,4-Glucanase- Aktivität (EC 3.2.1 .4) sind in WO 2002/099091 beschrieben, z.B. solche mit einer Sequenz von mindestens 97% Identität zu der Aminosäuresequenz der Positionen 1 bis 773 von SEQ ID NO:2 der WO 2002/099091. Ein weiteres Beispiel kann eine GH44-Xyloglucanase umfassen, z.B. ein Xyloglucanase-Enzym mit einer Sequenz von mindestens 60% Identität zu den Positionen 40 bis 559 der SEQ ID NO:2 der WO 2001/062903. Andere Beispiele für Cellulasen umfassen die in WO 96/29397 beschriebenen GH45-Cellulasen. Zu den kommerziell verfügbaren Cellulasen gehören Celluzyme™, Carezyme™, Carezyme Premium™, Celluclean™ (z.B. Celluclean™ 5000L ans Cellulclean™ 4000T), Celluclean Classic™, Cellusoft™, Endolase®, Renozyme® und Whitezyme™ (Novozymes A/S), Clazinase™ und Puradax HA™ (Genencor International Inc.), KAC-500(B)™ (Kao Corporation), Revitalenz™ 1000, Revitalenz™ 2000 und Revitalenz™ 3000 (DuPont), sowie Ecostone® und Biotouch® (AB Enzymes). Examples of amylases are the a-amylases from Bacillus licheniformis, Bacillus amyloliquefaciens or Bacillus stearothermophilus and in particular their further developments that have been improved for use in washing and/or cleaning agents. The enzyme from Bacillus licheniformis is available from Novozymes under the name Termamyl® and from Danisco/DuPont under the name Purastar® ST. Further developments of this a-amylase are available under the trade names Duramyl® and Termamyl® ultra (both from Novozymes), Purastar® OxAm (Danisco/DuPont) and Keistase® (Daiwa Seiko Inc.). The a-amylase from Bacillus amyloliquefaciens is sold by the company Novozymes under the name BAN®, and variants derived from the a-amylase from Bacillus stearothermophilus under the names BSG® and Novamyl®, also by the company Novozymes. Other products that are worth mentioning for this purpose are the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948). Fusion products of all of the molecules mentioned can also be used. In addition, the further developments of the a-amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are also suitable. Other commercial products that can be used advantageously are, for example, Amylase-LT® and Stainzyme® or Stainzyme® ultra or Stainzyme® plus as well as Amplify™ 12L or Amplify Prime™ 100L, the latter also from the company Novozymes, as well as the PREFERENZ S® series from the company Danisco/DuPont, including, for example, PREFERENZ S100®, PREFERENZ S1000® or PREFERENZ S210®. Variants of these enzymes that can be obtained by point mutations can also be used according to the invention. Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein-engineered mutants are included. Suitable cellulases are cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum, which are disclosed in US 4435307, US 5648263, US 5691178, US 5776757 and WO 89/09259. Particularly suitable cellulases are the alkaline or neutral cellulases with color-care properties. Examples of such cellulases are cellulases described in EP 0495257, EP 0531372, WO 96/11262, WO 96/29397, WO 98/08940. Other examples are cellulase variants as described in WO 94/07998, EP 0531315, EP 3212777, EP 3502243, EP 3653705, EP 3653706, US 5457046, US 5686593, US 5763254, WO 95/24471, WO 98/12307 and WO 99/01544 and WO 2019/122520. Examples of cellulases with endo-1,4-glucanase activity (EC 3.2.1.4) are described in WO 2002/099091, e.g. those having a sequence of at least 97% identity to the amino acid sequence of positions 1 to 773 of SEQ ID NO:2 of WO 2002/099091. Another example may comprise a GH44 xyloglucanase, e.g. a xyloglucanase enzyme having a sequence of at least 60% identity to positions 40 to 559 of SEQ ID NO:2 of WO 2001/062903. Other examples of cellulases include the GH45 cellulases described in WO 96/29397. Commercially available cellulases include Celluzyme™, Carezyme™, Carezyme Premium™, Celluclean™ (e.g. Celluclean™ 5000L and Cellulclean™ 4000T), Celluclean Classic™, Cellusoft™, Endolase®, Renozyme® and Whitezyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), KAC-500(B)™ (Kao Corporation), Revitalenz™ 1000, Revitalenz™ 2000 and Revitalenz™ 3000 (DuPont), as well as Ecostone® and Biotouch® (AB Enzymes).
Geeignete Lipasen sind z.B. aus Thermomyces, z.B. aus T. lanuginosus (früher Humicola lanuginosa), wie in EP 0258068 und EP 0305216 beschrieben, Lipase aus Stämmen von Pseudomonas (einige davon jetzt umbenannt in Burkholderia), z.B. P. alcaligenes oder P. pseudoalcaligenes, P. cepacia, P. sp. Stamm SD705, P. wisconsinensis, Streptomyces-Lipasen vom GDSL-Typ, Lipase aus Thermobifida fusca, Lipase aus Geobacillus stearothermophilus, Lipase aus Bacillus subtilis und Lipase aus Streptomyces griseus und S. pristinaespiralis. Zu bevorzugten Lipasen gehören z.B. die ursprünglich aus Humicola lanuginosa (Thermomyces lanuginosus) erhältlichen bzw. daraus weiterentwickelten Lipasen, insbesondere solche mit einem oder mehreren der folgenden Aminosäureaustausche ausgehend von der genannten Lipase in den Positionen D96L, T213R und/oder N233R, besonders bevorzugt T213R und N233R. Zu den bevorzugten kommerziellen Lipaseprodukten gehören Lipolase™, Lipex™, Lipolex™ und Lipoclean™ (Novozymes A/S), Lumafast (Genencor/DuPont) und Lipomax (Gist-Brocades). Suitable lipases are, for example, those from Thermomyces, e.g. from T. lanuginosus (formerly Humicola lanuginosa) as described in EP 0258068 and EP 0305216, lipase from strains of Pseudomonas (some of them now renamed Burkholderia), e.g. P. alcaligenes or P. pseudoalcaligenes, P. cepacia, P. sp. strain SD705, P. wisconsinensis, Streptomyces lipases of the GDSL type, lipase from Thermobifida fusca, lipase from Geobacillus stearothermophilus, lipase from Bacillus subtilis and lipase from Streptomyces griseus and S. pristinaespiralis. Preferred lipases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed therefrom, in particular those with one or more of the following amino acid substitutions starting from the lipase mentioned in positions D96L, T213R and/or N233R, particularly preferably T213R and N233R. The preferred commercial lipase products include Lipolase™, Lipex™, Lipolex™ and Lipoclean™ (Novozymes A/S), Lumafast (Genencor/DuPont) and Lipomax (Gist-Brocades).
Geeignete Mannanasen sind z.B. die Bacillus subtilis Endo-ß-Mannanase, Bacillus sp. I633 Endo-ß-Mannanase, Bacillus sp. AAI12 Endo-ß-Mannanase, Bacillus sp. AA349 Endo-ß-Mannanase, Bacillus agaradhaerens NCIMB 40482 Endo-ß-Mannanase, Bacillus halodurans Endo-ß-Mannanase, Bacillus clausii Endo-ß-Mannanase, Bacillus licheniformis Endo-ß-Mannanase, Humicola insolens Endo-ß-Mannanase und Caldocellulosiruptor sp. Endo-ß-Mannanase (vgl. z.B. US 6060299, WO 99/64573, US 6566114 und WO 99/64619). Suitable mannanases are, for example, the Bacillus subtilis endo-ß-mannanase, Bacillus sp. I633 Endo-ß-mannanase, Bacillus sp. AAI12 Endo-ß-mannanase, Bacillus sp. AA349 Endo-ß-mannanase, Bacillus agaradhaerens NCIMB 40482 Endo-ß-mannanase, Bacillus halodurans Endo-ß-mannanase, Bacillus clausii Endo-ß-mannanase, Bacillus licheniformis Endo-ß-mannanase, Humicola insolens Endo-ß-mannanase and Caldocellulosiruptor sp. endo-ß-mannanase (see e.g. US 6060299, WO 99/64573, US 6566114 and WO 99/64619).
Für Wasch- und Reinigungsmittel geeignete Pektatlyasen sind z.B. in WO 2003/095638 oder WO 2015/121133 beschrieben. Beispiele für geeignete pektinolytische Enzyme sind zudem die unter den Handelsbezeichnungen Gamanase®, Pektinex AR®, X-Pect® oder Pectaway® von dem Unternehmen Novozymes, unter den Handelsbezeichnungen Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® von dem Unternehmen AB Enzymes und unter der Handelsbezeichnung Pyrolase® von dem Unternehmen Diversa Corp, erhältlichen Enzyme und Enzym-Zubereitungen. Pectate lyases suitable for washing and cleaning agents are described, for example, in WO 2003/095638 or WO 2015/121133. Examples of suitable pectinolytic enzymes are also the enzymes and enzyme preparations available under the trade names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from the company Novozymes, under the trade names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® from the company AB Enzymes and under the trade name Pyrolase® from the company Diversa Corp.
In den hierin beschriebenen Reinigungsmitteln können die einzusetzenden Enzyme ferner zusammen mit Begleitstoffen, etwa aus der Fermentation, konfektioniert sein. In flüssigen Formulierungen werden die Enzyme bevorzugt als Enzymflüssigformulierung(en) eingesetzt. In the cleaning agents described here, the enzymes to be used can also be formulated together with accompanying substances, for example from fermentation. In liquid formulations, the enzymes are preferably used as enzyme liquid formulation(s).
Die Enzyme werden in der Regel nicht in Form des reinen Proteins, sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt. The enzymes are generally not provided in the form of pure protein, but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other additives.
Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale- Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil. Alternatively, the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer that is impermeable to water, air and/or chemicals. In addition, other active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents or dyes, can be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable in storage due to the coating.
Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist. Furthermore, it is possible to package two or more enzymes together so that a single granulate has several enzyme activities.
Die Enzyme können auch in wasserlösliche Filme, wie sie beispielsweise bei der Konfektionierung von Wasch- und Reinigungsmitteln in Einheitsdosisform verwendet werden, eingebracht werden. Ein derartiger Film ermöglicht die Freisetzung der Enzyme nach Kontakt mit Wasser. Wie hierin verwendet, bezieht sich "wasserlöslich" auf eine Filmstruktur, die vorzugsweise vollständig wasserlöslich ist. Bevorzugt besteht ein solcher Film aus (vollständig oder teilweise hydrolysiertem) Polyvinylalkohol (PVA). Die erfindungsgemäßen Mittel können einen oder mehrere reversible Enzyminhibitor(en)/- stabilisator(en) umfassen. Die erfindungsgemäßen Mittel können den/die reversiblen Enzyminhibitor(en)/-stabilisator(en) in einer Konzentration von 0,1 bis 2 Gew.-%, vorzugsweise 0,3 bis 1 ,5 Gew.-%, enthalten, bezogen auf das Gesamtgewicht des Mittels. Falls mehrere Inhibitoren/Stabilisatoren enthalten sind, beziehen sich diese Angaben auf die Gesamtkonzentration. The enzymes can also be incorporated into water-soluble films, such as those used in the packaging of detergents and cleaning agents in unit dosage form. Such a film enables the release of the enzymes after contact with water. As used herein, "water-soluble" refers to a film structure that is preferably completely water-soluble. Preferably, such a film consists of (fully or partially hydrolyzed) polyvinyl alcohol (PVA). The agents according to the invention can comprise one or more reversible enzyme inhibitors/stabilizers. The agents according to the invention can contain the reversible enzyme inhibitors/stabilizers in a concentration of 0.1 to 2% by weight, preferably 0.3 to 1.5% by weight, based on the total weight of the agent. If several inhibitors/stabilizers are included, these details refer to the total concentration.
Diese können insbesondere ausgewählt sein aus der aus Polyolen, wie Glycerin oder 1 ,2- Ethylenglycol, Benzamidinhydrochlorid, Borax, Borsäuren, Boronsäuren oder deren Salze oder Ester oder Derivate, insbesondere Phenylboronsäurederivate oder 4-Formylphenylboronsäure (4-FPBA), Antioxidantien, speziellen Peptidverbindungen und Kombinationen davon bestehenden Gruppe. These can in particular be selected from the group consisting of polyols, such as glycerin or 1,2-ethylene glycol, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters or derivatives, in particular phenylboronic acid derivatives or 4-formylphenylboronic acid (4-FPBA), antioxidants, special peptide compounds and combinations thereof.
Im Rahmen der vorliegenden Erfindung wird unter "Phenylboronsäurederivat" eine Verbindung mit der Formel (III) verstanden. Die Verbindung der Formel (III) weist folgende Strukturformel auf:
Figure imgf000050_0001
wobei R Wasserstoff, eine Hydroxyl-, eine C-i-6 Alkyl-, eine substituierte C-i-6 Alkyl-, eine C-i-6 Alkenyl oder eine substituierte C-i-6 Alkenyl-Gruppe ist. Bevorzugt ist der Rest R in dem Phenylboronsäurederivat eine C-i-6 Alkyl-Gruppe und hierunter weiter bevorzugt -CH3, -CH3CH2 oder - CH3CH2CH2 sein. Weiter bevorzugt ist der Rest R in dem Phenylboronsäurederivat Wasserstoff. Besonders bevorzugt ist das Phenylboronsäurederivat 4-Formyl-phenylboronsäure (4-FPBA). In the context of the present invention, "phenylboronic acid derivative" is understood to mean a compound with the formula (III). The compound of the formula (III) has the following structural formula:
Figure imgf000050_0001
where R is hydrogen, a hydroxyl, a C 1-6 alkyl, a substituted C 1-6 alkyl, a C 1-6 alkenyl or a substituted C 1-6 alkenyl group. Preferably, the radical R in the phenylboronic acid derivative is a C 1-6 alkyl group and more preferably -CH3, -CH3CH2 or -CH3CH2CH2. More preferably, the radical R in the phenylboronic acid derivative is hydrogen. The phenylboronic acid derivative is particularly preferably 4-formylphenylboronic acid (4-FPBA).
Die eingesetzte Inhibitor/Stabilisatorverbindung kann Borsäure sein. The inhibitor/stabilizer compound used can be boric acid.
In besonders bevorzugten Ausführungsformen ist das erfindungsgemäße Wasch- und/oder Reinigungsmittel im Wesentlichen frei von borhaltigen Verbindungen. "Im Wesentlichen frei von borhaltigen Verbindungen" bedeutet in diesem Zusammenhang, dass die erfindungsgemäßen Mittel weniger als 2 Gew.-%, vorzugsweise weniger als 1 Gew.-%, weiter bevorzugt weniger als 0,5 Gew.-% und besonders bevorzugt weniger als 0,1 Gew.-%, borhaltige Verbindungen, bezogen auf das Gesamtgewicht des Mittels, enthalten. In ganz besonders bevorzugten Ausführungsformen sind die erfindungsgemäßen Mittel frei von borhaltigen Verbindungen, d.h. sie enthalten insbesondere keine Borsäure und/oder Phenylboronsäurederivate. In particularly preferred embodiments, the washing and/or cleaning agent according to the invention is essentially free of boron-containing compounds. "Essentially free of boron-containing compounds" in this context means that the agents according to the invention contain less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight and particularly preferably less than 0.1% by weight, of boron-containing compounds, based on the total weight of the agent. In very particularly preferred embodiments, the agents according to the invention are free of boron-containing compounds, i.e. they contain in particular no boric acid and/or phenylboronic acid derivatives.
In verschiedenen Ausführungsformen können das Enzym und die Inhibitor/Stabilisatorverbindung in einer Enzymzusammensetzung vorformuliert vorliegen. Wie aus den vorherigen Ausführungen ersichtlich, bildet das Enzym-Protein nur einen Bruchteil des Gesamtgewichts üblicher Enzym- Zubereitungen. Bevorzugt eingesetzte Enzym-Zubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, besonders bevorzugt zwischen 0,4 und 20 Gew.-% und insbesondere zwischen 0,8 und 10 Gew.-% des Enzymproteins. In solchen Zusammensetzungen kann die Inhibitor/Stabilisatorverbindung in einer Menge von 0,05 bis 35 Gew.-%, vorzugsweise von 0,05 bis 10 Gew.-%, bezogen auf das Gesamtgewicht in der Enzymzusammensetzung, enthalten sein. Diese Enzymzusammensetzung, die ebenfalls ein Bestandteil der vorliegenden Erfindung ist, kann dann in erfindungsgemäßen Mitteln eingesetzt werden, und zwar in Mengen, die zu den oben angegeben Endkonzentrationen im Mittel führen. In various embodiments, the enzyme and the inhibitor/stabilizer compound can be pre-formulated in an enzyme composition. As can be seen from the previous statements, the enzyme protein only forms a fraction of the total weight of conventional enzyme preparations. Preferably used enzyme preparations contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein. In such compositions, the inhibitor/stabilizer compound can be present in an amount of 0.05 to 35% by weight, preferably from 0.05 to 10% by weight, based on the total weight in the enzyme composition. This enzyme composition, which is also a component of the present invention, can then be used in agents according to the invention in amounts which lead to the final concentrations in the agent indicated above.
Ein weiterer Erfindungsgegenstand ist ein Mittel zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt zur fasertiefen Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien, dadurch gekennzeichnet dass das Mittel ein Dispersin enthält, wobei das Dispersin ß-1 ,6-N-Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135, 138, 139, 140, 142, 145, 147, 148, 149, 150,A further subject matter of the invention is an agent for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, as well as for improving the hygiene of textiles, characterized in that the agent contains a dispersin, wherein the dispersin has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical and, with respect to the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72, 74, 77, 79, 80, 81, 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111, 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131, 135, 138, 139, 140, 142, 145, 147, 148, 149, 150,
151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175, 177, 178, 179, 181 , 185, 186, 187, 188, 189,151, 152, 163, 164, 167, 168, 170, 171, 173, 174, 175, 177, 178, 179, 181, 185, 186, 187, 188, 189,
199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221 , 222, 224, 225, 227, 230, 232, 233, 234,199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221, 222, 224, 225, 227, 230, 232, 233, 234,
235, 237, 244, 249, 251 , 252, 253, 254, 256, 260, 261 , 262, 263, 264, 265, 267, 268, 270, 271 , 272,235, 237, 244, 249, 251, 252, 253, 254, 256, 260, 261, 262, 263, 264, 265, 267, 268, 270, 271, 272,
273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 und 323 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion aufweist. 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291, 296, 300, 301, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, having at least one amino acid substitution and/or deletion.
Eine bevorzugte Ausführungsform betrifft ein Mittel zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt zur fasertiefen Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien, dadurch gekennzeichnet dass das Mittel ein Dispersin enthält, wobei das Dispersin ß-1 ,6-N-Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135, 138, 139, 140, 142, 145, 147, 148, 149, 150,A preferred embodiment relates to an agent for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, as well as for improving the hygiene of textiles, characterized in that the agent contains a dispersin, wherein the dispersin has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical and, with respect to the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72, 74, 77, 79, 80, 81, 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111, 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131, 135, 138, 139, 140, 142, 145, 147, 148, 149, 150,
151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175, 177, 178, 179, 181 , 185, 186, 187, 188, 189,151, 152, 163, 164, 167, 168, 170, 171, 173, 174, 175, 177, 178, 179, 181, 185, 186, 187, 188, 189,
199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221 , 222, 224, 225, 227, 230, 232, 233, 234,199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221, 222, 224, 225, 227, 230, 232, 233, 234,
235, 237, 244, 249, 251 , 252, 253, 254, 256, 260, 261 , 262, 263, 264, 265, 267, 268, 270, 271 , 272,235, 237, 244, 249, 251, 252, 253, 254, 256, 260, 261, 262, 263, 264, 265, 267, 268, 270, 271, 272,
273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 und 323 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion, die aus der aus D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52*, Y52M, G54L, G54M, G54N, S56T, S56W, S57W, E58N, N59A, N59C, N59D, N59E, N59F, N59M, N59R, N59V, N59W, T60V, N62C, N62D, N62H, N62Q, N62W, T63C, T63D, T63L, T63N, T63R, T63V, K67A, K67L, N68L, N68Q, L71 H, L71 N, L71 R, L71V, L71W, S72*, S72C, S72D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77A, D79V, K80*, K80E, K80H, K80L, K80N, K80Q, K80V, K80W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S, K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, V106N, V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K107T, K107V, K107W, N110M, N110R, N110V, D111A, D111 E, D111 M, D111 N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, S117*, S117D, S117H, S117N, S117P, E118*, E118A, E118D, E118G, E118L, E119G, E119W, T120I, T120L, T120M, T120V, T120W, D122*, D122H, D122R, Y123W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y124R, Y124T, Y124V, Y124W, D125C, D125G, D125K, D125Q, D125R, N126V, R127D, R127H, R127K, R127L, R127M, R127Q, R127W, V128C, V128L, V128T, D131V, Q135*, Q135A, Q135D, Q135E, Q135K, Q135M, Q135Y, D138K, D138L, D138M, D138Q, D138R, D138S, D138V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P147A, P147C, P147D, P147F, P147G, P147L, P147M, P147R, P147S, P147T, P147V, K148A, K148D, K148L, K148V, F149L, F149M, F149N, E150D, E150H, E150K, E150L, E150M, E150N, E150R, E150V, E150W, E150Y, G151A, G151C, G151 D, G151 L, G151 N, G151 P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G164H, G164S, G164V, V167D, V167E, V167L, V167P, V167Q, V167R, V167W, H168N, L170A, L170D, L170E, L170F, L170H, L170K, L170M, L170N, L170P, L170Q, L170R, L170S, L170V, L170W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, D171 M, D171Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D174V, D174W, F175Y, N177M, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181C, S181 D, S181 F, S181G, S181 N, S181 P, S181Q, S181T, S181V, S181W, E185M, E185R, E185V, E185W, S186D, S186E, S186H, S186I, S186K, S186L, S186M, S186N, S186Q, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K187V, K187W, Y188P, E189L, E189V, E189W, S199C, S199L, S199M, S199Y, E200D, E200F, E200K, E200L, E200M, E200N, E200R, E200W, A203C, A203D, A203E, A203G, A203L, A203M, A203P, A203R, A203S, A203T, A203V, A203W, N204L, N204M, N204V, N204W, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, D207Q, D207S, D207V, D207W, S208A, S208C, S208D, S208G, S208L, S208Q, S208T, S208V, S208W, S210T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G222D, E224A, E224P, N227A, N227Q, N227R, N227S, N227T, N227K, D230*, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N233R, N233W, W234R, G235W, G235A, G235E, G235F, G235H, G235I, G235L, G235M, G235N, G235P, G235S, G235V, S237C, S237G, S237M, S237N, S237W, S237Y, Y244C, Y244E, Y244M, L249H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S251 N, S251 R, S251W, N252P, N252C, G253D, G253W, F254I, F254L, F254M, F254Y, Q256E, Q256R, N260*, N260A, N260C, N260E, N260I, N260K, N260L, N260M, N260Q, N260R, N260V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q262W, Q262Y, M263K, M263L, M263Q, D264*, D264C, D264E, Y265F, N267S, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274R, K274A, K274H, F276A, F276C, F276K, F276N, F276G, F276L, F276M, F276P, F276S, F276V, F276W, I278A, I278K, I278N, I278Q, I278V, S279C, S279D, S279E, S279G, S279N, D280C, D280E, Y281*, Y281A, Y281C, Y281 H, Y281 K, Y281 N, Y281 P, Y282E, Y282N, H283I, A284I, A284L, A284N, A284P, A284T, A284V, T287N, S288D, S288K, S288N, V290I, K291 L, K291 R, K291V, T296C, E300A, E300D, H301C, H301 N, H301 R, T303A, T303C, T303G, T303K, T303Q, T303R, T303W, D304C, D304M, L305M, L305N, S306C, K308A, K308D, K308G, K308I, K308L, K308Q, K308S, K308T, K308V, K308Y, K309A, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R und Kombinationen davon bestehenden Gruppe ausgewählt ist, aufweist. 273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, at least one Amino acid substitution and/or deletion resulting from the amino acid sequence selected from D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52*, Y52M, G54L, G54M, G54N, S56T, S56W, S57W, E58N, N59A, N59C, N59D, N59 E. L71V, L71W, S72*, S72C, S72D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77A, D79V, K80*, K80E, K80H, K80L, K80N, K80Q, K80V, K80 W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S, K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, V106N, V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K107T, K107V, K107W, N110M, N110R, N110V, D111A, D111 E, D111 M, 1N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, S117*, S117D, S117H, S117N, S117P, E118*, E118A, E118D, E118L, E119G, E119W, T120I, T120L, T120M, T120V, T120W, D122*, D122H, D122R, Y123W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y124R, Y124T, Y124V, Y12 4W, D125C, D125G, D125K, D125Q, D125R, N126V, R127D, R127H, R127K, R127L, R127M, R127Q, R127W, V128C, V128L, V128T, D131V, Q135*, Q135D, Q135E, Q135K, Q135M, Q135Y, D138K, D138L, D138M, D138Q, D138R, D138S, D138V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P14 7A, P147C, P147D, P147F, P147G, P147L, P147M, P147R, P147S, P147T, P147V, K148A, K148D, K148L, K148V, F149L, F149M, F149N, E150D, E150K, E150L, E150M, E150N, E150R, E150V, E150W, E150Y, G151A, G151C, G151 D, G151 L, G151 N, G151 P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G16 4H, G164S, G164V, V167D, V167E, V167L, V167P, V167Q, V167R, V167W, H168N, L170A, L170D, L170E, L170F, L170H, L170K, L170M, L170N, L170P, L170R, L170S, L170V, L170W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, D171 M, D171Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D17 4V, D174W, F175Y, N177M, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181C, S181 D, S181 F, S181G, S181 N, S181 P, S181Q, S181T, S181V, S181W, E185R, E185V, E185W, S186D, S186E, S186H, S186I, S186K, S186L, S186M, S186N, S186Q, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K18 7V, K187W, Y188P, E189L, E189V, E189W, S199C, S199L, S199M, S199Y, E200D, E200F, E200K, E200L, E200M, E200N, E200R, E200W, A203C, A203D, A203G, A203L, A203M, A203P, A203R, A203S, A203T, A203V, A203W, N204L, N204M, N204V, N204W, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, 7Q, D207S, D207V, D207W, S208A, S208C, S208D, S208G, S208L, S208Q, S208T, S208V, S208W, S210T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G222D, E224A, E224P, N227A, N227Q, N227R, N227S, N227T, N227K, D230*, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N23 3R, N233W, W234R, G235W, G235A, G235E, G235F, G235H, G235I, G235L, G235M, G235N, G235P, G235S, G235V, S237C, S237G, S237M, S237N, S237Y, Y244C, Y244E, Y244M, L249H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S251 N, S251 R, S251W, N252P, N252C, G253D, G253W, F254I, F254L, F254M, F25 4Y, Q256E, Q256R, N260*, N260A, N260C, N260E, N260I, N260K, N260L, N260M, N260Q, N260R, N260V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q262W, Q262Y, M263K, M26 3L, M263Q, D264*, D264C, D264E, Y265F, N267S, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274R, K274A, K274H, F276A, F276C, F276K, F276N, F276G, F276L, F276M, F276P, F276S, F276V, F276W, I278A, I278K, I278N, I27 8Q, I278V, S279C, S279D, S279E, S279G, S279N, D280C, D280E, Y281*, Y281A, Y281C, Y281 H, Y281 K, Y281 N, Y281 P, Y282E, Y282N, H283I, A284I, A284N, A284P, A284T, A284V, T287N, S288D, S288K, S288N, V290I, K291 L, K291 R, K291V, T296C, E300A, E300D, H301C, H301 N, H301 R, T303A, T303C, T30 3G, T303K, T303Q, T303R, T303W, D304C, D304M, L305M, L305N, S306C, K308A, K308D, K308G, K308I, K308L, K308Q, K308S, K308T, K308V, K308Y, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R and combinations thereof.
Ein weiterer Erfindungsgegenstand betrifft ein Verfahren zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt zur fasertiefen Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien, dadurch gekennzeichnet, dass in mindestens einem Verfahrensschritt ein erfindungsgemäßes Dispersin, wie hierin beschrieben, und/oder ein erfindungsgemäßes Mittel, wie hierin beschrieben, angewendet wird, wobei das Verfahren vorzugsweise in einem Temperaturbereich von etwa 10°C bis etwa 60°C, bevorzugt etwa 15°C bis etwa 40°C, besonders bevorzugt etwa 20°C bis etwa 30°C. A further subject matter of the invention relates to a method for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, and for improving the hygiene of textiles, characterized in that in at least one method step a dispersin according to the invention, as described herein, and/or an agent according to the invention, as described herein, is used, wherein the method is preferably carried out in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
Hierunter fallen sowohl manuelle als auch maschinelle Verfahren, wobei maschinelle Verfahren aufgrund ihrer präziseren Steuerbarkeit, was z.B. die eingesetzten Mengen und Einwirkzeiten angeht, bevorzugt sind. Verfahren zur Reinigung von Textilien zeichnen sich im Allgemeinen dadurch aus, dass in mehreren Verfahrensschritten verschiedene reinigungsaktive Substanzen auf das Reinigungsgut aufgebracht und nach der Einwirkzeit abgewaschen werden, oder dass das Reinigungsgut in sonstiger Weise mit einem Waschmittel oder einer Lösung oder Verdünnung dieses Mittels behandelt wird. Mit umfasst sind dabei auch Verfahren unter Verwendung (halb-)automatisierter Wasch- oder Reinigungssysteme wie z.B. Wischrobotor oder Nassstaubsauger. This includes both manual and mechanical processes, with mechanical processes being preferred due to their more precise controllability, for example with regard to the quantities used and exposure times. Processes for cleaning textiles are generally characterized by the fact that various cleaning-active substances are applied to the item to be cleaned in several process steps and washed off after the exposure time, or that the item to be cleaned is treated in some other way with a detergent or a solution or dilution of this agent. This also includes processes using (semi-)automated washing or cleaning systems such as robot mops or wet vacuum cleaners.
Dieser Erfindungsgegenstand umfasst auch ein maschinelles Geschirrspülverfahren. Die Dosierung des erfindungsgemäßen Mittels in die Reinigungsflotte kann in einem solchen Verfahren z.B. mittels der Dosierkammer in der Tür oder mittels eines zusätzlichen Dosierbehälters im Innenraum der Geschirrspülmaschine erfolgen. Alternativ kann das Mittel auch direkt auf das verschmutzte Geschirr oder auf eine der Innenwände der Geschirrspülmaschine, z.B. die Innenseite der Tür aufgebracht werden. Die Durchführung des erfindungsgemäßen Verfahrens erfolgt im Innenraum einer handelsüblichen Geschirrspülmaschine. Das Reinigungsprogramm kann bei einer Geschirrspülmaschine in der Regel vor Durchführung des Geschirrspülverfahrens durch den Verbraucher gewählt und festgelegt werden. Das in dem erfindungsgemäßen Verfahren eingesetzte Reinigungsprogramm der Geschirrspülmaschine umfasst dabei mindestens einen Vorspülgang und einen Reinigungsgang. Erfindungsgemäß bevorzugt werden Reinigungsprogramme, die weitere Reinigungs- oder Spülgänge, z.B. einen Klarspülgang umfassen. Das erfindungsgemäße Verfahren ist mit besonderem Vorzug Bestandteil eines Reinigungsprogramms, umfassend einen Vorspülgang, einen Reinigungsgang sowie einen Klarspülgang. Das erfindungsgemäße Verfahren wird bevorzugt in Verbindung mit solchen Reinigungsprogrammen eingesetzt, bei denen die Waschflotte im Verlauf des Reinigungsgangs erwärmt wird. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens ist der Reinigungsgang, in dessen Verlauf das erfindungsgemäße Mittel in den Innenraum der Geschirrspülmaschine eindosiert wird dadurch gekennzeichnet, dass in seinem Verlauf die Temperatur der Reinigungsflotte auf Werte oberhalb 30°C, vorzugsweise oberhalb 40°C und insbesondere oberhalb 50°C ansteigt. This subject matter of the invention also includes a machine dishwashing process. The dosing of the agent according to the invention into the cleaning solution can be carried out in such a process, for example, by means of the dosing chamber in the door or by means of an additional dosing container in the interior of the dishwasher. Alternatively, the agent can also be applied directly to the soiled dishes or to one of the interior walls of the dishwasher, e.g. the inside of the door. The process according to the invention is carried out in the interior of a commercially available dishwasher. The cleaning program in a dishwasher can usually be selected and set by the consumer before the dishwashing process is carried out. The cleaning program of the dishwasher used in the process according to the invention comprises at least one pre-wash cycle and a cleaning cycle. According to the invention, cleaning programs are preferred which include further cleaning or rinsing cycles, e.g. a final rinse cycle. The method according to the invention is particularly preferably part of a cleaning program comprising a pre-rinse cycle, a cleaning cycle and a final rinse cycle. The method according to the invention is preferably used in conjunction with cleaning programs in which the washing liquor is heated during the cleaning cycle. In a preferred embodiment of the method according to the invention, the cleaning cycle, during which the agent according to the invention is metered into the interior of the dishwasher, is characterized in that during its course the temperature of the cleaning liquor rises to values above 30°C, preferably above 40°C and in particular above 50°C.
Alternative Ausführungsformen dieses Erfindungsgegenstandes stellen auch Verfahren zur Behandlung von Textilrohstoffen oder zur Textilpflege dar, bei denen in wenigstens einem Verfahrensschritt ein erfindungsgemäßes Mittel aktiv wird. Hierunter sind Verfahren für Textilrohstoffe, Fasern oder Textilien mit natürlichen Bestandteilen bevorzugt, und ganz besonders für solche mit Wolle oder Seide. Alternative embodiments of this subject matter of the invention also represent processes for treating textile raw materials or for textile care, in which an agent according to the invention is active in at least one process step. Among these, processes for textile raw materials, fibers or textiles with natural components are preferred, and very particularly for those with wool or silk.
Alle Sachverhalte, Gegenstände und Ausführungsformen, die für das erfindungsgemäße Mittel beschrieben sind, sind auch auf diese Erfindungsgegenstände anwendbar. Daher wird an dieser Stelle ausdrücklich auf die Offenbarung an entsprechender Stelle verwiesen mit dem Hinweis, dass diese Offenbarung auch für die vorstehende erfindungsgemäße Verwendung gilt. All facts, objects and embodiments described for the agent according to the invention are also applicable to these objects of the invention. Therefore, at this point, express reference is made to the disclosure at the appropriate point with the note that this disclosure also applies to the above use according to the invention.
BEISPIELE EXAMPLES
Beispiel 1 : Bestimmung der fasertiefen Reinigung Example 1: Determination of fibre-deep cleaning
Tabelle 1 : Verwendete Waschmittelmatrix
Figure imgf000055_0001
Table 1 : Detergent matrix used
Figure imgf000055_0001
Zur Vorbereitung wurden ca. 2,0 kg weiße Textilien (T-Shirts, Frottierhandtücher) und die verwendete Haushaltswaschmaschine (Miele Novotronic W1514) durch wiederholtes Waschen mit einem bleichehaltigen, handelsüblichen Vollwaschmittel im Intensivprogramm (95°C, 16°dH, 1400 U/min) gereinigt und desinfiziert, sowie die Textilien in einem Wäschetrockner getrocknet. Durch wiederholtes Waschen (30°C, 16°dH, 1400 U/min, 120 min) und Lagern unter standardisierten Bedingungen der so vorbereiten Wäsche in der so vorbereiteten Haushaltswaschmaschine wurden typische Haushaltswaschbedingungen simuliert und dadurch entsprechende (Bio-)belag-ZBiosoil- Bildung auf den so behandelten Textilien hervorgerufen. Nach 2 und 20 Waschzyklen wurde die luftgetrocknete Wäsche beurteilt und mittels eines Rasterelektronenmikroskops wurde die fasertiefe Reinigung untersucht und beurteilt. In preparation, approximately 2.0 kg of white textiles (T-shirts, terry towels) and the domestic washing machine used (Miele Novotronic W1514) were cleaned and disinfected by repeated washing with a commercially available heavy-duty detergent containing bleach in the intensive program (95°C, 16°dH, 1400 rpm), and the textiles were dried in a tumble dryer. By repeatedly washing (30°C, 16°dH, 1400 rpm, 120 min) and storing the laundry prepared in this way under standardized conditions in the domestic washing machine prepared in this way, typical domestic washing conditions were simulated and the corresponding (bio)deposit ZBiosoil formation was induced on the textiles treated in this way. After 2 and 20 wash cycles, the air-dried laundry was assessed and the fiber-deep cleaning was examined and assessed using a scanning electron microscope.
Die Ergebnisse sind in Figur 1 und Tabelle 2 gezeigt. The results are shown in Figure 1 and Table 2.
Figur 1 zeigt Rasterelektronenmikroskop-Aufnahmen von Fasern nach dem Waschen (Vergrößerung: 50 pm). Figur 1 A zeigt eine Aufnahme von Fasern nach zweimaligem Waschen mit einem nicht-erfindungsgemäßen Waschmittel (V1 ; ohne Dispersin). Figur 1 B zeigt eine Aufnahme von Fasern nach zwanzigmaligem Waschen mit einem nicht-erfindungsgemäßen Waschmittel (V1 ; ohne Dispersin). Figur 1C zeigt eine Aufnahme von Fasern nach zweimaligem Waschen mit einem erfindungsgemäßen Waschmittel (E1 ; mit Dispersin). Figur 1 D zeigt eine Aufnahme von Fasern nach zwanzigmaligem Waschen mit einem erfindungsgemäßen Waschmittel (E1 ; mit Dispersin). Figure 1 shows scanning electron microscope images of fibers after washing (magnification: 50 pm). Figure 1 A shows a picture of fibers after washing twice with a non-inventive detergent (V1; without dispersin). Figure 1B shows a photo of fibers after washing twenty times with a non-inventive detergent (V1; without dispersin). Figure 1C shows a photo of fibers after washing twice with a detergent according to the invention (E1; with dispersin). Figure 1D shows a photo of fibers after washing twenty times with a detergent according to the invention (E1; with dispersin).
Im Vergleich der Rasterelektronenmikroskop-Aufnahmen erkennt man sehr gut die fasertiefe Reinigung. Die Textilien, die mit dem erfindungsgemäßen Waschmittel (E1) gewaschen wurden, zeigten kaum bis keine Ablagerungen zwischen und/oder an den Fasern. Wie man in Figur 1 erkennt, nehmen die Ablagerungen bei den Textilien, die mit einem Waschmittel ohne Dispersin (V1) gewaschen wurden, mit Anzahl der Waschzyklen zu, während die Textilien, die mit dem erfindungsgemäßen Waschmittel (E1) gewaschen wurde, auch nach mehreren Waschzyklen kaum bis keine Ablagerungen zwischen und/oder an den Fasern aufweisen. When comparing the scanning electron microscope images, the deep fiber cleaning can be clearly seen. The textiles that were washed with the detergent according to the invention (E1) showed little to no deposits between and/or on the fibers. As can be seen in Figure 1, the deposits in the textiles that were washed with a detergent without dispersin (V1) increase with the number of wash cycles, while the textiles that were washed with the detergent according to the invention (E1) show little to no deposits between and/or on the fibers even after several wash cycles.
Tabelle 2: Biobelaqsbildunq zwischen den Fasern der Textilien
Figure imgf000056_0001
Table 2: Biobelaq formation between the fibres of the textiles
Figure imgf000056_0001
(- = kein Biobelag, + = leichter Biobelag, ++ = starker Biobelag) (- = no organic coating, + = light organic coating, ++ = strong organic coating)
Beispiel 2: Beispielformulierunqen Example 2: Sample formulations
Das erfindungsgemäße Dispersin kann in verschiedenen Wasch- und Reinigungsmitteln eingesetzt werden und seinen Effekt verwirklichen. The dispersin according to the invention can be used in various washing and cleaning agents and realize its effect.
Tabelle 3: Flüssiqwaschmittel
Figure imgf000056_0002
Table 3: Liquid detergents
Figure imgf000056_0002
Figure imgf000057_0001
Figure imgf000057_0001
Tabelle 4: Flüssiqwaschmittel
Figure imgf000057_0002
Tabelle 5: Feste Waschmittel
Figure imgf000058_0001
Table 4: Liquid detergents
Figure imgf000057_0002
Table 5: Solid detergents
Figure imgf000058_0001
Tabelle 6: Handqeschirrspülmittel
Figure imgf000058_0002
Table 6: Hand dishwashing detergent
Figure imgf000058_0002
Tabelle 7: Zweiphasiqes Geschirrspülmittel
Figure imgf000058_0003
Table 7: Two-phase dishwashing detergent
Figure imgf000058_0003
Figure imgf000059_0001
Figure imgf000059_0001

Claims

PATENTANSPRÜCHE PATENT CLAIMS
1 . Verwendung eines Dispersin, das ß-1 ,6-N-Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135, 138, 139, 140, 142, 145, 147, 148, 149, 150, 151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175, 177, 178, 179, 181 , 185, 186, 187, 188, 189,1 . Use of a dispersin which has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which is at least 70% and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length and, based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72, 7 4, 77, 79, 80, 81, 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111, 113, 114, 116, 117, 118, 119, 120, 122, 123, 125, 126, 127, 128, 131, 135, 138, 139, 140, 142, 145, 147, 148, 149, 150, 151, 152, 163, 164, 167, 168, 170, 171, 174, 175, 177, 178, 179, 181, 185, 186, 187, 188, 189,
199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221 , 222, 224, 225, 227, 230, 232, 233, 234, 235, 237, 244, 249, 251 , 252, 253, 254, 256, 260, 261 , 262, 263, 264, 265, 267, 268, 270, 271 , 272, 273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 und 323 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion aufweist, zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt zur fasertiefen Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien. 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221, 222, 224, 225, 227, 230, 232, 233, 234, 235, 237, 244, 249, 2 51, 252, 253, 254, 256, 260, 261, 262, 263, 264, 265, 267, 268, 270, 271, 272, 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, at least one amino acid substitution and/ or deletion, for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for fiber-deep cleaning of textiles, as well as for improving the hygiene of textiles.
2. Verwendung nach Anspruch 1 , wobei die mindestens eine Aminosäuresubstitution und/oder -deletion aus der aus D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52*, Y52M, G54L, G54M, G54N, S56T, S56W, S57W, E58N, N59A, N59C, N59D, N59E, N59F, N59M, N59R, N59V, N59W, T60V, N62C, N62D, N62H, N62Q, N62W, T63C, T63D, T63L, T63N, T63R, T63V, K67A, K67L, N68L, N68Q, L71 H, L71 N, L71 R, L71V, L71W, S72*, S72C, S72D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77A, D79V, K80*, K80E, K80H, K80L, K80N, K80Q, K80V, K80W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S, K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, V106N, V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K107T, K107V, K107W, N110M, N110R, N110V, D111A, D111 E, D111 M, D111 N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, S117*, S117D, S117H, S117N, S117P, E118*, E118A, E118D, E118G, E118L, E119G, E119W, T120I, T120L, T120M, T120V, T120W, D122*, D122H, D122R, Y123W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y124R, Y124T, Y124V, Y124W, D125C, D125G, D125K, D125Q, D125R, N126V, R127D, R127H, R127K, R127L, R127M, R127Q, R127W, V128C, V128L, V128T, D131V, Q135*, Q135A, Q135D, Q135E, Q135K, Q135M, Q135Y, D138K, D138L, D138M, D138Q, D138R, D138S, D138V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P147A, P147C, P147D, P147F, P147G, P147L, P147M, P147R, P147S, P147T, P147V, K148A, K148D, K148L, K148V, F149L, F149M, F149N, E150D, E150H, E150K, E150L, E150M, E150N, E150R, E150V, E150W, E150Y, G151A, G151C, G151 D, G151 L, G151 N, G151 P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G164H, G164S, G164V, V167D, V167E, V167L, V167P, V167Q, V167R, V167W, H168N, L170A, L170D, L170E, L170F, L170H, L170K, L170M, L170N, L170P, L170Q, L170R, L170S, L170V, L170W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, D171 M, D171Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D174V, D174W, F175Y, N177M, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181C, S181 D, S181 F, S181G, S181 N, S181 P, S181Q, S181T, S181V, S181W, E185M, E185R, E185V, E185W, S186D, S186E, S186H, S186I, S186K, S186L, S186M, S186N, S186Q, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K187V, K187W, Y188P, E189L, E189V, E189W, S199C, S199L, S199M, S199Y, E200D, E200F, E200K, E200L, E200M, E200N, E200R, E200W, A203C, A203D, A203E, A203G, A203L, A203M, A203P, A203R, A203S, A203T, A203V, A203W, N204L, N204M, N204V, N204W, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, D207Q, D207S, D207V, D207W, S208A, S208C, S208D, S208G, S208L, S208Q, S208T, S208V, S208W, S210T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G222D, E224A, E224P, N227A, N227Q, N227R, N227S, N227T, N227K, D230*, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N233R, N233W, W234R, G235W, G235A, G235E, G235F, G235H, G235I, G235L, G235M, G235N, G235P, G235S, G235V, S237C, S237G, S237M, S237N, S237W, S237Y, Y244C, Y244E, Y244M, L249H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S251 N, S251 R, S251W, N252P, N252C, G253D, G253W, F254I, F254L, F254M, F254Y, Q256E, Q256R, N260*, N260A, N260C, N260E, N260I, N260K, N260L, N260M, N260Q, N260R, N260V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q262W, Q262Y, M263K, M263L, M263Q, D264*, D264C, D264E, Y265F, N267S, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274R, K274A, K274H, F276A, F276C, F276K, F276N, F276G, F276L, F276M, F276P, F276S, F276V, F276W, I278A, I278K, I278N, I278Q, I278V, S279C, S279D, S279E, S279G, S279N, D280C, D280E, Y281*, Y281A, Y281C, Y281 H, Y281 K, Y281 N, Y281 P, Y282E, Y282N, H283I, A284I, A284L, A284N, A284P, A284T, A284V, T287N, S288D, S288K, S288N, V290I, K291 L, K291 R, K291V, T296C, E300A, E300D, H301C, H301 N, H301 R, T303A, T303C, T303G, T303K, T303Q, T303R, T303W, D304C, D304M, L305M, L305N, S306C, K308A, K308D, K308G, K308I, K308L, K308Q, K308S, K308T, K308V, K308Y, K309A, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R und Kombinationen davon bestehenden Gruppe ausgewählt ist. 2. Use according to claim 1, wherein the at least one amino acid substitution and/or deletion is selected from the group consisting of D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52*, Y52M, G54L, G54M, G54N, S56T, S56W, S57W, E58N, N59 A. L71 H, L71 N, L71 R, L71V, L71W, S72*, S72C, S72D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77A, D79V, K80*, K80E, K80H, K80L, K80 N, K80Q, K80V, K80W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S, K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, V106N, V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K107T, K107V, K107W, N110M, N110R, N110V, D11 1A, D111 E, D111 M, D111 N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, S117*, S117D, S117H, S117N, S117P, E118*, E118D, E118G, E118L, E119G, E119W, T120I, T120L, T120M, T120V, T120W, D122*, D122H, D122R, Y123W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y12 4R, Y124T, Y124V, Y124W, D125C, D125G, D125K, D125Q, D125R, N126V, R127D, R127H, R127K, R127L, R127M, R127Q, R127W, V128C, V128L, V128T, Q135*, Q135A, Q135D, Q135E, Q135K, Q135M, Q135Y, D138K, D138L, D138M, D138Q, D138R, D138S, D138V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P147A, P147C, P147D, P147F, P147G, P147L, P147M, P147R, P147S, P147T, P147V, K148A, K148D, K148L, K14 8V, F149L, F149M, F149N, E150D, E150H, E150K, E150L, E150M, E150N, E150R, E150V, E150W, E150Y, G151A, G151C, G151 D, G151 L, G151 N, G151 P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G164H, G164S, G164V, V167D, V167E, V167L, V167P, V167Q, V167R, V167W, H168N, L170A, L170D, L17 0E, L170F, L170H, L170K, L170M, L170N, L170P, L170Q, L170R, L170S, L170V, L170W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, D171 M, D171Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D174V, D174W, F175Y, N177M, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181C, S181 D, S181 F, 1G, S181 N, S181 P, S181Q, S181T, S181V, S181W, E185M, E185R, E185V, E185W, S186D, S186E, S186H, S186I, S186K, S186L, S186M, S186N, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K187V, K187W, Y188P, E189L, E189V, E189W, S199C, S199L, S199M, S199Y, E200D, E200F, E200K, E20 0L, E200M, E200N, E200R, E200W, A203C, A203D, A203E, A203G, A203L, A203M, A203P, A203R, A203S, A203T, A203V, A203W, N204L, N204M, N204V, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, D207Q, D207S, D207V, D207W, S208A, S208C, S208D, S208G, S208L, S208Q, S208T, S208V, S208W, S21 0T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G222D, E224A, E224P, N227A, N227Q, N227R, N227S, N227T, N227K, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N233R, N233W, W234R, G235W, G235A, G235E, G235F, G235H, G235I, G235L, G235M, G235N, G235P, G23 5S, G235V, S237C, S237G, S237M, S237N, S237W, S237Y, Y244C, Y244E, Y244M, L249H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S251 N, S251 R, N252P, N252C, G253D, G253W, F254I, F254L, F254M, F254Y, Q256E, Q256R, N260*, N260A, N260C, N260E, N260I, N260K, N260L, N260M, N260Q, N260R, 0V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q262W, Q262Y, M263K, M263L, M263Q, D264*, D264C, D264E, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274R, K274A, K274H, F276A, F27 6C, F276K, F276N, F276G, F276L, F276M, F276P, F276S, F276V, F276W, I278A, I278K, I278N, I278Q, I278V, S279C, S279D, S279E, S279G, S279N, D280E, Y281*, Y281A, Y281C, Y281 H, Y281 K, Y281 N, Y281 P, Y282E, Y282N, H283I, A284I, A284L, A284N, A284P, A284T, A284V, T287N, S288D, S288K, S28 8N, V290I, K291 L, K291 R, K291V, T296C, E300A, E300D, H301C, H301 N, H301 R, T303A, T303C, T303G, T303K, T303Q, T303R, T303W, D304C, D304M, L305M, L305N, S306C, K308A, K308D, K308G, K308I, K308L, K308Q, K308S, K308T, K308V, K308Y, K309A, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R and combinations thereof.
3. Verwendung eines Dispersin nach Anspruch 1 oder 2 zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen. 3. Use of a dispersin according to claim 1 or 2 for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces.
4. Verwendung eines Dispersin nach Anspruch 1 oder 2 zur fasertiefen Reinigung von Textilien. 4. Use of a dispersin according to claim 1 or 2 for the fiber-deep cleaning of textiles.
5. Verwendung eines Dispersin nach Anspruch 1 oder 2 zur Verbesserung der Hygiene von Textilien. 5. Use of a dispersin according to claim 1 or 2 for improving the hygiene of textiles.
6. Verwendung nach einem der vorhergehenden Ansprüche, wobei das Dispersin in einem Wasch- und Reinigungsmittel enthalten ist, wobei das Wasch- und Reinigungsmittel im Wesentlichen frei von borhaltigen Verbindungen ist, vorzugsweise frei von borhaltigen Verbindungen ist; und/oder das Wasch- und Reinigungsmittel in 1 Gew.-%iger Lösung in entionisiertem Wasser bei 20°C einen pH-Wert in einem Bereich von etwa 6 bis etwa 11 , insbesondere von etwa 6,5 bis etwa 10,5, weiter bevorzugt von etwa 7 bis etwa 10, besonders bevorzugt von etwa 8 bis etwa 9 aufweist. 6. Use according to one of the preceding claims, wherein the dispersin is contained in a washing and cleaning agent, wherein the washing and cleaning agent is substantially free of boron-containing compounds, preferably free of boron-containing compounds; and/or the washing and cleaning agent in 1 wt. % solution in deionized water at 20°C has a pH in a range from about 6 to about 11, in particular from about 6.5 to about 10.5, more preferably from about 7 to about 10, particularly preferably from about 8 to about 9.
7. Verwendung nach einem der vorhergehenden Ansprüche, vorzugsweise in einem Temperaturbereich von etwa 10°C bis etwa 60°C, bevorzugt etwa 15°C bis etwa 40°C, besonders bevorzugt etwa 20°C bis etwa 30°C. 7. Use according to one of the preceding claims, preferably in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
8. Mittel, vorzugsweise Wasch- und/oder Reinigungsmittel, zur Verhinderung und/oder8. Agents, preferably washing and/or cleaning agents, for preventing and/or
Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt zur fasertiefen Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien, dadurch gekennzeichnet dass das Mittel ein Dispersin enthält, wobei das Dispersin ß-1 ,6-N-Acetylglucosaminidase-Aktivität aufweist, eine Aminosäuresequenz umfasst, die zu der in SEQ ID NO:1 angegebenen Aminosäuresequenz über deren Gesamtlänge zu mindestens 70% und zunehmend bevorzugt zu mindestens 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% oder 99% identisch ist und bezogen auf die Nummerierung gemäß SEQ ID NO:1 , an mindestens einer der Positionen, die den Positionen 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71 , 72, 74, 77, 79, 80, 81 , 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111 , 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131 , 135, 138, 139, 140, 142, 145,Reduction and/or removal of microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, as well as for improving the hygiene of textiles, characterized in that the agent contains a dispersin, wherein the dispersin has ß-1,6-N-acetylglucosaminidase activity, comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% identical and, based on the numbering according to SEQ ID NO:1, at least one of the positions corresponding to positions 2, 3, 12, 15, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 34, 43, 44, 45, 49, 52, 54, 56, 57, 58, 59, 60, 62, 63, 67, 68, 71, 72, 74, 77, 79, 80, 81, 82, 90, 99, 100, 103, 104, 105, 106, 107, 110, 111, 113, 114, 116, 117, 118, 119, 120, 122, 123, 124, 125, 126, 127, 128, 131, 135, 138, 139, 140, 142, 145,
147, 148, 149, 150, 151 , 152, 163, 164, 167, 168, 170, 171 , 173, 174, 175, 177, 178, 179, 181 , 185,147, 148, 149, 150, 151, 152, 163, 164, 167, 168, 170, 171, 173, 174, 175, 177, 178, 179, 181, 185,
186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221 , 222, 224, 225, 227,186, 187, 188, 189, 199, 200, 203, 204, 205, 207, 208, 210, 215, 217, 218, 221, 222, 224, 225, 227,
230, 232, 233, 234, 235, 237, 244, 249, 251 , 252, 253, 254, 256, 260, 261 , 262, 263, 264, 265, 267,230, 232, 233, 234, 235, 237, 244, 249, 251, 252, 253, 254, 256, 260, 261, 262, 263, 264, 265, 267,
268, 270, 271 , 272, 273, 274, 276, 278, 279, 280, 281 , 282, 283, 284, 287, 288, 290, 291 , 296, 300, 301 , 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 und 323 entsprechen, mindestens eine Aminosäuresubstitution und/oder -deletion aufweist. 268, 270, 271, 272, 273, 274, 276, 278, 279, 280, 281, 282, 283, 284, 287, 288, 290, 291, 296, 300, 301, 303, 304, 305, 306, 308, 309, 312, 314, 315, 319, 321 and 323, having at least one amino acid substitution and/or deletion.
9. Mittel nach Anspruch 8, wobei die mindestens eine Aminosäuresubstitution und/oder - deletion aus der aus D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52*, Y52M, G54L, G54M, G54N, S56T, S56W, S57W, E58N, N59A, N59C, N59D, N59E, N59F, N59M, N59R, N59V, N59W, T60V, N62C, N62D, N62H, N62Q, N62W, T63C, T63D, T63L, T63N, T63R, T63V, K67A, K67L, N68L, N68Q, L71 H, L71 N, L71 R, L71V, L71W, S72*, S72C, S72D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77A, D79V, K80*, K80E, K80H, K80L, K80N, K80Q, K80V, K80W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S, K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, V106N, V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K107T, K107V, K107W, N110M, N110R, N110V, D111A, D111 E, D111 M, D111 N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, S117*, S117D, S117H, S117N, S117P, E118*, E118A, E118D, E118G, E118L, E119G, E119W, T120I, T120L, T120M, T120V, T120W, D122*, D122H, D122R, Y123W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y124R, Y124T, Y124V, Y124W, D125C, D125G, D125K, D125Q, D125R, N126V, R127D, R127H, R127K, R127L, R127M, R127Q, R127W, V128C, V128L, V128T, D131V, Q135*, Q135A, Q135D, Q135E, Q135K, Q135M, Q135Y, D138K, D138L, D138M, D138Q, D138R, D138S, D138V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P147A, P147C, P147D, P147F, P147G, P147L, P147M, P147R, P147S, P147T, P147V, K148A, K148D, K148L, K148V, F149L, F149M, F149N, E150D, E150H, E150K, E150L, E150M, E150N, E150R, E150V, E150W, E150Y, G151A, G151C, G151 D, G151 L, G151 N, G151 P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G164H, G164S, G164V, V167D, V167E, V167L, V167P, V167Q, V167R, V167W, H168N, L170A, L170D, L170E, L170F, L170H, L170K, L170M, L170N, L170P, L170Q, L170R, L170S, L170V, L170W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, D171 M, D171Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D174V, D174W, F175Y, N177M, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181C, S181 D, S181 F, S181G, S181 N, S181 P, S181Q, S181T, S181V, S181W, E185M, E185R, E185V, E185W, S186D, S186E, S186H, S186I, S186K, S186L, S186M, S186N, S186Q, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K187V, K187W, Y188P, E189L, E189V, E189W, S199C, S199L, S199M, S199Y, E200D, E200F, E200K, E200L, E200M, E200N, E200R, E200W, A203C, A203D, A203E, A203G, A203L, A203M, A203P, A203R, A203S, A203T, A203V, A203W, N204L, N204M, N204V, N204W, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, D207Q, D207S, D207V, D207W, S208A, S208C, S208D, S208G, S208L, S208Q, S208T, S208V, S208W, S210T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G222D, E224A, E224P, N227A, N227Q, N227R, N227S, N227T, N227K, D230*, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N233R, N233W, W234R, G235W, G235A, G235E, G235F, G235H, G235I, G235L, G235M, G235N, G235P, G235S, G235V, S237C, S237G, S237M, S237N, S237W, S237Y, Y244C, Y244E, Y244M, L249H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S251 N, S251 R, S251W, N252P, N252C, G253D, G253W, F254I, F254L, F254M, F254Y, Q256E, Q256R, N260*, N260A, N260C, N260E, N260I, N260K, N260L, N260M, N260Q, N260R, N260V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q262W, Q262Y, M263K, M263L, M263Q, D264*, D264C, D264E, Y265F, N267S, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274R, K274A, K274H, F276A, F276C, F276K, F276N, F276G, F276L, F276M, F276P, F276S, F276V, F276W, I278A, I278K, I278N, I278Q, I278V, S279C, S279D, S279E, S279G, S279N, D280C, D280E, Y281*, Y281A, Y281C, Y281 H, Y281 K, Y281 N, Y281 P, Y282E, Y282N, H283I, A284I, A284L, A284N, A284P, A284T, A284V, T287N, S288D, S288K, S288N, V290I, K291 L, K291 R, K291V, T296C, E300A, E300D, H301C, H301 N, H301 R, T303A, T303C, T303G, T303K, T303Q, T303R, T303W, D304C, D304M, L305M, L305N, S306C, K308A, K308D, K308G, K308I, K308L, K308Q, K308S, K308T, K308V, K308Y, K309A, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R und Kombinationen davon bestehenden Gruppe ausgewählt ist. 9. Agent according to claim 8, wherein the at least one amino acid substitution and/or deletion is selected from the group consisting of D2A, D2L, D2N, D2R, D2V, D2W, Q3F, Q3I, Q3L, Q3M, Q3P, Q3V, Q3Y, Q3T, S12A, H15F, H15Y, T17W, T17C, T17E, T17F, T17M, T17R, T17V, V18L, E19D, E19N, E19P, K22A, K22M, K22V, S23C, S23E, S23I, S23L, S23R, S23T, S23V, V25R, D26M, Y30*, Y30D, Y30L, Y30M, Y30N, Y30R, Y30T, Y30V, G32L, G32M, G32R, N43*, N43H, N43 L, E44*, N45D, N45L, N45V, A49W, A49Y, Y52*, Y52M, G54L, G54M, G54N, S56T, S56W, S57W, E58N, N59A, N59C, N59D, N59E, N59F, N59M, N59R, N59V, N59W, T60V, N62C, N62D, N62H, N62Q, N62W, T63C, T63D, T63L, T63N, T63R, T63V, K67A, K67L, N68L, N68Q, L71 H, L71 N, L71 R, L71V, L71W, S72*, S72C, S72 D, S72E, S72F, S72G, S72I, S72M, S72N, S72R, S72T, S72Y, I74L, S77A, D79V, K80*, K80E, K80H, K80L, K80N, K80Q, K80V, K80W, D81A, D81G, D81 L, D81 R, D81S, D81T, D81V, D81W, I82V, L90F, E99Q, E99R, L100S, K103A, K103R, K104N, K104W, D105N, V106A, V106D, V106E, V106H, V106K, V106L, V106M, , V106Q, V106W, V106Y, K107A, K107C, K107L, K107M, K107T, K107V, K107W, N110M, N110R, N110V, D111A, D111 E, D111 M, D111 N, D111Q, D111 R, D111V, D111W, V113T, T114C, T114S, Y116D, Y116N, Y116R, S117*, S117D, S117H, S117N, S117P, E118*, E118A, E118D, E118G, E118L, E119G, E119W, T120I, T12 0L, T120M, T120V, T120W, D122*, D122H, D122R, Y123W, Y124C, Y124I, Y124K, Y124L, Y124M, Y124Q, Y124R, Y124T, Y124V, Y124W, D125C, D125K, D125Q, D125R, N126V, R127D, R127H, R127K, R127L, R127M, R127Q, R127W, V128C, V128L, V128T, D131V, Q135*, Q135A, Q135D, Q135E, Q135K, Q135M, 5Y, D138K, D138L, D138M, D138Q, D138R, D138S, D138V, D138W, E139W, D142R, D142W, Y145*, Y145H, Y145L, Y145N, Y145V, P147A, P147C, P147F, P147G, P147L, P147M, P147R, P147S, P147T, P147V, K148A, K148D, K148L, K148V, F149L, F149M, F149N, E150D, E150H, E150K, E150L, E150M, E150N, 0R, E150V, E150W, E150Y, G151A, G151C, G151 D, G151 L, G151 N, G151 P, G151S, G151W, K152D, K152L, K152R, G164D, G164E, G164H, G164S, G164V, V167E, V167L, V167P, V167Q, V167R, V167W, H168N, L170A, L170D, L170E, L170F, L170H, L170K, L170M, L170N, L170P, L170Q, L170R, L170S, L170V, L17 0W, L170Y, D171A, D171C, D171 E, D171 K, D171 L, D171 M, D171Q, D171 R, D171V, D171W, D171Y, I173C, D174H, D174M, D174N, D174V, D174W, F175Y, Q178*, Q178A, Q178K, Q178R, Q178W, I179T, S181C, S181 D, S181 F, S181G, S181 N, S181 P, S181Q, S181T, S181V, S181W, E185M, E185R, E185V, E185W, S18 6D, S186E, S186H, S186I, S186K, S186L, S186M, S186N, S186Q, S186R, S186V, S186W, K187C, K187D, K187G, K187R, K187S, K187V, K187W, Y188P, E189V, E189W, S199C, S199L, S199M, S199Y, E200D, E200F, E200K, E200L, E200M, E200N, E200R, E200W, A203C, A203D, A203E, A203G, A203L, A203M, A20 3P, A203R, A203S, A203T, A203V, A203W, N204L, N204M, N204V, N204W, N204Y, L205I, D207A, D207C, D207E, D207G, D207N, D207Q, D207S, D207V, S208A, S208C, S208D, S208G, S208L, S208Q, S208T, S208V, S208W, S210T, Q215R, Q215M, Q215L, Q215*, S217V, T218A, T218L, T218Q, T218R, T218V, G22 2D, E224A, E224P, N227A, N227Q, N227R, N227S, N227T, N227K, D230*, D230R, D230T, D230W, E232D, E232V, N233H, N233Q, N233R, N233W, W234R, G235A, G235E, G235F, G235H, G235I, G235L, G235M, G235N, G235P, G235S, G235V, S237C, S237G, S237M, S237N, S237W, S237Y, Y244C, Y244E, Y244M, L24 9H, L249K, L249Q, L249R, L249W, L249Y, S251 L, S251 N, S251 R, S251W, N252P, N252C, G253D, G253W, F254I, F254L, F254M, F254Y, Q256E, Q256R, N260A, N260C, N260E, N260I, N260K, N260L, N260M, N260Q, N260R, N260V, N260W, N260Y, E261*, E261A, E261 D, E261 R, E261W, Q262*, Q262F, Q262H, Q26 2W, Q262Y, M263K, M263L, M263Q, D264*, D264C, D264E, Y265F, N267S, N267T, W268C, W268E, W268M, W268R, Y270F, A271 D, A271G, H272D, H272I, Y281 P, Y282E, Y282N, Y281 R, H272W, N273W, K274R, K274A, K274H, F276A, F276C, F276K, F276N, F27 6G, F276L, F276M, F276P, F276S, F276V, F276W, I278A, I278K, I278N, I278Q, I278V, S279C, S279D, S279E, S279G, S279N, D280C, D280E, Y281*, Y281A, Y281C, Y281 H, Y281 K, Y281 N, Y281 P, Y282E, Y282N, H283I, A284I, A284L, A284N, A284P, A284T, A284V, T287N, S288D, S288K, S288N, V290I, K29 1L, K291 R, K291V, T296C, E300A, E300D, H301C, H301 N, H301 R, T303A, T303C, T303G, T303K, T303Q, T303R, T303W, D304C, D304M, L305M, L305N, K308A, K308D, K308G, K308I, K308L, K308Q, K308S, K308T, K308V, K308Y, K309A, K309C, K309D, K309H, K309L, K309M, K309N, K309Q, K309S, K309T, K309I, K312A, K312L, K312M, K312N, K312Q, K312S, K312W, E314I, E314L, E314V, L315I, L315V, R319A, N323R and combinations thereof.
10. Mittel nach Anspruch 8 oder 9, wobei das Mittel im Wesentlichen frei von borhaltigen Verbindungen ist, vorzugsweise frei von borhaltigen Verbindungen ist; und/oder das Mittel in 1 Gew.- %iger Lösung in entionisiertem Wasser bei 20°C einen pH-Wert in einem Bereich von etwa 6 bis etwa 11 , insbesondere von etwa 6,5 bis etwa 10,5, weiter bevorzugt von etwa 7 bis etwa 10, besonders bevorzugt von etwa 8 bis etwa 9 aufweist. 10. Agent according to claim 8 or 9, wherein the agent is substantially free of boron-containing compounds, preferably free of boron-containing compounds; and/or the agent in 1 wt. % solution in deionized water at 20°C has a pH in a range from about 6 to about 11, in particular from about 6.5 to about 10.5, more preferably from about 7 to about 10, particularly preferably from about 8 to about 9.
11 . Verfahren zur Verhinderung und/oder Reduzierung und/oder Entfernung mikrobiell bedingter Ablagerungen auf Textilien, Geschirr und anderen Oberflächen, insbesondere Haushaltsoberflächen, besonders bevorzugt zur fasertiefen Reinigung von Textilien, sowie zur Verbesserung der Hygiene von Textilien, dadurch gekennzeichnet, dass in mindestens einem Verfahrensschritt ein Dispersin nach Anspruch 1 oder 2 oder ein Mittel nach einem der Ansprüche 8 bis 10 angewendet wird, wobei das Verfahren vorzugsweise in einem Temperaturbereich von etwa 10°C bis etwa 60°C, bevorzugt etwa 15°C bis etwa 40°C, besonders bevorzugt etwa 20°C bis etwa 30°C. 11. Method for preventing and/or reducing and/or removing microbial deposits on textiles, dishes and other surfaces, in particular household surfaces, particularly preferably for deep fiber cleaning of textiles, as well as for improving the hygiene of textiles, characterized in that in at least one method step a dispersin according to claim 1 or 2 or an agent according to one of claims 8 to 10 is used, wherein the method is preferably carried out in a temperature range of about 10°C to about 60°C, preferably about 15°C to about 40°C, particularly preferably about 20°C to about 30°C.
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