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WO2024175294A1 - Détergents et agents de nettoyage contenant une dispersine - Google Patents

Détergents et agents de nettoyage contenant une dispersine Download PDF

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Publication number
WO2024175294A1
WO2024175294A1 PCT/EP2024/051749 EP2024051749W WO2024175294A1 WO 2024175294 A1 WO2024175294 A1 WO 2024175294A1 EP 2024051749 W EP2024051749 W EP 2024051749W WO 2024175294 A1 WO2024175294 A1 WO 2024175294A1
Authority
WO
WIPO (PCT)
Prior art keywords
washing
water
agent
dispersin
amino acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2024/051749
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German (de)
English (en)
Inventor
Mirko Weide
Michael KANDZIA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to KR1020257027693A priority Critical patent/KR20250153783A/ko
Priority to EP24702294.0A priority patent/EP4669734A1/fr
Priority to CN202480014339.9A priority patent/CN120752325A/zh
Publication of WO2024175294A1 publication Critical patent/WO2024175294A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0068—Deodorant compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—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)
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the 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 a dispersin-containing agent for preventing and/or reducing bad smells on surfaces, in particular household surfaces, preferably in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, washing or sink basins, toilet bowls, cisterns, toilet rims, siphons, water pipes and/or lines, water inlets and/or outlets, and/or for preventing and/or reducing and/or removing microbially caused deposits on surfaces, in particular household surfaces, preferably in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, washing or sink basins, toilet bowls, cisterns, toilet rims, siphons, water pipes and/or lines, water inlets and/or outlets, and/or for improving the hygiene of surfaces, in particular household surfaces,
  • 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.
  • 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 odors resulting from microbial bio-deposits.
  • Another example of unpleasant odors is sweat or body odor that adheres to an object that has come into contact with people or animals.
  • Bad smells 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, especially household surfaces that come into contact with dirty objects and/or water, especially used water, and/or washing/cleaning solution, such as 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.
  • Deposits, bio-deposits, body soils and the like not only lead to bad smells, but can also become visible as soiling on textiles and/or surfaces, in particular household surfaces, such as 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, e.g. in the form of deposits, smears, encrustations, yellowing, armpit stains and greying.
  • Bio-deposits and the like due to their typically adhesive texture, also enable other bad smell and/or dirt particles to adhere. However, bad smells can also be present before the microbial deposits lead to visible soiling.
  • biodeposit 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 biodeposits, biosoils, 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.
  • 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 that grow in a biofilm differ physiologically from the planktonic cells of the same organism, which in contrast are single 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.
  • One 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 microbially caused bad odors as well as microbially caused deposits, bio-deposits and the like from surfaces, in particular household surfaces, such as 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.
  • 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 bad odors on surfaces, in particular household surfaces, preferably in washing machines or dishwashers, pump sumps, Storage containers, water reservoirs, washing drums, rinsing chambers, wash or sink basins, toilet bowls, cisterns, WC rims, siphons, water pipes and/or lines, water inlets and/or outlets, and/or for preventing and/or reducing and/or removing microbial deposits on surfaces, in particular household surfaces, preferably in washing machines or dishwashers, pump sumps, Storage containers, water reservoirs, washing drums, rins
  • 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 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 cleaning surfaces in particular household surfaces, preferably in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, wash basins or sinks, toilet bowls, cisterns, WC rims, siphons, water pipes and/or lines, water inlets and/or outlets, in particular for preventing and/or reducing bad odors and/or for preventing and/or reducing and/or removing microbial deposits and/or for improving hygiene, characterized in that the agent contains a dispersin according to the invention, and a method for cleaning surfaces, in particular household surfaces, preferably in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, wash basins or sinks, toilet bowls, cisterns, WC rims, siphons, water pipes and/or lines, water inlets and/or outlets, in particular for preventing and/or reducing Bad odor and/or
  • 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.
  • washing and/or cleaning agent 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.
  • deep cleaning means the dissolution or removal of visible and invisible components of organic substances, e.g. sebum, cell residues, body dirt (body oil), 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 deposits, biodeposits and the like between individual fibers of textiles.
  • organic substances e.g. sebum, cell residues, body dirt (body oil), 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 deposits
  • the term "textile” as used herein means any textile material, including yarns, yarn precursors, fibres, 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 knitted fabrics, woven fabrics, denims, nonwovens, felts, yarns and terry cloth.
  • the textile can be cellulose-based, such as natural cellulose fibres such as cotton, flax/linen, jute, ramie, sisal or coconut fibres, or man-made cellulose fibres (e.g. from wood pulp) such as viscose/rayon, cellulose acetate fibres (tricell), lyocell or mixtures thereof.
  • the textile or woven fabric can also consist of non-cellulose 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 cellulose fibres and non-cellulose fibres.
  • non-cellulose 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 cellulose fibres and non-cellulose fibres.
  • blends are blends 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
  • the fabric may be conventional washable linen, e.g. soiled household linen.
  • 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 microbially caused bad odors as well as microbially caused deposits, bio-deposits and the like from surfaces, in particular household surfaces, such as 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.
  • 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 bad odors on surfaces, in particular household surfaces, preferably in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, wash basins or sinks, toilet bowls, cisterns, WC rims, siphons, Water pipes and/or lines, water inlets and/or outlets, and/or for preventing and/or reducing and/or removing microbial deposits on surfaces, in particular household surfaces, preferably in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, wash basins or sinks, toilet bowls, cisterns
  • 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-deposits and other so-called biosoils (i.e. 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 corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length by at least 70% and increasingly preferably by 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%, 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
  • 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 deletion selected from the amino acid sequence given in SEQ
  • 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 corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length by 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, 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, Q
  • 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. This means that the enzyme can interact directly with all components of the agent and, if the agent is a liquid agent, that the enzyme is in direct contact with the agent's solvent (e.g. water).
  • an agent can contain enzymes that form an interaction complex with other molecules or that 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.
  • an agent can contain cells of Bacillus pumilus or Bacillus subtilus that 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.
  • sequence comparison The identity of nucleic acid or amino acid sequences is determined by sequence comparison. This sequence comparison is based on the state-of-the-art and commonly used BLAST algorithm (see e.g. 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. Commonly 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 can also be carried out 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, sequence identity reported herein is determined using the BLAST algorithm.
  • Such a comparison also allows a statement to be made about the similarity of the sequences being compared to one another. This is usually expressed in percent identity, i.e. the proportion of identical nucleotides or amino acid residues at the same positions or positions that correspond to one another in an alignment.
  • the broader term homology includes conserved amino acid exchanges in amino acid sequences, i.e. amino acids with similar chemical activity, since these usually perform similar chemical activities within the protein. Therefore, the similarity of the sequences being compared can also be expressed 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 may therefore be useful to relate sequence matches only to individual, possibly small regions. Unless otherwise stated, identity or homology statements in the present application refer to the total length of the respective nucleic acid or amino acid sequence specified.
  • 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 For the description of substitutions that affect exactly one amino acid position (amino acid exchanges), the following convention is used: first, the naturally occurring amino acid is designated in the form of the internationally used one-letter code, then follows 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 indicated 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 understood to mean the ability of an agent to partially or completely remove existing soiling, in particular the brightening performance of one or more soilings on textiles.
  • the cleaning performance in the context of the present invention also includes the ability to remove microbial deposits, bio-deposits and the like from surfaces, in particular household surfaces, preferably 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.
  • both the 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 specified below.
  • washing or cleaning liquor refers to the solution containing the washing or cleaning agent that acts on the textiles or fabrics or surfaces, particularly 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 in the same concentration (based on active protein).
  • 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 ie the lightening of the soiling, as a measure of the cleaning performance is determined using optical measuring methods, preferably photometric.
  • a suitable device for this is for example the Minolta CM508d spectrometer.
  • the devices used for the measurement are usually calibrated beforehand with a white standard, preferably a supplied white standard.
  • the cleaning performance on surfaces in particular household surfaces, preferably in washing machines or dishwashers, pump sumps, storage containers, water reservoirs, washing drums, rinsing chambers, wash basins or sinks, toilet bowls, cisterns, WC rims, siphons, water pipes and/or lines, water inlets and/or outlets, can be determined as described in Example 1.
  • Preferred embodiments of uses and agents according to the invention achieve such advantageous cleaning performance even at low temperatures, in particular in the temperature ranges between 10°C and 60°C, preferably between 15°C and 50°C, more preferably between 20°C and 40°C and particularly preferably 30°C.
  • the dispersin according to the invention can be used in a washing and/or cleaning agent.
  • washing and cleaning agents according to the invention include all conceivable types of washing or cleaning agents, both concentrates and agents that can be used undiluted, for use on a commercial scale, in the washing machine or for hand washing or cleaning. These include, for example, washing agents for textiles, carpets or natural fibers, for which the term washing agent 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.
  • washing and cleaning agents within the scope of the invention also include washing aids that 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, crease-freeness or low static charge.
  • the latter agents include fabric softeners, among others. 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 customary in such agents, with preferably at least one further Ingredient is present in the agent.
  • the agents according to the invention can contain in particular 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 as well as colorants and fragrances.
  • Advantageous ingredients of agents according to the invention are disclosed in the international patent application WO 2009/121725, starting 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 a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably 0.2 to 6% by weight, 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 can 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 can also be present as a one-component system. Such agents consist of one phase. Alternatively, an agent can also consist of several phases. Such an agent 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 polymers.
  • Polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and their copolymers are particularly suitable as water-soluble polymers.
  • 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 containing sulfate or sulfonate groups with preferably alkali ions as cations.
  • Soaps that can be used are preferably the alkali salts of saturated or unsaturated Ci2-18 fatty acids. Such fatty acids can also be used in not completely neutralized form.
  • Useful surfactants of the sulfate type include the salts of the sulfuric acid half esters of Ci2-18 fatty alcohols and the sulfation products of the above-mentioned non-ionic surfactants with a low degree of ethoxylation.
  • the usable surfactants of the sulfonate type include, for example, Cg-u-alkylbenzenesulfonates, alkanesulfonates which are obtained from Ci2-is-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 Ci2-18-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
  • 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 Cw-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 produced 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 C13-16 alkyl sulfates are preferred.
  • sulfuric acid monoesters of straight-chain or branched C1-2i-alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C1-n-alcohols with an average of 3.5 moles of ethylene oxide (EO) or C12-is-fatty alcohols with 1 to 4 EO.
  • Suitable alkyl ether sulfates are, for example, compounds of the formula R 1 -O-(AO) n -SO 3 - X + .
  • 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 12-18 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 NE T % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and mixtures thereof.
  • the stated degree of ethoxylation represents a statistical mean value which can be a whole or a fractional number for a specific product.
  • the stated degrees of alkoxylation represent statistical mean values which can be a whole or a fractional number for a specific product.
  • 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, C18-19 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-19 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 methyl-branched in the 2-position, 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 having 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 optionally interrupted by heteroatoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms 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 stand for four identical or different, in particular two long-chain and two short-chain, alkyl radicals and X- stands for 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 neutrally reacting sodium salts, e.g. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
  • the preferred builder from the class of phosphonates is HEDP.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity.
  • 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 salts thereof; ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and/or salts thereof;
  • 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 builder substances 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 may, if desired, be present 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 adjust 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.
  • 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. These include, 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 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 provides realistic molar weight values due to its structural similarity to the polymers examined. These details differ significantly from the molar weight details 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 copolymers of 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 to be 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.
  • Water-soluble inorganic builder materials that can be used are in particular alkali silicates, alkali carbonates, Alkali hydrogen carbonates, alkali phosphates and/or sesquicarbonates, which can be in the form of their alkaline, neutral or acidic sodium or potassium salts, come into consideration.
  • 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 which 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 of 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 ⁇ - and ⁇ -sodium disilicates (Na2Si2Os • 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, such as can be produced from sand and soda.
  • Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further embodiment of the inventive agent.
  • 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 (Na2SiuO29 • x H2O, Magadiite), Na-SKS-3 (Na2SisOi7 • x H2O) or Na-SKS-4 (Na2Si4Og • x H2O, Makatite).
  • Na-SKS e.g. Na-SKS-1 (Na2Si22O45 • x H2O, Kenyaite), Na-SKS-2 (Na2SiuO29 • x H2O, Magadiite), Na-SKS-3 (Na2SisOi7 • x H2O) or Na-SKS-4 (Na2Si4Og • x H2O, Makatite).
  • Na-SKS-5 ( ⁇ -Na 2 Si 2 O5), Na-SKS-7 ( ⁇ -Na 2 Si 2 O5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 • 3 H 2 O), Na-SKS-10 (NaHSi 2 O 5 • 3 H 2 O, kanemite), Na-SKS-11 ( ⁇ -Na 2 Si 2 O5) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na2Si2Os) 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, such as is commercially available under the name Nabion® 15, is used.
  • Such water-soluble inorganic builder materials are preferably contained in the agents according to the invention 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 hydrogen carbonates), in particular sodium carbonate, and phosphonic acids/phosphonates.
  • the agents according to the invention are preferably free of phosphate builders, ie 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.
  • Suitable aluminosilicates in particular have no 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 usually 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, i.e. 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 coated in a manner known in principle.
  • the peroxygen compounds can be added to the washing solution as such or in the form of agents containing them, which can in principle contain all the usual washing, cleaning or disinfectant components.
  • alkali percarbonate or alkali perborate monohydrate is used.
  • 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 can be used as bleach activators in the agents are those which, under perhydrolysis conditions, give rise to aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid. 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 preferably used.
  • 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 graying 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 preferably used.
  • the soil-release agents commonly used include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
  • the proportion of graying inhibitors and/or soil-release agents 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 for textiles made of cellulose fibers in particular 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 carry 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 are particularly suitable for polyamide fibers, e.g. 1-(p- Sulfoamoylphenyl)-3-(p-chlorophenyl)-2-pyrazoline and similarly structured compounds.
  • 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-is-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 the agents according to the invention is preferably 0.1 to 10% by weight, preferably 0.2 to 8.0% by weight and more preferably 0.5 to 5.0% by weight.
  • 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% by weight, preferably 0.2 to 8.0% by weight and more preferably 0.5 to 5.0% by weight.
  • 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% by weight, preferably 0.2 to 8.0% by weight and more preferably 0.5 to 5.0% by weight, 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 other 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 also comprise one or more other enzymes.
  • All enzymes which can develop 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, can preferably be used as further enzymes.
  • Other 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 enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.
  • 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.
  • 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 include Amylase-LT® and Stainzyme® or Stainzyme® ultra or Stainzyme® plus as well as AmplifyTM 12L or Amplify PrimeTM 100L, the latter also from Novozymes, and the PREFERENZ S® series from Danisco/DuPont, including 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.
  • cellulases examples include 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 are described in WO 2002/099091, e.g.
  • cellulases include those described in WO 96/29397. 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).
  • 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, 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 (cf., for example, US 6060299, WO 99/64573, US 6566114 and WO 99/64619).
  • Pectate lyases suitable for washing and/or 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 products, solutions of the Enzymes, preferably as concentrated as possible, low in 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.
  • 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).
  • 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, an Ove alkyl, a substituted Ove alkyl, an Ove alkenyl or a substituted Ove alkenyl group.
  • R is hydrogen, a hydroxyl, an Ove alkyl, a substituted Ove alkyl, an Ove alkenyl or a substituted Ove alkenyl group.
  • the radical R in the Phenylboronic acid derivative can be a C1-6 alkyl group and among these more preferably -CH3, -CH3CH2 or - CH3CH2CH2. More preferably, the radical R in the phenylboronic acid derivative is hydrogen.
  • the phenylboronic acid derivative 4-formylphenylboronic acid (4-FPBA) is particularly preferred.
  • 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 that lead to the final concentrations in the agent specified above.
  • a further subject matter of the invention is an agent for cleaning surfaces, in particular household surfaces, preferably 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, in particular for preventing and/or reducing bad odors and/or for preventing and/or reducing and/or removing microbial deposits and/or for improving hygiene, 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%,
  • 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.
  • This also includes agents for (semi-)automated washing or cleaning systems such as robot mops or wet vacuum cleaners.
  • a preferred embodiment relates to an agent for cleaning surfaces, in particular household surfaces, preferably 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, in particular for preventing and/or reducing bad odors and/or for preventing and/or reducing and/or removing microbial deposits and/or for improving hygiene, 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%,
  • Another subject matter of the invention relates to a method for cleaning surfaces, in particular household surfaces, preferably 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, in particular for preventing and/or reducing bad odors and/or for preventing and/or reducing and/or removing microbial deposits and/or for improving hygiene, 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, the method preferably being 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 liquor 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. In a dishwasher, the cleaning program 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 one cleaning cycle.
  • cleaning programs are preferred which comprise further cleaning or rinsing cycles, e.g. a final rinse cycle.
  • the process according to the invention is particularly preferably part of a cleaning program comprising a pre-wash cycle, a cleaning cycle and a final rinse cycle.
  • the process according to the invention is preferably used in conjunction with cleaning programs in which the washing liquor is
  • 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.
  • Example 1 Determination of bad smell & bio-beta formation
  • the dispersin according to the invention can be used in various washing and cleaning agents and realize its effect.

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Abstract

L'invention concerne des détergents et des agents de nettoyage, en particulier des détergents et des agents de nettoyage contenant une enzyme. L'invention concerne l'utilisation d'une dispersine ou d'un agent contenant une dispersine pour prévenir et/ou réduire de mauvaises odeurs sur des surfaces, en particulier des surfaces ménagères, de préférence dans des machines à laver ou des lave-vaisselle, des puisards de pompe, des récipients de stockage, des réservoirs d'eau, des tambours de lavage, des chambres de rinçage, des éviers de lavage ou de rinçage, des cuvettes de toilettes, des citernes, des rebords de toilettes, des siphons, des tuyaux et/ou des conduits d'eau, ou des arrivées et/ou des drains d'eau, et/ou pour prévenir et/ou réduire et/ou éliminer des dépôts induits par voie microbienne sur des surfaces, en particulier des surfaces ménagères, de préférence dans des machines à laver ou des lave-vaisselle, des puisards de pompe, des récipients de stockage, des réservoirs d'eau, des tambours de lavage, des chambres de rinçage, des éviers de lavage ou de rinçage, des cuvettes de toilettes, des citernes, des rebords de toilettes, des siphons, des tuyaux et/ou des conduits d'eau, ou des arrivées et/ou des drains d'eau, et/ou pour améliorer l'hygiène de surfaces, en particulier des surfaces ménagères, de préférence dans des machines à laver ou des lave-vaisselle, des puisards de pompe, des récipients de stockage, des réservoirs d'eau, des tambours de lavage, des chambres de rinçage, des éviers de lavage ou de rinçage, des cuvettes de toilettes, des citernes, des rebords de toilettes, des siphons, des tuyaux et/ou des conduits d'eau, ou des arrivées et/ou des drains d'eau.
PCT/EP2024/051749 2023-02-24 2024-01-25 Détergents et agents de nettoyage contenant une dispersine Ceased WO2024175294A1 (fr)

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KR1020257027693A KR20250153783A (ko) 2023-02-24 2024-01-25 디스퍼신을 포함하는 세척 및 세정 작용제
EP24702294.0A EP4669734A1 (fr) 2023-02-24 2024-01-25 Détergents et agents de nettoyage contenant une dispersine
CN202480014339.9A CN120752325A (zh) 2023-02-24 2024-01-25 包含分散素的洗涤和清洁试剂

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DE102023201695.8A DE102023201695A1 (de) 2023-02-24 2023-02-24 Wasch- und reinigungsmittel mit dispersin
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