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WO2025103667A1 - Agent de nettoyage contenant une protéase - Google Patents

Agent de nettoyage contenant une protéase Download PDF

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Publication number
WO2025103667A1
WO2025103667A1 PCT/EP2024/078314 EP2024078314W WO2025103667A1 WO 2025103667 A1 WO2025103667 A1 WO 2025103667A1 EP 2024078314 W EP2024078314 W EP 2024078314W WO 2025103667 A1 WO2025103667 A1 WO 2025103667A1
Authority
WO
WIPO (PCT)
Prior art keywords
particularly preferably
amino acid
agent
protease
toilet
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.)
Pending
Application number
PCT/EP2024/078314
Other languages
German (de)
English (en)
Inventor
Nadine BLUHM
Helga Werner
Sabine Schuemann
Fabian Falkenberg
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
Publication of WO2025103667A1 publication Critical patent/WO2025103667A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
    • C11D3/38618—Protease or amylase in liquid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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 lies in the field of cleaning agents, in particular cleaning agents for hard surfaces, preferably liquid cleaning agents for cleaning sanitary surfaces such as toilets, toilet bowls, toilet bowls, cisterns, and toilet rims.
  • cleaning agents according to the invention which contain surfactant and protease and have a neutral pH value, represent a gentle cleaning agent alternative with very good cleaning performance.
  • the invention therefore relates, in a first aspect, to a cleaning agent, preferably a liquid cleaning agent, preferably a liquid cleaning agent for cleaning hard surfaces, particularly preferably a liquid cleaning agent for cleaning sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, comprising at least one protease, preferably in an amount of 0.0001 to 5 wt.%, preferably 0.001 to 2.5 wt.%, particularly preferably 0.005 to 1 wt.%, very particularly preferably 0.01 to 0.5 wt.%, based on active protein and total weight of the agent, at least one surfactant, wherein the surfactant is selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof, preferably in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, particularly preferably 0.05 to 5%
  • agents according to the invention comprise a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length and, in each case based on the numbering according to SEQ ID NO:1 (i) at least one of the positions corresponding to positions 3, 4, 99 and 199, at least one amino acid substitution selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least one of the positions corresponding to positions 74, 136, 143, 154, 160, 161, 163, 171, 181, 183,
  • the agent comprises a protease which has proteolytic activity and which 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and which has one of the following amino acid substitution combinations: S3T- V4I-R99E-V199I-Q200L-Y203W; S3T-V4I-R99E-V199I-N212S; S3T-V4I-R99E-V199I-N74D; S3T-V4I-R99E-V199I-S154D-L256E; S3T-V4I-R
  • the agent comprises at least one reversible protease inhibitor or stabilizer, wherein the inhibitor/stabilizer is selected from the group consisting of polyols such as glycerol 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, peptide inhibitors, preferably in an amount of 0.1 to 2 wt.%, preferably 0.3 to 1.5 wt.%, based on the total weight of the agent.
  • the inhibitor/stabilizer is selected from the group consisting of polyols such as glycerol 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, peptide
  • the agent comprises at least two surfactants, wherein the second surfactant is different from the first surfactant and is selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof, preferably in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, particularly preferably 0.05 to 5 wt.%, very particularly preferably 0.1 to 2.5 wt.%, based on active substance and total weight of the agent.
  • the second surfactant is different from the first surfactant and is selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof, preferably in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, particularly preferably 0.05 to 5 wt.%,
  • the first and second surfactants are different from each other and are selected from the group consisting of alcohol ethoxylates and alkyl polyglycosides.
  • the first surfactant is an alcohol ethoxylate, in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, particularly preferably 0.05 to 5 wt.%, very particularly preferably 0.1 to 2.5 wt.% and the second surfactant is an alkyl polyglycoside, in an amount of 0.0005 to 6.5 wt.%, preferably 0.005 to 5 wt.%, particularly preferably 0.03 to 3 wt.%, very particularly preferably 0.05 to 1.5 wt.%, in each case based on the active substance and the total weight of the agent.
  • the first surfactant and the second surfactant are present in a ratio of 1:0.1 to 1:1.5, preferably 1:0.2 to 1:1.2, particularly preferably 1:0.25 to 1:1, very particularly preferably 1:0.5 to 1:0.75, e.g. 1:0.1, 1:0.2, 1:0.25, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.25, 1:3, 1 :4, 1 :5.
  • Method for cleaning hard surfaces in particular sanitary surfaces such as toilets, toilet bowls, toilet bowls, cisterns, toilet rims, characterized in that a cleaning agent described herein is used in at least one method step, the method preferably being carried out in a temperature range of about 15°C to about 30°C, preferably about 18°C to about 25°C, particularly preferably about 25°C, most particularly preferably about 20°C;
  • a protease in a cleaning agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, preferably in a temperature range of about 15°C to about 30°C, preferably about 18°C to about 25°C, more preferably about 25°C, most preferably about 20°C, wherein the protease is as defined herein;
  • a cleaning agent described herein for cleaning hard surfaces in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, preferably in a temperature range of about 15°C to about 30°C, preferably about 18°C to about 25°C, more preferably about 25°C, most preferably about 20°C.
  • Numerical ranges specified in the format "from x to y" include the specified values. If multiple preferred numerical ranges are specified in this format, it goes without saying that all ranges resulting from the combination of the different endpoints will also be included.
  • 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.
  • cleaning agent as used herein is synonymous with the term “agent” and refers to a composition for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, as explained in the description.
  • Liquid 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 1,013 mbar.
  • a substance e.g., a composition or agent, is liquid according to the invention's definition if it is in the liquid state at 25°C and 1,013 mbar. Liquid also includes gel.
  • Variant refers to natural or artificially produced variations of a native enzyme that have a modified amino acid sequence compared to the reference form.
  • the present invention is based on the surprising finding of the inventors that cleaning agents according to the invention which contain surfactant and protease and have a neutral pH represent a gentle cleaning agent alternative with very good cleaning performance.
  • a protease is used in a cleaning agent.
  • the use of a protease in a cleaning agent according to the invention or the use of a cleaning agent according to the invention leads to improved cleaning of hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, and toilet rims.
  • Agents according to the invention contain a protease.
  • suitable proteases are subtilisins BPN' from Bacillus amyloliquefaciens and Carlsberg from Bacillus licheniformis, protease PB92, subtilisins 147 and 309, protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and 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 Novozymes.
  • Subtilisins 147 and 309 are marketed by Novozymes under the trade names Esperase® and Savinase®, respectively.
  • Protease variants are derived from the protease from Bacillus lentus DSM 5483, described in e.g. WO 95/23221, WO 92/21760, WO 2013/060621 and EP 3660151.
  • Other useful proteases are e.g.
  • proteases from Bacillus gibsonii and Bacillus pumilus which are disclosed in WO 2008/086916, WO 2007/131656, WO 2017/215925, WO 2021/175696 and WO 2021/175697, are also particularly preferably used.
  • Other usable proteases are those that are naturally present in the microorganisms Stenotrophomonas maltophilia, in particular Stenotrophomonas maltophilia K279a, Bacillus intermedius and Bacillus sphaericus.
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least one and increasingly preferably at least two, three or four of the positions corresponding to positions 3, 4, 99 or 199, at least one and increasingly preferably at least two, three or four amino acid substitution(s) selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least one of the Positions corresponding to positions 3, 4, 99 or 199, at least one amino acid substitution selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least one of the positions corresponding to positions 74, 136, 143, 154, 160, 161,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least two of the Positions corresponding to positions 3, 4, 99 or 199, at least two amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least one of the positions corresponding to positions 74, 136, 143, 154, 160, 16
  • the protease contained in agents according to the invention is a protease which has proteolytic activity and comprises an amino acid sequence which is identical to the amino acid sequence given in SEQ ID NO:1 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%, 99% and less than 100%, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least three of the positions which corresponding to positions 3, 4, 99 or 199, at least three amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least one of the positions corresponding to positions 74, 136, 143, 154, 160, 161, 16
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at the positions which positions 3, 4, 99 or 199, the amino acid substitutions S3T, V4I, R99E and V199I, and (ii) at least one of the positions corresponding to positions 74, 136, 143, 154, 160, 161, 163, 171, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic activity and comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% and less than 100% identical, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least one and increasingly preferably two, three or four of the positions corresponding to positions 3, 4, 99 or 199, at least one and increasingly preferably two, three or four amino acid substitution(s) selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least one
  • the protease contained in the agent according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least one of the positions, corresponding to positions 3, 4, 99 or 199, at least one amino acid substitution selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least one of the positions corresponding to positions 154, 160, 181, 183, 185, 200
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least two of the Positions corresponding to positions 3, 4, 99 or 199, at least two amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least one of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1 , (i) at least three of the positions corresponding to positions 3, 4, 99 or 199, at least three amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least one of the positions corresponding to positions 154, 160, 181, 183, 185, 200
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at the positions which corresponding to positions 3, 4, 99 or 199, the amino acid substitutions S3T, V4I, R99E and V199I, and (ii) at least one of the positions corresponding to positions 154, 160, 181, 183, 185, 200, 203, 209 or 256, at least
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least one of the Positions corresponding to positions 3, 4, 99 or 199, at least one amino acid substitution selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least two of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least two of the Positions corresponding to positions 3, 4, 99 or 199, at least two amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least two of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least three of the Positions corresponding to positions 3, 4, 99 or 199, at least three amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least two of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at the positions which corresponding to positions 3, 4, 99 or 199, the amino acid substitutions S3T, V4I, R99E and V199I, and (ii) at least two of the positions corresponding to positions 154, 160, 181, 183, 185, 200, 203, 209 or 256, at least
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least one of the Positions corresponding to positions 3, 4, 99 or 199, at least one amino acid substitution selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least three of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least two of the Positions corresponding to positions 3, 4, 99 or 199, at least two amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least three of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least three of the Positions corresponding to positions 3, 4, 99 or 199, at least three amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least three of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in the agent according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at the positions which positions 3, 4, 99 or 199, the amino acid substitutions S3T, V4I, R99E and V199I, and (ii) at least three of the positions corresponding to positions 154, 160, 181, 183, 185, 200, 203, 209 or 256, at least three amino acid
  • the protease contained in the agents according to the invention is a protease which has proteolytic activity and comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% and less than 100% identical, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least one of the positions corresponding to positions 3, 4, 99 or 199, at least one amino acid substitution selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least four of the positions corresponding to positions 154, 160, 181, 183, 185,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least two of the Positions corresponding to positions 3, 4, 99 or 199, at least two amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least four of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least three of the Positions corresponding to positions 3, 4, 99 or 199, at least three amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least four of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at the positions which correspond to positions 3, 4, 99 or 199, the amino acid substitutions S3T, V4I, R99E and V199I, and (ii) at least four of the positions corresponding to positions 154, 160, 181, 183, 185, 200, 203, 209 or 256, at least four amino acid sequence which
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least one of the Positions corresponding to positions 3, 4, 99 or 199, at least one amino acid substitution selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least five of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least two of the Positions corresponding to positions 3, 4, 99 or 199, at least two amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least five of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least three of the Positions corresponding to positions 3, 4, 99 or 199, at least three amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least five of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at the positions which corresponding to positions 3, 4, 99 or 199, the amino acid substitutions S3T, V4I, R99E and V199I, and (ii) at least five of the positions corresponding to positions 154, 160, 181, 183, 185, 200, 203, 209 or 256, at least
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least one of the Positions corresponding to positions 3, 4, 99 or 199, at least one amino acid substitution selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least six of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least two of the Positions corresponding to positions 3, 4, 99 or 199, at least two amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least six of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at least three of the Positions corresponding to positions 3, 4, 99 or 199, at least three amino acid substitutions selected from the group consisting of S3T, V4I, R99E and V199I, and (ii) at least six of the positions corresponding to positions 154, 160, 181, 183, 185, 200,
  • the protease contained in agents according to the invention is a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and, in each case based on the numbering according to SEQ ID NO:1, (i) at the positions which corresponding to positions 3, 4, 99 or 199, the amino acid substitutions S3T, V4I, R99E and V199I, and (ii) at least six of the positions corresponding to positions 154, 160, 181, 183, 185, 200, 203, 209 or 256, at least
  • cleaning agents according to the invention contain a protease which has proteolytic 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%, 99% and less than 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length, and which has one of the following amino acid substitution combinations: S3T-V4I-R99E-V199I-Q200L-Y203W; S3T-V4I-R99E-V199I-N212S; S3T-V4I-R99E-V199I-N74D; S3T-V4I-R99E-V199I-S154D-L256E; S3T-
  • cleaning agents according to the invention contain a protease which has proteolytic activity and has one of the following amino acid substitution combinations: S3T-V4I-R99E-V199I-Q200L-Y203W; S3T-V4I-R99E-V199I-N212S; S3T-V4I-R99E-V199I-N74D; S3T-V4I-R99E-V199I-S154D-L256E; S3T-V4I-R99E-V199I-Q200L-Y203W-S154D-L256E; S3T-V4I-R99E-V199I-N74D-Q200L-Y203W; S3T-V4I-R99E-V199I-N74D-S154D-Q200L-Y203W-L256E; S3T-V4I-R99E-V199I-N74D-N212S; S3T-V4I-R99E-V199I-
  • agents according to the invention contain the protease 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, based on active protein and total weight of the agent.
  • agents according to the invention contain the protease according to the invention in an amount of 0.0001 to 5 wt.%, preferably 0.001 to 2.5 wt.%, particularly preferably 0.005 to 1 wt.%, very particularly preferably 0.01 to 0.5 wt.%, based on active protein and total weight of the agent.
  • the protein concentration can be determined using known methods, e.g., 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 determination of the active protein concentration can be carried out by titration of the active sites using a suitable irreversible inhibitor and determination of the residual activity (Bender et al., J. Am. Chem. Soc., 1966, 88, 24, 5890-5913).
  • the enzymes described herein 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 may contain enzymes that form an interaction complex with other molecules or that contain an "envelope.” In this case, a single or multiple enzyme molecules may be separated from the other components of the agent by a surrounding structure. Such a separating structure may be formed by, but is not limited to, vesicles, such as a micelle or a liposome.
  • the surrounding structure may also be a virus particle, a bacterial cell, or a eukaryotic cell.
  • an agent may contain cells of Bacillus pumilus or Bacillus subtilus that express enzymes, or cell culture supernatants of such cells.
  • an enzyme has the indicated substitution(s) (or deletion or insertion) means that it contains one of the indicated substitution(s) (or deletion or insertion) at the respective position, i.e., at least the indicated positions are not otherwise mutated or deleted, e.g., by fragmentation of the enzyme.
  • the enzymes described herein, with the exception of the explicitly mentioned substitutions have the sequence of the respective reference sequence, i.e., apart from the substituted positions, they are 100% identical to the respective reference sequence.
  • sequence comparison is based on the BLAST algorithm, which is established and commonly used in the state of the art (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 essentially achieved by matching similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences. A tabular assignment of the relevant positions is called an alignment.
  • Another algorithm available in the state of the art is the FASTA algorithm.
  • Sequence comparisons are created using computer programs. Frequently used are, for example, the Clustal series (Chenna et al., Multiple sequence alignment with the Clustal series of programs, Nucleic Acid Res., 2003, 31 , 3497-3500), T-Coffee (Notredame et al., T-Coffee: A novel method for multiple sequence alignments, J. Mol. Biol., 2000, 302, 205-217) or programs based on these Programs or algorithms.
  • Sequence comparisons are also possible using the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the specified standard parameters, whose AlignX module for sequence comparisons is based on ClustalW, or Clone Manager 10 (using the BLOSUM 62 scoring matrix for sequence alignment at the amino acid level). Unless otherwise stated, the sequence identity stated herein is determined using the BLAST algorithm.
  • Such a comparison also allows a statement to be made about the similarity of the compared sequences. This is usually expressed as percent identity, i.e., the proportion of identical nucleotides or amino acid residues at the same or corresponding positions in an alignment.
  • the broader term "homology" in amino acid sequences includes conserved amino acid substitutions, i.e., amino acids with similar chemical activity, since these usually exert similar chemical activities within the peptide, protein, or enzyme. Therefore, the similarity of the compared sequences 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 comprise only a few nucleotides or amino acids. Such small regions often perform essential functions for the overall activity of the peptide, protein, or enzyme. It may therefore be useful to refer sequence matches only to individual, possibly small regions. Unless otherwise stated, identity or homology statements in this application refer to the entire length of the respective nucleic acid or amino acid sequence.
  • an amino acid position corresponds to a numerically designated position in SEQ ID NO:1 therefore means that the corresponding position is assigned to the numerically designated position in SEQ ID NO:1 in an alignment as defined above.
  • amino acid exchanges amino acid exchanges
  • 130D/V thus means that position 130 is mutated to D or V.
  • additional amino acids are named after the sequence position.
  • deletions the missing amino acid is replaced by a symbol, e.g., an asterisk or a dash, or an A is indicated before the corresponding position.
  • P9T describes the substitution of proline at position 9 with threonine
  • P9TH the insertion of histidine after the amino acid threonine at position 9
  • P9* or AP9 the deletion of proline at position 9.
  • 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 enzymes to be used can also be formulated together with accompanying substances, such as those from fermentation.
  • the enzymes are preferably used as liquid enzyme 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, liquid or gel-like products, solutions of the enzymes, preferably as concentrated as possible, with little water content, and/or containing stabilizers or other additives.
  • agents according to the invention can comprise one or more reversible protease inhibitors/stabilizers, preferably in an amount of 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight, based on the total weight of the agent. If several inhibitors/stabilizers are present, these details refer to the total concentration. In preferred embodiments, these are selected from the group consisting of polyols, such as glycerol 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 glycerol 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
  • agents according to the invention may contain boric acid as a stabilizer/inhibitor, preferably in an amount of 0.05 to 5.5 wt% and increasingly preferably 0.075 to 4.5 wt%, 0.09 to 3.5 and 0.1 to 2.49 wt%.
  • agents according to the invention can contain a phenylboronic acid derivative as a stabilizer/inhibitor, preferably in an amount of 0.0005 to 2.0% by weight, preferably 0.001 to 1.0% by weight, particularly preferably 0.01 to 0.5% by weight and very particularly preferably 0.02 to 0.2% by weight.
  • phenylboronic acid derivative is understood to mean a compound of formula (I): where R is hydrogen, a hydroxyl, a C1-8-alkyl, a substituted C1-8-alkyl, a C1-6-alkenyl, or a substituted C1-6-alkenyl group.
  • the radical R in the phenylboronic acid derivative is a C1-6-alkyl group, and more preferably -CH3, -CH3CH2, or -CH3CH2CH2. More preferably, the radical R in the phenylboronic acid derivative is hydrogen.
  • the phenylboronic acid derivative is particularly preferably 4-formylphenylboronic acid (4-FPBA).
  • Phenylboronic acid derivatives which can be used according to the invention can also have further chemical modifications on the phenyl ring, in particular they can have one or more methyl, amino, nitro, chloro, fluoro, bromo, hydroxyl, formyl, ethyl, acetyl, t-butyl, anisyl, benzyl, trifluroacetyl, N-hydroxysuccinimide, t-butyloxycarbonyl, benzoyl, 4-methylbenzyl, thioanicyl, thiocresyl, benzyloxymethyl, 4-nitrophenyl, benzyloxycarbonyl, 2-nitrobenzoyl, 2-nitrophenylsulphenyl, 4-toluenesulphonyl, pentafluorophenyl, diphenylmethyl, 2-chlorobenzyloxycarbonyl, 2,4,5-trichlorophenyl, 2-bromobenzyloxycarbonyl,
  • agents according to the invention can contain at least one peptide inhibitor as a stabilizer/inhibitor, preferably in a concentration of 0.01 to 50 mM, more preferably 0.05 to 5 mM, and particularly preferably 0.1 to 0.5 mM. If multiple peptide inhibitors are present, these details refer to the total concentration.
  • peptide inhibitor is understood to mean a compound of general formula (II) or a compound of general formula (III), optionally the compound of formula (II) or (III) being present together with a salt of formula (IV).
  • the compound of formula (II) has the following structural formula:
  • ZA-NH-CH(R)-C(O)-X (II), where A is an amino acid residue; X is hydrogen; Z is an N-capping residue selected from phosphoramidate [(R'O)2(O)P-], sulfenamide [(SR')2-], sulfonamide [(R'(O)2S-], sulfonic acid [SO3H], phosphinamide [(R')2(O)P-], sulfamoyl derivatives [R'O(O)2S-], thiourea [(R')2N(O)C-], thiocarbamate [R'O(S)C-], phosphonate [R'-P(O)OH], amidophosphate [R'O(OH)(O)P-], carbamate (R'O(O)C-) and urea (R'NH(O)C-), wherein each R' is independently selected from straight-chain or branched C1-C8 un
  • the compound of formula (III) has the following structural formula:
  • Y-B1-B0-X (III), wherein X is hydrogen; Bi is a single D- or L-amino acid residue; Bo is an amino acid residue and Y consists of one or more, preferably one or two, amino acid residues and optionally of an N-capping residue, wherein the N-capping residue is as defined under (I).
  • the salt of formula (IV) has the following structural formula:
  • C is a cation selected from the group consisting of Al3 + , Ca2 + , Li + , Mg2 + , Mn2 + , Ni2 + , K + , NRV and Na + , wherein each R" independently represents H or a linear or branched, substituted or unsubstituted alkyl, aryl or alkenyl group, all of which may optionally contain one or more heteroatom(s);
  • E is an integer from 1 to 3 and corresponds to the valence of the cation; p corresponds to the number of cations in the salt;
  • D is an anion selected from the group consisting of CH5COO-, Br, CO5 2 ', CI', C3H5O(COO)3 3 ', HCOO-, HCO5', HSO4', C2O4 2 ', SO4 2 ' and SO3 2- is;
  • F is an integer from 1 to 3 and correspond
  • Preferred radicals R are selected from methyl, iso-propyl, sec-butyl, iso-butyl, -CeHs, -CH2-C6H5, and -CH2-CH2-C6H5, such that the part -NH-CH(R)-C(O)-X of the compound of formula (II) is derived from the amino acids Ala, Val, Ile, Leu, PGly (phenylglycine), Phe and HPhe (homophenylalanine) by converting the carboxyl group into an aldehyde or trifluoromethyl ketone group.
  • aldehydes of the peptide inhibitors used herein can be prepared from the corresponding amino acids by converting the C-terminal carboxyl group of the amino acid into an aldehyde group.
  • aldehydes can be prepared by known methods, as described, for example, in US 5015627, EP 0185930, EP 0583534, and DE 3200812.
  • trifluoromethyl ketones used herein can also be prepared from the corresponding amino acids by converting the C-terminal carboxyl group into a trifluoromethyl ketone group.
  • Such trifluoromethyl ketones can be prepared by known methods, such as those described in EP 0583535.
  • substituent A is selected from Ala, Gly, Val, Ile, Leu, Phe and Lys.
  • the N-terminal end of the peptide inhibitor according to formula (II) and/or the peptide inhibitor according to formula (III) is protected by a protecting group which caps the N-terminus, wherein the group is selected from the group consisting of carbamates, ureas, sulfonamides, phosphonamides, thioureas, sulfenamides, sulfonic acids, phosphinamides, thiocarbamates, amidophosphates and phosphonamides.
  • the N-terminal end is protected by a methyl, ethyl or benzylcarbamate group [CH3O-(O)C-; CH3CH2O-(O ) C-; or C6H5CH2O- (O)C-], a methyl, ethyl or benzylurea group [ CH3NH- (O)C-; CH3CH2NH- (O)C-; or C6H5CH2NH- (O)C-], a methyl, ethyl or benzylsulfonamide group [ CH3SO2- ; CH3CH2SO2- ; or C6H5CH2SO2- ], or a methyl, ethyl or benzylamidophosphate group [CH3O(OH)(O)P-; CH3CH2O ( OH )(O)P-; or C6H5CH2O ( OH )(O)P-].
  • N-capping groups can be carried out using methods known to the person skilled in the art, see, for example, EP 3263289 or the references cited therein.
  • agents according to the invention may comprise, in addition to a peptide inhibitor of formula (II) or (III), salts of formula (IV). These salts may be present in a concentration of 50 to 2,000 mM, preferably 70 to 1,500 mM, more preferably 100 to 1,000 mM, more preferably 150 to 500 mM, and most preferably 200 mM.
  • the salt of formula (IV) is particularly preferred: Na2SO4 .
  • alkyl refers to an aliphatic hydrocarbon group, which may be straight or branched and comprises 1 to 20 carbon atoms in the chain.
  • aryl refers to an aromatic monocyclic or multicyclic ring system comprising 6 to 14 carbon atoms.
  • alkenyl refers to an aliphatic hydrocarbon group containing at least one carbon-carbon double bond, which may be straight or branched and comprises 2 to 15 carbon atoms in the chain.
  • Bo is a D- or L-amino acid residue selected from the group consisting of Tyr, m-tyrosine, 3,4-dihydroxyphenylalanine, Phe, Val, Met, Nva, Leu, Ile and Nie
  • Bi is a D- or L-amino acid residue with an (optionally substituted) small aliphatic side group, preferably Ala, Cys, Gly, Pro, Ser, Thr, Val, Nva or Nie.
  • B 2 and B3 are each independently an amino acid residue and Z is an N-capping residue, the N-capping residue being as defined above.
  • B 2 selected from Val, Gly, Ala, Arg, Leu, Phe and Thr
  • B3 selected from Phe, Tyr, Trp, phenylglycine, Leu, Val, Nva, Nie and Ile.
  • peptide inhibitors of formulas (II) and (III) that can be used in agents according to the invention include, but are not limited to, Cbz-Arg-Ala-Tyr-H, Ac-Gly-Ala-Tyr-H, Cbz-Gly-Ala-Tyr-H, Cbz-Gly-Ala-Tyr-H, Cbz-Val-Ala-Tyr-H, Cbz-Gly-Ala-Phe-H, Cbz-Gly-Ala-Val-H, Cbz-Gly-Gly-Tyr-H, Cbz-Gly-Gly-Phe-H, Cbz-Arg-Val-Tyr-H, Cbz-Leu-Val-Tyr-H, Ac-Le
  • Cbz refers to the benzyloxycarbonyl group with the molecular formula C7H7O. This is used as a protecting group.
  • Other terminal groups in the peptide inhibitors of the present invention may be: "Ph”: phenyl; “Ac”: acetyl; and “Me”: methyl.
  • urea is synonymous with urea.
  • the invention also encompasses all stereoisomers, in particular enantiomers and diastereomers, tautomers and salts of the compounds described above.
  • a salt of formula (IV) to a peptide inhibitor of formula (II) or (III) further stabilizes the enzyme-peptide inhibitor complex by removing free reactive water molecules. This increases the binding efficiency of the peptide inhibitor to the enzyme and/or increases the ionic strength, which ultimately stabilizes the enzyme-peptide inhibitor complex.
  • at least one salt of formula (IV) it is possible to employ the peptide inhibitors in moderate concentrations (0.01 to 50 mM).
  • the protease and any other proteins contained therein, in particular other enzymes are thus protected against proteolysis by this enzyme, in particular proteases (stabilized against proteolysis) and thus retain their full effectiveness even after storage.
  • these peptide inhibitor compounds have good water solubility, so that they can be easily incorporated into corresponding agents and precipitation during storage is avoided.
  • All compounds that can be used as stabilizers/inhibitors in the present invention can be present in the compositions in all profaned or deprotonated forms. Furthermore, all such compounds, especially their deprotonated forms, can be associated with cations. Preferred cations In this regard, monovalent or polyvalent, in particular divalent, cations are preferred, in particular Na ions (Na + ), K ions (K + ), Li ions (Li + ), Ca ions (Ca 2+ ), Mg ions (Mg 2+ ), Mn ions (Mn 2+ ), and Zn ions (Zn 2+ ). Na ions (Na + ) are particularly preferred.
  • agents according to the invention can contain an enzyme composition in which the protease and the stabilizer-inhibitor compound are preformulated.
  • the enzyme protein constitutes only a fraction of the total weight of conventional enzyme preparations.
  • the protease preparations contain between 0.1 and 40 wt.%, preferably 0.2 and 30 wt.%, particularly preferably 0.4 and 20 wt.%, and most preferably 0.8 and 10 wt.% of the enzyme protein.
  • the stabilizer compound can be present in an amount of 0.05 to 35 wt.%, preferably 0.05 to 10 wt.%, based on the total weight in the enzyme composition.
  • Agents according to the invention contain at least one surfactant.
  • the surfactant can be selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
  • agents according to the invention contain at least one non-ionic surfactant.
  • agents according to the invention contain at least two surfactants, wherein the two surfactants are different from one another and are selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof.
  • agents according to the invention contain at least two nonionic surfactants which are different from one another.
  • agents according to the invention contain at least two non-ionic surfactants, wherein the two surfactants are different from one another and are selected from the group consisting of alcohol ethoxylates and alkyl polyglycosides.
  • agents according to the invention contain at least two non-ionic surfactants, the first surfactant being an alcohol ethoxylate and the second surfactant being an alkyl polyglycoside.
  • At least one further surfactant may be included, which is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof.
  • agents according to the invention contain the surfactant or surfactants in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, particularly preferably 0.05 to 5 wt.%, very particularly preferably 0.1 to 2.5 wt.%, in each case based on active substance and total weight of the agent.
  • agents according to the invention contain a first surfactant, wherein the first surfactant is an alcohol ethoxylate, in an amount of 0.1 to 10 wt.%, preferably 0.25 to 7.5 wt.%, preferably 0.3 to 6 wt.%, particularly preferably 0.5 to 5 wt.%, and a second surfactant, wherein the second surfactant is an alkyl polyglycoside, in an amount of 0.05 to 6.5 wt.%, preferably 0.1 to 5.5 wt.%, preferably 0.2 to 4 wt.%, particularly preferably 0.3 to 3.5 wt.%, in each case based on the active substance and the total weight of the agent.
  • agents according to the invention contain a first surfactant, wherein the first surfactant is an alcohol ethoxylate, in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, preferably 0.05 to 5 wt.%, very particularly preferably 0.1 to 2.5 wt.%, and a second surfactant, wherein the second surfactant is an alkyl polyglycoside, in an amount of 0.0005 to 6.5 wt.%, preferably 0.005 to 5 wt.%, very particularly preferably 0.03 to 3 wt.%, very particularly preferably 0.05 to 1.5 wt.%, in each case based on the active substance and the total weight of the agent.
  • agents according to the invention contain a first surfactant, wherein the first surfactant is an alcohol ethoxylate, and a second surfactant, wherein the second surfactant is an alkyl polyglycoside, wherein the first surfactant and the second surfactant are present in a ratio of 1:0.1 to 1:1.5, preferably 1:0.2 to 1:1.2, particularly preferably 1:0.25 to 1:1, very particularly preferably 1:0.5 to 1:0.75, e.g. 1:0.1, 1:0.2, 1:0.25, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.9, 1:1, 1:1,1, 1:1,2, 1:1,25, 1:3, 1:4, 1:5.
  • agents according to the invention contain a first surfactant, wherein the first surfactant is an alcohol ethoxylate, in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, preferably 0.05 to 5 wt.%, very particularly preferably 0.1 to 2.5 wt.%, and a second surfactant, wherein the second surfactant is an alkyl polyglycoside, in an amount of 0.0005 to 6.5 wt.%, preferably 0.005 to 5 wt.%, particularly preferably 0.03 to 3 wt.%, very particularly preferably 0.05 to 1.5 wt.%, in each case based on active substance and total weight of the agent, wherein the first surfactant and the second surfactant are present in a ratio of 1:0.1 to 1:1.5, preferably 1:0.2 to 1:1.2, particularly preferably 1:0.25 to 1:1, very particularly preferably 1:0.5 to 1:0.75, e.g.
  • 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 carbon 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, with regard to the alkyl moiety, correspond to the aforementioned long-chain alcohol derivatives, as well as of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, are also suitable.
  • nonionic surfactants which can be 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 having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
  • Nonionic surfactants within the scope of the invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters.
  • Ethylene oxide/propylene oxide block polymers fatty acid alkanolamides and fatty acid polyglycol ethers can also be used.
  • Another important class of nonionic surfactants that can be used according to the invention are polyol surfactants, and here in particular glycosurfactants, such as alkyl polyglycosides and fatty acid glucamides.
  • the alkyl polyglycosides in particular the alkyl polyglucosides, wherein the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched Cs to Cis-alkyl chains and the degree of oligomerization (DP) of the sugars is between 1 and 10, preferably 1 to 6, preferably 1.1 to 3, particularly preferably 1.1 to 1.7, e.g. Cs-io-alkyl-1.5-glucoside (DP of 1.5).
  • the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched Cs to Cis-alkyl chains and the degree of oligomerization (DP) of the sugars is between 1 and 10, preferably 1 to 6, preferably 1.1 to 3, particularly preferably 1.1 to 1.7, e.g. Cs-io-alkyl-1.5-glucoside (DP of 1.5).
  • fatty alcohol alkoxylates are also preferred, in particular unbranched or branched, saturated or unsaturated Cs-22 alcohols alkoxylated with ethylene oxide (EO) and/or propylene oxide (PO) and having a degree of alkoxylation of up to 30, preferably ethoxylated Cs-22 fatty alcohols having a degree of ethoxylation of less than 30, preferably 12 to 28, particularly preferably 20 to 28, very particularly preferably 25, e.g. Cs-16-18 fatty alcohol ethoxylates with 25 EO.
  • EO ethylene oxide
  • PO propylene oxide
  • 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.
  • the alcohol radical can be linear or, preferably, methyl-branched in the 2-position, or can contain linear and methyl-branched radicals in a mixture, as is usually the case in oxo alcohol radicals.
  • 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 particularly preferred.
  • Preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 EO or 4 EO, C8-C14 alcohols with 7 EO, C13-C15 alcohols with 3 EO, 5 EO, 7 EO, or 8 EO, C18-C19 alcohols with 3 EO, 5 EO, or 7 EO, and mixtures thereof, such as mixtures of C12-C14 alcohol with 3 EO and C12-C18 alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which can be a whole or 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.
  • APG alkyl polyglycosides
  • RO(G) Z in which R is a linear or branched, in particular 2-methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol that represents a glycose unit with 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1 and 4, preferably between 1 and 2, and more preferably between 1.1 and 1.4.
  • Linear alkyl polyglycosides are preferred, i.e., alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the agent according to the invention can contain at least one anionic surfactant.
  • anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ethersulfonates, n-alkyl ether sulfonates, estersulfonates, and ligninsulfonates.
  • fatty acid cyanamides sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-Ca-is-alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids, and alkyl (ether) phosphates, as well as ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates, and alkyl ethers of glycerol disulfate.
  • sulfosuccinates sulfosuccinic acid esters
  • sulfosuccinic acid mono- and di-Ca-is-alkyl esters sulfosuccinamates, sulf
  • linear alkylbenzenesulfonates, fatty alcohol sulfates, and/or fatty alcohol ether sulfates, in particular fatty alcohol sulfates are preferred within the scope of the present invention.
  • Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols
  • fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably with longer-chain alcohols within the meaning of the present invention.
  • n moles of ethylene oxide and one mole of alcohol generally form a complex mixture of addition products with varying degrees of ethoxylation.
  • Another embodiment of the alkoxylation involves the use of mixtures of alkylene oxides, preferably a mixture of ethylene oxide and propylene oxide.
  • Preferred fatty alcohol ether sulfates are the sulfates of low-ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, e.g., 1,3 EO.
  • EO ethylene oxide units
  • alkylbenzenesulfonates those with about 12 C atoms in the alkyl moiety are particularly preferred, such as linear sodium C10-18-alkylbenzenesulfonate.
  • Preferred olefinsulfonates have a carbon chain length of 14 to 16.
  • the anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, e.g., magnesium salts, or in the form of ammonium or mono-, di-, tri-, or tetraalkylammonium salts; in the case of sulfonates, also in the form of their corresponding acid, e.g., dodecylbenzenesulfonic acid.
  • Sophorolipids can also be used as further surfactants. These are to be assumed to be anionic in alkaline conditions and are therefore to be understood as anionic surfactants in the context of the present application.
  • the agent according to the invention may also contain cationic surfactants and/or amphoteric surfactants.
  • Suitable amphoteric surfactants are, for example, betaines of the formula
  • R iii )(R iv )(R v )N + CH 2 COO- in which " represents an alkyl radical having 8 to 25, preferably 10 to 21, carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R iv and R v represent identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10-18 alkyldimethylcarboxymethylbetaine and C n-17 alkylamidopropyldimethylcarboxymethylbetaine.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (Rvi)(Rvii)( R viii)( R ix) N + X; in which R vi to R ix represent four identical or different, in particular two long-chain and two short-chain, alkyl radicals and X- represents 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 those containing a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be given an antimicrobial effect or its already existing antimicrobial effect, which may be due to other ingredients, can be improved.
  • the total surfactant content of such a preferably aqueous cleaning agent formulation is preferably 0.001 to 10% by weight, preferably 0.01 to 7.5% by weight, particularly preferably 0.05 to 5% by weight, very particularly preferably 0.1 to 2.5% by weight, based on the active substance and the total weight of the formulation.
  • Agents according to the invention have a pH in a range from about 7 to about 10, preferably about 7 to about 9, particularly preferably about 7.5 to about 8, most particularly preferably about 7, in a 1% by weight solution in deionized water at 20°C.
  • 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 metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides, preferably sodium hydroxide.
  • Such pH regulators are preferably present in agents according to the invention in a concentration of no more than 10% by weight, preferably 0.5 to 6% by weight, particularly preferably 0.3 to 2% by weight, based on the total weight of the agent.
  • agents according to the invention may further contain one or more buffer substances, usually in amounts of 0.001 to 5 wt.%, preferably 0.005 to 3 wt.%, more preferably 0.01 to 2 wt.%, particularly preferably 0.05 to 1 wt.%, very particularly preferably 0.1 to 0.5 wt.%, e.g., 0.2 wt.%.
  • buffer substances that are also complexing agents or even chelating agents.
  • Particularly preferred buffer substances are citric acid or citrate, in particular sodium and potassium citrate, e.g., trisodium citrate 2 H2O and tripotassium citrate H2O.
  • agents according to the invention in a 1 wt.% solution in deionized water at 20°C have a pH in a range from about 7 to about 10, preferably about 7 to about 9, particularly preferably about 7.5 to about 8, most particularly preferably about 7, the pH being adjusted by adding citric acid or NaOH.
  • cleaning performance refers to the ability of a cleaning agent to partially or completely remove existing soiling.
  • an agent and the cleaning liquor formed by this agent have a respective cleaning performance.
  • the cleaning performance is preferably determined as indicated in Examples 2 and 3.
  • cleaning liquor refers to the working solution containing the cleaning agent that acts on the surfaces to be cleaned, especially sanitary surfaces such as toilets, toilet bowls, toilet cisterns, and toilet rims, and thus comes into contact with the soiling present on the surfaces.
  • the cleaning liquor is usually created when the cleaning process begins and the agent is diluted with water, for example, in a suitable container.
  • Preferred embodiments of uses and agents according to the invention achieve such advantageous cleaning performance even at low temperatures, in particular in a temperature range from about 10°C to about 30°C, preferably about 15°C to about 30°C, preferably about 18°C to about 25°C, particularly preferably about 25°C, very particularly preferably about 20°C.
  • the protease according to the invention is used in cleaning agents.
  • the combination of surfactant(s) and protease according to the invention is used in cleaning agents.
  • cleaning agents according to the invention include all conceivable types of cleaning agents, both concentrated and undiluted, for use on a commercial scale in hand cleaning. These include, for example, 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., also scouring agents, glass cleaners, toilet air fresheners, etc.
  • Preferred embodiments include all liquid, gel-like, or pasty dosage forms of agents according to the invention, which may optionally also consist of multiple phases and may be present in compressed or non-compressed form, e.g., in the form of a non-aqueous cleaning agent or a non-aqueous paste, or in the form of an aqueous cleaning agent or a water-containing paste.
  • Liquid agents are generally preferred.
  • the agent may be present as a single-component system. Such agents consist of one phase. Alternatively, an agent may also consist of multiple phases. Such an agent is therefore divided into multiple components.
  • the agent according to the invention is a liquid cleaning agent.
  • the agent according to the invention is a Liquid cleaning agent for cleaning sanitary surfaces such as toilets, toilet bowls, toilet cisterns, and toilet rims.
  • agents according to the invention when they are in liquid form, they preferably contain, based on their total weight, more than 40% by weight and increasingly preferably more than 50% by weight, 60% by weight, 70% by weight, 80% by weight, 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight, 96% by weight or 97% by weight, and less than 100% by weight, of water.
  • Agents according to the invention can contain, in addition to the inventive combination of surfactant(s) and protease, all known ingredients customary in such agents, with at least one further ingredient preferably being present in the agent.
  • Agents according to the invention can, in particular, contain further surfactants, builders, complexing agents, polymers, glass corrosion inhibitors, corrosion inhibitors, fillers, bleaching agents, bleach activators or bleach catalysts, water-miscible organic solvents, further enzymes, enzyme stabilizers, sequestering agents, electrolytes, pH regulators and/or further auxiliaries such as foam regulators, as well as dyes and fragrances.
  • the cleaning agent according to the invention is an aqueous cleaning agent for hard surfaces, in particular for cleaning sanitary surfaces such as toilets, toilet bowls, toilet cisterns, and toilet rims.
  • it may contain one or more other water-soluble organic solvents, typically in an amount of 0 to 15 wt.%, preferably 1 to 12 wt.%, more preferably 3 to 8 wt.%.
  • the solvents are used as needed, particularly as hydrotropes and viscosity regulators. They act as solubilizers, particularly for surfactants and electrolytes, as well as perfumes and dyes, and thus contribute to their incorporation, prevent the formation of liquid-crystalline phases, and contribute to the formation of clear products.
  • the viscosity of the compositions according to the invention decreases with increasing solvent quantity.
  • the cold turbidity and clear point of the compositions according to the invention decrease with increasing solvent quantity.
  • Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C1-20 hydrocarbons, preferably C2-15 hydrocarbons, having at least one hydroxyl group and optionally one or more ether functions COC, i.e. oxygen atoms interrupting the carbon atom chain.
  • Preferred solvents are C2-6 alkylene glycols and poly-C2-3 alkylene glycol ethers, optionally etherified on one side with a C1-6 alkanol, having an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule, as well as C1-6 alcohols, preferably ethanol, n-propanol or isopropanol.
  • solvents include: buteth-3, butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyloctanol, diethylene glycol, dimethoxydiglycol, dimethyl ether, dipropylene glycol, ethoxydiglycol, ethoxyethanol, ethylhexanediol, glycol, hexanediol, 1 ,2,6-Hexanetriol, Hexylalcohol, Hexylene glycol, Isobutoxypropanol, Isopentyldiol, Isopropyl alcohol (isopropanol), 3-Methoxybutanol, Methoxydiglycol, Methoxyethanol, Methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG-10, Methylal, Methyl alcohol,
  • the solvent is preferably selected from the group comprising ethanol, propanol, isopropanol, ethylene glycol, butyl glycol, propylene glycol, polypropylene glycols, and alcohol amines, in particular monoethanolamine, and mixtures thereof.
  • Particularly preferred solvents are the C2 and C8 alcohols, ethanol, n-propanol, and/or isopropanol, as well as the polyalkylene glycols, especially polypropylene glycols, in particular PPG-400, and alcohol amines, in particular monoethanolamine, and mixtures thereof.
  • 1-Butoxypropan-2-ol and/or ethanol and/or isopropanol are very particularly preferably used as the organic solvent.
  • agents according to the invention can contain one or more complexing agents.
  • Complexing agents ICI chelating agents
  • sequestering agents are ingredients capable of complexing and inactivating metal ions to prevent their adverse effects on the stability or appearance of the agents according to the invention, e.g., cloudiness.
  • it is important to complex the calcium and magnesium ions of water hardness, which are incompatible with numerous ingredients.
  • the complexing of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents. Furthermore, the complexing agents support the cleaning effect.
  • Suitable complexing agents are selected from, for example: aminotrimethylenephosphonic acid, ß-alaninediacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediaminetetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriaminepentamethylenephosphonic acid, dipotassium EDTA, disodium azacycloheptanediphosphonate, disodium EDTA, disodium pyrophosphate, EDTA, etidronic acid, galactaric acid, gluconic acid, glucuronic acid, HEDTA, hydroxypropylcyclodextrin, methylcyclodextrin, pentapotassium triphosphate, pentasodium aminotrimethylenephosphonate, pentasodium ethylenediaminetetramethylenephosphonate, pentasodium pentetate, pentasodium triphosphate,
  • phosphonates particularly preferred complexing agents are phosphonates, provided their use is permitted by regulations.
  • the complexing phosphonates include a number of different compounds, such as diethylenetriaminepenta(methylenephosphonic acid) (DTPMP).
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • hydroxyalkane and aminoalkanephosphonates are particularly preferred.
  • 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues. They are preferably used in the form of neutral sodium salts, e.g., as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. HEDP, a preferred builder from the phosphonate class, is used. Aminoalkanephosphonates also possess pronounced heavy metal binding capacity.
  • agents also contain bleach, to use aminoalkanephosphonates, particularly DTPMP, or mixtures of the aforementioned phosphonates.
  • a preferred agent within the scope of this application contains one or more phosphonate(s) from the group consisting of aminotrimethylenephosphonic acid (ATMP) and/or salts thereof;
  • Ethylenediaminetetra(methylenephosphonic acid) Ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and/or its salts; diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and/or its salts; 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and/or its salts; 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and/or its salts; hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) and/or its salts; nitrilotri(methylenephosphonic acid) (NTMP) and/or its salts.
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • PBTC 2-phosphonobutane-1,2,4-tricarboxylic acid
  • HDTMP hexamethylenedi
  • agents which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.
  • agents according to the invention can contain two or more different phosphonates.
  • agents according to the invention can contain 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 from 0.1 to 8.0 wt.%, preferably 0.2 to 5.0 wt.%, particularly preferably 0.3 to 3.0 wt.% and most preferably 0.5 to 2.0 wt.%.
  • agents according to the invention are substantially free of phosphonate-containing compounds.
  • substantially free of phosphonate-containing compounds in this context means that the corresponding agents or compositions contain less than 2 wt.%, preferably less than 1 wt.%, more preferably less than 0.5 wt.%, and particularly preferably less than 0.1 wt.%, of phosphonate-containing compounds, based on the total weight of the agent.
  • these agents/compositions are free of phosphonate-containing compounds.
  • agents according to the invention may further contain builders, preferably at least one water-soluble and/or water-insoluble, organic and/or inorganic builder.
  • 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, preferably up to 25% by weight, more preferably from 1 to 8% by weight, and particularly preferably from 0.01 to 4% by weight, based on the total weight of the composition.
  • Useful organic builders include, for example, polycarboxylic acids, which can be used in the form of the free acid and/or their sodium salts. Polycarboxylic acids are understood to be carboxylic acids that carry more than one acid function.
  • Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids and carboxymethyl inulins, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, glutaminediacetic acid, nitrilotriacetic acid (NTA), iminodisuccinate such as ethylenediamine-N,N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), lysinetetra(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids
  • Such organic builder substances can, if desired, be present in amounts of up to 50% by weight, preferably up to 25% by weight, preferably from 10 to 20% by weight, more preferably from 1 to 5% by weight and particularly preferably from 0.01 to 3% by weight, based on the total weight of the agent.
  • 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 Citric acid or citric acid salts are particularly preferred as the builder substance.
  • MGDA methylglycinediside acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • EDDS ethylenediamine disuccinate
  • citric acid and/or citrate is used as the water-soluble, organic builder. Particular preference is given to using, based on the total weight of the agent, from 0.001 to 25 wt. %, preferably from 0.005 to 12.5 wt. %, preferably from 0.0075 to 10 wt. %, particularly preferably from 0.01 to 4 wt. %, citric acid and/or 0.001 to 25 wt. %, preferably from 0.005 to 12.5 wt. %, preferably from 0.0075 to 10 wt. %, particularly preferably from 0.01 to 4 wt. %, citrate, preferably alkali metal citrate, preferably sodium citrate.
  • Citric acid/citrate can each be used in the form of their hydrates; for example, citric acid can be used in the form of the monohydrate, and citrate in the form of the trisodium citrate dihydrate.
  • the builder substances can be selected from MGDA and GLDA.
  • MGDA includes, among others, methylglycinediacetic acid, ⁇ -alaninediacetic acid, N-(1-carboxyethyl)iminodiacetic acid, and N,N-bis(carboxymethyl)-DL-alanine, including the free acid forms and the corresponding salts, preferably alkali salts, especially trisodium salts.
  • GLDA includes, among others, glutamic acid diacetic acid, L-glutamic acid N,N-diacetic acid, and N,N-bis(carboxylatomethyl)-L-glutamate, including the free acid forms and the corresponding salts, preferably alkali salts, especially tetrasodium salts.
  • higher MGDA or GLDA concentrations are possible, preferably up to 25% by weight, based on the total weight of the agent, 0.2 to 5% by weight, more preferably 0.25 to 3% by weight, and particularly preferably 0.5 to 2% by weight of MGDA, preferably MGDA trisodium salt (MGDA-Nas), is preferably used.
  • GLDA preferably GLDA tetrasodium salt (GLDA-Na4), based on the total weight of the agent.
  • 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 weight of 500 to 70,000 g/mol.
  • the molar masses stated for polymeric polycarboxylates are weight-average molar masses Mw of the respective acid form, which were generally determined by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which, due to its structural similarity to the polymers investigated, provides realistic molar weight values. These figures differ significantly from the molar weight figures used for polystyrenesulfonic acids as standards.
  • Suitable polymers include, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular weights of 2,000 to 10,000 g/mol, and particularly preferably of 3,000 to 5,000 g/mol, may in turn be preferred.
  • Copolymeric polycarboxylates are also suitable, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have proven particularly suitable.
  • Their relative molecular weight, based on free acids is generally 2,000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol, and in particular 30,000 to 40,000 g/mol.
  • Agents according to the invention are preferably free of phosphate builders, i.e. they contain, based on the total weight of the agent, less than 1% by weight, preferably no deliberately added phosphate builder.
  • cleaning-active polymers can be contained in the inventive agents in addition to the previously described builders.
  • the weight fraction of cleaning-active polymers in the total weight of the inventive agents is preferably 0.1 to 20 wt. %, more preferably 1.0 to 15 wt. %, and particularly preferably 2.0 to 12 wt. %.
  • agents according to the invention may contain one or more other auxiliaries and additives which are customary, particularly in cleaning agents for hard surfaces.
  • auxiliaries and additives include, for example, organic suspending agents (e.g. sugar, sugar alcohols, glycerin, glycols and polymers thereof), hydrophobicity enhancers (e.g. paraffin), UV stabilizers, perfume oils, antimicrobial agents, pearlescent agents (opacifying agents; e.g. glycol distearate, e.g. Cutina® AGS from BASF, or mixtures containing it, e.g. Euperlane® from BASF), other opacifiers, dyes, corrosion inhibitors, bittering agents, preservatives (e.g.
  • 2-bromo-2-nitropropane-1,3-diol which is commercially available, for example, as Myacide® BT or Boots Bronopol BT from Boots, or Bronopol-containing mixtures such as Preventol® (ex Lanxess) or Parmetol® (ex Schülke & Mayr)), disinfectants, Enzymes, pH adjusters, fragrances, and skin-feel-improving or skin-care additives (e.g., dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D, panthenol, sericerin, collagen partial hydrolysate, various vegetable protein partial hydrolysates, protein hydrolysate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, A.H.A. complexes, g
  • agents according to the invention may contain one or more fragrances, preferably in an amount of 0.001 to 10% by weight, preferably 0.05 to 1 Wt.%, particularly preferably from 0.1 to 5 wt.%.
  • suitable perfume components d-limonene, essential oils, such as pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil, clary sage, chamomile, lavender, clove, lemon balm, mint, cinnamon leaf, linden blossom, juniper berry, vetiver, olibanum, galbanum, labdanum, orange blossom, neroli, orange peel, and sandalwood oil.
  • agents according to the invention can contain one or more antimicrobial active ingredients, preferably in an amount of 0.01 to 1 wt. %, preferably 0.02 to 0.8 wt. %, more preferably 0.05 to 0.5 wt. %, particularly preferably 0.1 to 0.3 wt. %, most particularly preferably 0.2 wt.
  • the terms disinfection, sanitation, antimicrobial effect and antimicrobial active ingredient, as used herein, have the customary technical meaning.
  • disinfection in the narrower sense of medical practice means the killing of - theoretically all - infectious germs
  • sanitation is understood to mean the elimination as far as possible of all germs - including saprophytic germs that are normally harmless to humans.
  • the extent of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing content of antimicrobial active ingredient or increasing dilution of the agent for application.
  • Suitable antimicrobial agents can be selected from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynylbutylcarbamate, iodine, iodophores, active chlorine-releasing compounds and peroxides.
  • Preferred antimicrobial agents can be selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine) dihydrochloride, N,N'-bis-(4-chlorophenyl)-3,12-diimino-2,
  • Preferred antimicrobial quaternary surfactants contain an ammonium, sulfonium, phosphonium, iodonium, or arsonium group.
  • antimicrobially active essential oils can also be used, which simultaneously provide fragrance for the cleaning product.
  • particularly preferred antimicrobial active ingredients are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite, sodium dichloroisocyanurate and mixtures thereof.
  • agents according to the invention may contain preservatives. These can essentially be the substances mentioned under the antimicrobial active ingredients.
  • agents according to the invention can contain one or more dyes.
  • Both water-soluble and oil-soluble dyes can be used as dyes, whereby compatibility with other ingredients, e.g., bleaching agents, must be taken into account, and the dye used should not have a substantive effect on the metal and ceramic, even after prolonged exposure.
  • the dyes are preferably present in an amount of 0.0001 to 0.1 wt. %, preferably 0.0005 to 0.05 wt. %, particularly preferably 0.001 to 0.01 wt. %.
  • agents according to the invention can contain corrosion inhibitors.
  • Suitable corrosion inhibitors include, for example: cyclohexylamine, diammonium phosphate, dilithium oxalate, dimethylaminomethylpropanol, dipotassium oxalate, dipotassium phosphate, disodium phosphate, disodium pyrophosphate, disodium tetrapropenylsuccinate, hexoxyethyldiethylammonium, phosphate, nitromethane, potassium silicate, sodium aluminate, sodium hexametaphosphate, sodium metasilicate, sodium molybdate, sodium nitrite, sodium oxalate, sodium silicate, stearamidopropyl dimethicone, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, and triisopropanolamine.
  • agents according to the invention can contain rinse-off regulators.
  • the substances referred to as rinse-off regulators primarily serve to control the consumption of the agents during use so that the intended service life is maintained.
  • Suitable regulators are preferably solid long-chain fatty acids, such as stearic acid, but also salts of such fatty acids, fatty acid ethanolamides, such as coconut fatty acid monoethanolamide, or solid polyethylene glycols, such as those with molecular weights between 10,000 and 50,000.
  • agents according to the invention can contain foam regulators.
  • foam regulators 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 crosslinked polysiloxane resins and mixtures thereof.
  • 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 carbon atoms, e.g., sodium behenate, and alkali metal salts of phosphoric acid mono- and/or dialkyl esters in which the alkyl chains each have 12 to 22 carbon atoms.
  • sodium monoalkyl phosphate and/or dialkyl phosphate with C 16-18 alkyl groups is preferably used.
  • the proportion of foam regulators may preferably be 0.2 to 2% by weight, preferably not more than 1% by weight, based on the total weight of the agent.
  • agents according to the invention may contain, in addition to the protease described herein, further hydrolytic enzymes or other enzymes in a form suitable for The enzymes are preferably used in concentrations appropriate for the effectiveness of the agent.
  • Enzymes that can exhibit catalytic activity in agents according to the invention are selected in particular from proteases, lipases, amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, xyloglucanases, ß-glucosidases, pectinases, carrageenases, perhydrolases, oxidases, oxidoreductases, and mixtures thereof.
  • Enzymes are advantageously contained in the agent in an amount of 1 x 10 -8 to 5 wt.%, based on the active protein and the total weight of the agent. Increasingly preferably, each enzyme is present in agents according to the invention in an amount of 1 x 10 -7 to 3 wt.%, 0.00001 to 1 wt.%, 0.00005 to 0.5 wt.%, 0.0001 to 0.1 wt.%, and particularly preferably 0.0001 to 0.05 wt.%, based on active protein and total weight of the agent. Enzymes particularly preferably exhibit synergistic cleaning performance against certain soils or stains, i.e., the enzymes contained in the agent composition mutually support each other in their cleaning performance.
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5 wt.%, preferably 0.001 to 2.5 wt.%, particularly preferably 0.005 to 1 wt.%, most preferably 0.01 to 0.5 wt.%, based on active protein and total weight of the agent, at least two surfactants, wherein the first surfactant and the second surfactant are different from one another and are selected from the group consisting of alcohol ethoxylates and alkyl polyglycosides, preferably the first surfactant is an alcohol ethoxylate, in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, particularly preferably 0.05 to 5 wt.%, most
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5 wt.%, preferably 0.001 to 2.5 wt.%, particularly preferably 0.005 to 1 wt.%, very particularly preferably 0.01 to 0.5 wt.%, based on active protein and total weight of the agent, wherein the protease is a protease which has proteolytic activity and comprises an amino acid sequence which belongs to the amino acid sequence described in SEQ ID NO:1 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%,
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5% by weight, preferably 0.001 to 2.5% by weight, particularly preferably 0.005 to 1% by weight, very particularly preferably 0.01 to 0.5% by weight, based on active protein and total weight of the agent, wherein the protease has proteolytic activity and comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5 wt.%, preferably 0.001 to 2.5 wt.%, particularly preferably 0.005 to 1 wt.%, most preferably 0.01 to 0.5 wt.%, based on active protein and total weight of the agent, at least two surfactants, wherein the first surfactant and the second surfactant are different from one another and are selected from the group consisting of alcohol ethoxylates and alkyl polyglycosides, preferably the first surfactant is an alcohol ethoxylate, in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, particularly preferably 0.05 to 5 wt.%, most
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5% by weight, preferably 0.001 to 2.5% by weight, particularly preferably 0.005 to 1% by weight, very particularly preferably 0.01 to 0.5% by weight, based on active protein and total weight of the agent, wherein the protease is a protease which has proteolytic activity and 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 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%,
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5% by weight, preferably 0.001 to 2.5% by weight, particularly preferably 0.005 to 1% by weight, very particularly preferably 0.01 to 0.5% by weight, based on active protein and total weight of the agent, wherein the protease has proteolytic activity and comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5 wt.%, preferably 0.001 to 2.5 wt.%, particularly preferably 0.005 to 1 wt.%, most preferably 0.01 to 0.5 wt.%, based on active protein and total weight of the agent, at least two surfactants, wherein the first surfactant and the second surfactant are different from one another and are selected from the group consisting of alcohol ethoxylates and alkyl polyglycosides, preferably the first surfactant is an alcohol ethoxylate, in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, particularly preferably 0.05 to 5 wt.%, most
  • the agent in 1 wt.% solution in deionized water at 20°C has a pH in a range from about 7 to about 10, preferably about 7 to about 9, more preferably about 7.5 to about 8, most preferably about 7.
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, Toilet bowl, cistern, WC rim, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5% by weight, preferably 0.001 to 2.5% by weight, particularly preferably 0.005 to 1% by weight, very particularly preferably 0.01 to 0.5% by weight, based on active protein and total weight of the agent, wherein the protease is a protease which has proteolytic activity and comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%
  • the agent in 1 wt.% solution in deionized water at 20°C has a pH in a range of about 7 to about 10, preferably about 7 to about 9, more preferably about 7.5 to about 8, most preferably about 7.
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, WC rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5% by weight, preferably 0.001 to 2.5% by weight, particularly preferably 0.005 to 1% by weight, very particularly preferably 0.01 to 0.5% by weight, based on active protein and total weight of the agent, wherein the protease has proteolytic 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%, 99% and less than
  • the agent in 1 wt.% solution in deionized water at 20°C has a pH in a range of about 7 to about 10, preferably about 7 to about 9, more preferably about 7.5 to about 8, most preferably about 7.
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, WC rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5 wt.%, preferably 0.001 to 2.5 wt.%, particularly preferably 0.005 to 1 wt.%, most preferably 0.01 to 0.5 wt.%, based on active protein and total weight of the agent, at least two surfactants, wherein the first surfactant and the second surfactant are different from one another and are selected from the group consisting of alcohol ethoxylates and alkyl polyglycosides, preferably the first surfactant is an alcohol ethoxylate, in an amount of 0.001 to 10 wt.%, preferably 0.01 to 7.5 wt.%, particularly preferably 0.05 to 5 wt.%, most
  • inhibitor/stabilizer is selected from the group consisting of polyols, such as glycerol 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, peptide inhibitors, preferably in an amount of 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight, based on the total weight of the agent; wherein the agent in 1 wt.% solution in deionized water at 20°C has a pH in a range of polyols, such as glycerol 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, peptide inhibitors, preferably in an
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5% by weight, preferably 0.001 to 2.5% by weight, particularly preferably 0.005 to 1% by weight, very particularly preferably 0.01 to 0.5% by weight, based on active protein and total weight of the agent, wherein the protease is a protease which has proteolytic activity and 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 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%,
  • inhibitor/stabilizer is selected from the group consisting of polyols, such as glycerol 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, peptide inhibitors, preferably in an amount of 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight, based on the total weight of the agent; wherein the agent, in a 1% by weight solution in deionized water at 20°C, has a pH in a range from
  • the invention relates to an agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, characterized in that the agent is a cleaning agent, preferably a liquid cleaning agent, and comprises at least one protease, preferably in an amount of 0.0001 to 5% by weight, preferably 0.001 to 2.5% by weight, particularly preferably 0.005 to 1% by weight, very particularly preferably 0.01 to 0.5% by weight, based on active protein and total weight of the agent, wherein the protease has proteolytic activity and comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO:1 over its entire length to at least 70% and increasingly preferably to at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%
  • inhibitor/stabilizer is selected from the group consisting of polyols, such as glycerol 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, peptide inhibitors, preferably in an amount of 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight, based on the total weight of the agent; wherein the agent, in a 1% by weight solution in deionized water at 20°C, has a pH in a range from
  • the invention relates to a method for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, WC rims, characterized in that in at least one method step a cleaning agent described herein is used, wherein the method preferably in a temperature range of about 20°C to about 30°C, preferably about 25°C, particularly preferably about 20°C.
  • Processes for cleaning surfaces 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 contact time, or that the item to be cleaned is treated in some other way with an agent or a solution or dilution of this agent.
  • the invention relates to the invention
  • a protease in a cleaning agent for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, preferably in a temperature range of about 15°C to about 30°C, preferably about 18°C to about 25°C, particularly preferably about 25°C, most particularly preferably about 20°C, wherein the protease is as defined in any one of claims 1 to 3;
  • a protease in a cleaning agent for improving the hygiene of hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet cisterns, toilet rims, preferably in a temperature range of about 15°C to about 30°C, preferably about 18°C to about 25°C, particularly preferably about 25°C, most particularly preferably about 20°C, wherein the protease is as defined in any one of claims 1 to 3;
  • a cleaning agent according to one of claims 1 to 7 for cleaning hard surfaces, in particular sanitary surfaces such as toilets, toilet bowls, toilet bowls, cisterns, toilet rims, preferably in a temperature range of about 15°C to about 30°C, preferably about 18°C to about 25°C, particularly preferably about 25°C, most particularly preferably about 20°C.
  • Example 1 Cleaning agents and proteases used
  • sample preparations shown in Table 3 were prepared from the detergent matrices shown in Table 1 and the proteases listed in Table 2.
  • the different proteases were used with equal activity, so that each sample contained 0.1 ppm of protease (based on active protein).
  • a soil a mixture of carbohydrates, fats, proteins, microorganisms (lactic acid bacteria: Streptococcus sp., Lactobacillus sp., Bifidobacterium sp.), and organic salts
  • the soil was applied to porcelain plaques and left to dry for 24 h at 40°C.
  • the soiled porcelain plaques were weighed before soiling and before and after treatment with a cleaning agent. 25 g of cleaning agent was applied to the soiled and dried porcelain plaques, left to act for 30 min, and then rinsed off (artificial waterfall to mimic a toilet flush, 3 L, 10 see). All experiments were conducted in duplicate.
  • FIGS 1 A & B show porcelain tablets with soiling before treatment
  • Figures 1C & D show porcelain tablets from Figures 1A & B after treatment with
  • FIGS 1 E & F show porcelain tablets with soiling before treatment
  • Figures 1 G & H show porcelain tablets from Figures 1 E & F after treatment with
  • FIGS 11 & J show porcelain tablets with soiling before treatment
  • Figures 1 K & L show porcelain tablets from Figures 11 & J after treatment with
  • Figures 1 M & N show porcelain tablets with soiling before treatment
  • Figures 1O & P show porcelain tablets from Figures 1M & N after treatment with
  • FIGS 1 Q & R show porcelain tablets with soiling before treatment
  • Figures 1S & T show porcelain tablets from Figures 1Q & R after treatment with
  • Figures 1 U & V show porcelain tablets with soiling before treatment
  • Figures 1W & X show porcelain tablets from Figures 1 U & V after treatment with
  • Figures 1 AA & AB show porcelain tablets from Figures 1 Y & Z after treatment with
  • FIGS. 2A & B show porcelain tablets with soiling before treatment
  • Figures 2C & D show porcelain tablets from Figures 2A & B after treatment with
  • FIGS. 2E & F show porcelain tablets with soiling before treatment
  • Figures 2G & H show porcelain tablets from Figures 2E & F after treatment with
  • FIGS. 3A & B show porcelain tablets with soiling before treatment
  • Figures 3C & D show porcelain tablets from Figures 3A & B after treatment with
  • FIGS. 3E & F show porcelain tablets with soiling before treatment
  • Figures 3G & H show porcelain tablets from Figures 3E & F after treatment with
  • FIGS. 3I & K show porcelain tablets with soiling before treatment
  • Figures 3K & L show porcelain tablets from Figures 3I & K after treatment with
  • Figures 3M & N show porcelain tablets with soiling before treatment
  • Figures 30 & P show porcelain tablets from Figures 3M & N after treatment with
  • Figures 3Q & R show porcelain tablets with soiling before treatment
  • Figures 3S & T show porcelain tablets from Figures 3Q & R after treatment with
  • Figures 3U & V show porcelain tablets with soiling before treatment
  • Figures 3W & X show porcelain tablets from Figures 3U & V after treatment with
  • the results show that the protease-containing detergents exhibit improved cleaning performance.
  • the cleaning performance of a combination of two surfactants and a protease shows significantly improved cleaning performance.
  • Example 2 To determine the cleaning performance of various cleaning agents, the fecal soil described in Example 2 was evenly applied to the inside surface of a toilet bowl. Each half of the toilet bowl was treated with a sample to be tested (25 g of sample applied, allowed to act for 30 minutes). The toilet was then flushed.
  • Figures 4A & B show a toilet bowl with soiling before treatment
  • Figure 4C shows half of the toilet bowl from Fig. 4A after treatment with
  • Figure 4D shows half of the toilet bowl from Fig. 4B after treatment with
  • Figures 4E & F show a toilet bowl with soiling before treatment
  • Figure 4G shows half of the toilet bowl from Fig. 4E after treatment with a conventional cleaner (V1)
  • Figure 4H shows half of the toilet bowl from Fig. 4F after treatment with
  • Figures 4I & J show a toilet bowl with soiling before treatment
  • Figure 4K shows half of the toilet bowl from Fig. 4I after treatment with
  • Sample preparation A2 Figure 4L shows half of the toilet bowl from Fig. 4J after treatment with

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Abstract

L'invention appartient au domaine des agents de nettoyage, en particulier des agents de nettoyage pour des surfaces dures, de préférence des agents de nettoyage liquides pour nettoyer des surfaces sanitaires telles que des toilettes, des cuvettes de toilettes, des corps de toilettes, des cuves à chasse d'eau, le rebord de toilettes. L'invention concerne un agent de nettoyage, de préférence un agent de nettoyage liquide, de préférence un agent de nettoyage liquide pour nettoyer des surfaces dures, en particulier, de préférence, un agent de nettoyage liquide pour nettoyer des surfaces sanitaires telles que des toilettes, des cuvettes de toilettes, des corps de toilettes, des cuves à chasse d'eau, le rebord de toilettes. L'agent de nettoyage comprend : au moins une protéase, de préférence en une quantité de 0,0001 à 5 % en poids, de préférence de 0,001 à 2,5 % en poids, de manière particulièrement préférée de 0,005 à 1 % en poids, de manière particulièrement mieux préférée de 0,01 à 0,5 % en poids, sur la base de la protéine active et du poids total de l'agent ; au moins un tensioactif, le tensioactif étant choisi dans le groupe constitué par les tensioactifs non ioniques, les tensioactifs anioniques, les tensioactifs cationiques, les tensioactifs zwitterioniques, les tensioactifs amphotères et leurs mélanges, de préférence en une quantité de 0,001 à 10 % en poids, de préférence de 0,001 à 5 % en poids, de manière particulièrement préférée de 0,001 à 1 % en poids, de manière particulièrement mieux préférée de 0,01 à 0,5 % en poids, sur la base du poids total de l'agent ; dans une solution à 1 % en poids dans de l'eau désionisée à 20 °C, l'agent présentant un pH dans une plage allant d'environ 7 à environ 10, en particulier d'environ 7 à environ 9, plus préférentiellement d'environ 7,5 à environ 8, de manière particulièrement préférée d'environ 7.
PCT/EP2024/078314 2023-11-14 2024-10-09 Agent de nettoyage contenant une protéase Pending WO2025103667A1 (fr)

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Citations (20)

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