EP2313483B1 - Procédé pour améliorer le pouvoir de nettoyage d'un produit détergent ou nettoyant - Google Patents

Procédé pour améliorer le pouvoir de nettoyage d'un produit détergent ou nettoyant Download PDF

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Publication number
EP2313483B1
EP2313483B1 EP09780409.0A EP09780409A EP2313483B1 EP 2313483 B1 EP2313483 B1 EP 2313483B1 EP 09780409 A EP09780409 A EP 09780409A EP 2313483 B1 EP2313483 B1 EP 2313483B1
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EP
European Patent Office
Prior art keywords
cleaning
washing
protease
agent
enzyme
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.)
Revoked
Application number
EP09780409.0A
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German (de)
English (en)
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EP2313483A2 (fr
Inventor
Timothy O'connell
Petra Siegert
Karl-Heinz Maurer
Marc-Steffen Schiedel
Inga Kerstin Vockenroth
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP14152971.9A priority Critical patent/EP2727990A3/fr
Publication of EP2313483A2 publication Critical patent/EP2313483A2/fr
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/3869Enzyme enhancers or mediators
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/32Protein hydrolysates; Fatty acid condensates thereof
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/201Monohydric alcohols linear
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
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    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2044Dihydric alcohols linear
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
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    • C11D3/2003Alcohols; Phenols
    • C11D3/2065Polyhydric alcohols
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
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    • C11D3/2072Aldehydes-ketones
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
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    • C11D3/2075Carboxylic acids-salts thereof
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
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    • C11D3/2082Polycarboxylic acids-salts thereof
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
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    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
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    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/221Mono, di- or trisaccharides or derivatives thereof
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719Polyamides or polyimides
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753Polyvinylalcohol; Ethers or esters thereof
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/381Microorganisms
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627Preparations containing enzymes, e.g. protease or amylase containing lipase
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    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38636Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
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    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

  • the present application is directed to the use of a polyanionic substance to improve the cleaning performance of a detergent containing a protease.
  • enzymes in detergents and cleaners serve to extend the range of services of the funds concerned according to their specific activities. These include in particular hydrolytic enzymes such as proteases, amylases, lipases and cellulases. The first three hydrolyze proteins, starches and fats and thus contribute directly to soil removal. Cellulases are used in particular because of their tissue effect.
  • Another group of washing and cleaning agent enzymes are oxidative enzymes, in particular oxidases, which, if appropriate, in combination with other components, are preferably used to bleach soiling or to produce the bleaching agents in situ.
  • enzymes which are subjected to constant optimization, further enzymes are constantly being made available for use in detergents and cleaners in order to be able to optimally address particular soiling, such as pectinases, ⁇ -glucanases, mannanases or other hemicellulases for hydrolysis, in particular more specific vegetable polymers.
  • proteases and in particular serine proteases, which include the subtilases. They cause the degradation of protein-containing stains on the items to be cleaned.
  • proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are attributed to the serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases, that is, they hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range.
  • Subtilases Subtilisin-like Proteases "by R. Siezen, pages 75-95 in”
  • Subtilisin enzymes edited by R. Bott and C. Betzel, New York, 1996
  • Subtilases are naturally produced by microorganisms; Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
  • subtilisin-type proteases preferably used in detergents and cleaners are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, Subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are assigned to the subtilases, but no longer to the subtilisins in the narrower sense.
  • proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime and Properase ® from Genencor, sold under the trade name Protosol® by Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P From Amano Pharmaceuticals Ltd., Nagoya, Japan, and that available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • a disadvantage of these enzymes used in detergents and cleaning agents, in particular proteases, from the prior art is that they are especially at low temperatures, for example between 10 ° C and 40 ° C, in particular between 10 ° C and 30 ° C or even between 10 ° C and 25 ° C, have no satisfactory hydrolytic activity, in particular proteolytic activity, and therefore in particular in detergents and dishwashing detergents in this temperature range show no optimal cleaning performance.
  • US 6,235,697 B1 describes protease-containing detergents which additionally contain surfactants, cellulase and an acrylic acid-based homo- or copolymer.
  • EP 2 083 067 A1 describes the use of organic complexing agents and / or polymeric carboxylic acid group-containing compounds in a liquid detergent or cleaning composition to improve the washing or cleaning performance at a temperature of 40 ° C.
  • the present invention is therefore based on the object to improve the cleaning performance (washing power) of detergents or cleaning agents, in particular with regard to soiling, which are sensitive to degradation by proteases in a temperature range between 10 ° C and 30 ° C and 10 ° C. and 25 ° C.
  • Another object of the invention is the cleaning performance of hydrolytic enzymes, in particular proteases, in detergents or cleaning or the to improve by the washing or cleaning agent formed wash liquor, in particular with regard to soiling, which are sensitive to degradation by proteases in a temperature range between 10 ° C and 30 ° C and 10 ° C and 25 ° C.
  • the invention thus relates to the use of a polyanionic substance for achieving a synergistic enzyme-based cleaning performance in interaction with a protease in a washing or cleaning agent when using the washing or cleaning agent, characterized in that it is carried out in a temperature range of 10 to 30 ° C. becomes.
  • Preferred embodiments are given in claims 2-7.
  • cleaning performance is significantly improved if these agents comprise at least one protease (also referred to herein as component (a)) with one or more polyanionic substances ( Also referred to herein as component (b)) is combined.
  • cleaning performance is understood to mean the whitening performance of one or more soiling, in particular laundry soiling, which are sensitive to degradation by proteases. Examples of such stains are blood milk / ink on cotton, full egg / pigment on cotton, chocolate milk / ink on cotton, peanut oil pigment / ink on polyester / cotton, grass on cotton or cocoa on cotton, especially such as indicated below.
  • both the washing or cleaning agent which comprises the hydrolytic enzyme or the washing or cleaning liquor formed by this agent
  • the hydrolytic enzyme itself have a respective cleaning performance.
  • the cleaning performance of the hydrolytic enzyme thus contributes to the cleaning performance of the agent or the washing or cleaning liquor formed by the agent.
  • component (b) The cleaning performance of detergents and cleaning agents based on the enzymatic activity used, in particular on the proteolytic activity, is improved by the addition of component (b).
  • component (a) and (b) With regard to the interaction of these components (a) and (b), a synergistic effect results, ie a better performance compared to the individual performances of the respective component in one-component systems (ie detergents or cleaners, each containing only the hydrolytic, in particular proteolytic enzyme, or contain component (b)) and also with respect to the sum of the individual performances of components (a) and (b), ie the sum of two one-component systems each having the component (a) and (b ) alone.
  • hydrolytic enzyme (a), ie protease, with a component (b) according to the invention provides a further possibility in order to improve the performance of detergents with regard to their cleaning performance, in particular their enzyme-based cleaning performance, especially with regard to their cleaning performance, which is brought about by a protease contained.
  • the washing or cleaning liquor is understood to mean the use solution containing the washing or cleaning agent which acts on textiles or fabrics (wash liquor) or hard surfaces (cleaning liquor) and thus comes into contact with the soiling present on textiles or fabrics or hard surfaces .
  • the washing or cleaning liquor arises when the washing or cleaning process begins and the detergent or cleaning agent, for example, in a washing machine or other suitable container dissolved in water or diluted with water.
  • Hydrolytic enzymes in the sense of component (a) are proteases. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • subtilisin type those of the subtilisin type are preferable.
  • subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsv ⁇ rd, Denmark.
  • subtilisins 147 and 309 are sold under the trade names Esperase®, and Savinase® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP® protease variants derived.
  • proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, sold under the trade name Protosol® by Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather ® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • the proteases are also used with particular preference Bacillus gibsonii and Bacillus pumilus disclosed in international patent applications WO2008 / 086916 and WO2007 / 131656 ,
  • the enzymes may be formulated together with accompanying substances, for example from the fermentation or with stabilizers.
  • Agents used in a method according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -8 to 5 percent by weight based on active protein.
  • the enzymes are from 0.001 to 5% by weight, more preferably from 0.01 to 5% by weight, even more preferably from 0.05 to 4% by weight and most preferably from 0.075 to 3.5% by weight. % contained in these agents, wherein each enzyme contained can be present in the stated amounts.
  • the protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ).
  • BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
  • the biuret method Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 .
  • the hydrolytic enzyme at least one of which is present in a detergent or cleaning agent used in the method according to the invention (namely as component (a)), supports the cleaning performance of the composition with respect to certain soils or stains.
  • a detergent or cleaning agent used in the method according to the invention namely as component (a)
  • an agent used in a method according to the invention contains a plurality of enzymes, wherein the enzymes may belong to the same or different enzyme classes.
  • the enzymes exhibit synergistic effects on their action against certain soils or stains, i. the enzymes contained in the middle composition mutually support each other in their cleaning performance.
  • a hydrolytic enzyme (a) is combined therewith with a component (b), ie at least one substance which, in conjunction with the hydrolytic enzyme (a), produces a synergistic cleaning performance when the agent is used and which is a polyanionic substance.
  • a polymer having at least one negatively charged monomer preferably having a plurality of negatively charged monomers.
  • this polymer is therefore a negatively charged polymer.
  • polymers of organic acids or their salts in particular polyacrylates and / or poly-sugar acids and / or polyarcylate copolymers and / or poly-sugar copolymers, are preferred.
  • further preferred compounds are polyacrylic sulfonates or polycarboxylates and their salts, copolymers or salts of the copolymers.
  • Acusol 587D polyacrylic sulfonate, Rohm & Haas / Dow Chemical Company
  • Acusol 445N polycarboxylate sodium salt, Rohm & Haas / Dow Chemical Company
  • Acusol 590 polyacrylate copolymer; Rohm & Haas / Dow Chemical
  • Acusol 916 polyarcrylate sodium salt, Rohm & Haas / Dow Chemical Company
  • Sokalan CP42 modified polycarboxylate sodium salt, BASF Company
  • Sokalan PA 30CL polycarboxylate sodium salt, BASF Company
  • Dequest P 9000 polymaleic acid, Thermphos Company
  • alginic acid Poly-2-acrylamido-2-methyl-1-propane-sulfonic acid, poly-4-styrene sulfonic acid-co-maleic acid sodium salt, poly-acrylamido-co-acrylic acid sodium salt, poly-me
  • component (b) is added to the detergent or cleaning agent as a separate single substance, i. not as a component of another ingredient of the washing or cleaning agent.
  • component (b) is therefore free in the detergent, i. it is distributed in this and distributed as homogeneously as possible.
  • component (b) is preferably dissolved or dispersed in them.
  • the washing or cleaning agent particularly preferably does not contain component (b) as part of the dosage form of the hydrolytic enzyme (a), in particular not as a constituent of an enzyme granulate.
  • liquid or gel-shaped i. non-solid detergents or cleaners.
  • the washing process is determined by measuring the whiteness of the washed textiles, the washing process for at least 30 minutes, optionally 60 minutes, carried out at a temperature of 20 ° C and the water has a water hardness between 15.5 and 16.5 ° (German hardness).
  • a preferred liquid detergent for such a washing system is composed as follows (all figures in weight percent): 0.3- 0.5% xanthan gum, 0.2-0.4% anti-foaming agent, 6-7% glycerol, 0.3-0.5% ethanol, 4-7% FAEOS (fatty alcohol ether sulfate), 24-28% nonionic surfactants, 1% boric acid, 1-2% sodium citrate (dihydrate), 2-4% soda, 14-16% coconut Fatty acids, 0.5% HEDP (1-hydroxyethane- (1,1-di-phosphonic acid)), 0-0.4% PVP (polyvinylpyrrolidone), 0-0.05% optical brightener, 0-0.001% dye, Rest demineralized water.
  • the dosage of the liquid detergent is between 4.5 and 5.5 grams per liter of wash liquor, for example, 4.9 grams per liter of wash liquor. Preference is given to washing in a pH range between pH 8 and pH 10.5, preferably between pH 8 and pH 9.
  • a preferred powdered detergent for such a washing system is composed as follows (all figures in weight percent): 10% linear alkylbenzenesulfonate (sodium salt), 1.5% C12-C18 fatty alcohol sulfate (sodium salt), 2.0% C12-C18 fatty alcohol with 7 EO, 20% sodium carbonate, 6.5% sodium bicarbonate, 4.0% amorphous sodium disilicate, 17% sodium carbonate peroxohydrate, 4.0% TAED, 3.0% polyacrylate, 1.0% carboxymethyl cellulose, 1.0% phosphonate, 25% sodium sulfate, balance: optional foam inhibitors, optical brightener, fragrances and, if necessary, water ad 100%.
  • the dosage of the liquid detergent is between 6.0 and 7.0 grams per liter of wash liquor, for example, 6.7 grams per liter of wash liquor.
  • a liquid detergent is used.
  • the degree of whiteness i. the brightening of the stains, is preferably determined by optical measuring methods, preferably photometrically.
  • a suitable device for this purpose is for example the spectrometer Minolta CM508d.
  • the devices used for the measurement are previously calibrated with a white standard, preferably a supplied white standard.
  • the activity-like use ensures that, even if the ratio of active substance to total protein (the values of the specific activity) diverge, the respective enzymatic properties, for example the washing performance of certain soils, are compared. In general, a low specific activity can be compensated by adding a larger amount of protein.
  • Methods for the determination of the enzyme activities are familiar to the expert in the field of enzyme technology and are routinely used by him. For example Method for determining protease activity disclosed in Tenside, Vol. 7 (1970), pp. 125-132 , The protease activity is preferably indicated in PE (protease units). For example, suitable protease activities are 5 or 10 PE (protease units) per ml wash liquor. However, the enzymatic activity used is not equal to zero.
  • the synergistic cleaning performance is based on a novel mechanism of action, i. There is no increase in the enzyme activity per se in the classical sense, as they would - in terms of proteases - would be measured in one of the following methods. Accordingly, a synergism according to the invention is also present in particular if an improved cleaning performance in the presence of components (a) and (b) is found compared to the sum of the cleaning powers of component (a) alone and component (b) alone, and the component (b) in at least one of the subsequent test methods, preferably in both subsequent test methods, has no effect of increasing the hydrolytic activity of component (a), in particular with regard to increasing the hydrolytic activity of a protease, beyond the standard measurement error:
  • the protease activity is determined quantitatively by the release of the chromophore para-nitroaniline (pNA) from the substrate.
  • the substrate is: suc-L-Ala-L-Ala-L-Pro-L-Phe-p-Nitroanilide (substrate solution: 110 mM in DMSO).
  • the protease cleaves the substrate and releases pNA.
  • the release of pNA causes an increase in absorbance at 410 nm, the time course of which is a measure of enzymatic activity (see Del Mar et al., 1979).
  • the measurement is carried out at a temperature of 25 ° C, at pH 8.6 and a wavelength of 410 nm.
  • the measurement time is 5 min and the measurement interval 20s to 60s.
  • the use buffer (Tris-HCl pH 8.6) is used as a blank sample, 10 ⁇ L of the substrate solution are added to each cuvette, 1000 ⁇ L of buffer are added to each cuvette, 1-300 ⁇ l of buffer (s) are added Add component (b) (0.1, 0.2, 0.5 or 1% by weight in working buffer) to the cuvette and place 1-300 ⁇ l of the protease or blank sample in the cuvette The measurement is started by mixing the sample After mixing, the cuvettes are immediately transferred to the photometer and the measurement is started.An activation or stabilization of the protease can be quantified by means of the measurement data.
  • Tris-HCl pH 8.6 Tris-HCl pH 8.6
  • Protease activity is determined via the hydrolysis of casein and subsequent reaction of TCA-soluble peptides with Folin &Ciocalteu's phenol reagent. The absorbance of the resulting complex is measured at 660 nm and compared to a tyrosine standard.
  • Reaction mixtures contain 3 ml of 0.8% (w / v) casein and 0.5 ml of a suitable enzyme dilution with or without the component (b) to be tested (concentration 0.1, 0.2, 0.5 or 1 wt. %), both in universal buffer 1 from Britton and Robinson, pH 9.5 (see J. Chem. Soc., 1931, p 1451).
  • the mixtures are incubated for 30 minutes at 25 ° C, then the reaction is stopped by adding Stop Reagent (TCA). In control reactions, the stop reagent is added before enzyme addition with or without the substance to be tested. After 20 minutes at 25 ° C, the reaction mixtures are filtered through Whatman # 42 filter paper or centrifuged.
  • the method is characterized in that the substances used as component (b) have specific molecular weights.
  • the method is therefore characterized in that this component has a molecular weight (MW) from 150 to 5x10 6 daltons, in particular from 200 to 1x10 6 daltons, from 220 to 0,75x10 6 Dalton and in particular from 400 to 0.5x10 6 daltons.
  • MW molecular weight
  • composition in a concentration of 0.15 to 50 wt .-%, in particular from 0.9 to 30 wt .-%.
  • a particularly advantageous synergistic cleaning performance also results from the fact that the substance used as component (b) is present in a certain concentration in the washing or cleaning liquor.
  • the method is therefore characterized in that this component in the washing or cleaning liquor is present in a concentration of 0.00025 to 0.6 wt .-%, in particular from 0.0003 to 0.5 wt .-%.
  • Detergents and cleaning agents which can be used in the process according to the invention include all conceivable types of detergents or cleaners, both concentrates and undiluted agents, for use on a commercial scale, in the washing machine or in hand washing or cleaning. These include detergents for textiles, carpets, or natural fibers, for which the term detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term detergent is used, ie in addition to manual and machine Dishwashing agents, for example, scouring agents, glass cleaners, toilet scenters, etc.
  • washing and cleaning agents in the invention also include washing aids which are added to the actual detergent in the manual or machine textile laundry to achieve a further effect.
  • laundry detergents and cleaners in the context of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example to dissolve stubborn soiling, and also agents which are in one of the actual Textile laundry downstream step to give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge. Among the latter, i.a. calculated the fabric softener.
  • the detergents or cleaning agents which can be used in the process according to the invention which can be in the form of homogeneous solutions or suspensions, in particular in powdered solids, can in addition to the active compounds used according to the invention - the components (a) and (b) - in principle all known and contain usual ingredients in such agents, wherein preferably at least one further ingredient is present in the agent.
  • the agents may, in particular, builders, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as optical brighteners, grayness inhibitors, foam regulators and dyes and perfumes and Combinations of these included.
  • a further combination of the active compounds according to the invention with one or more further ingredient (s) of the agents proves advantageous, since then a further improved cleaning performance can be achieved by further resulting synergisms.
  • the combination with a surfactant and / or a builder and / or a bleaching agent such a further synergism is achieved.
  • Such preferred others Ingredients of the detergent or cleaning agent are disclosed in the international publication WO 2009/021867 , whose disclosure is therefore expressly referred to or the disclosure thereof is therefore expressly incorporated into the present application.
  • the ingredients to be selected as well as the conditions under which the agent is used, such as temperature, pH, ionic strength, redox ratios or mechanical influences, should be optimized for the respective cleaning problem.
  • conventional temperatures for the use of detergents and cleaners in the ranges of 10 ° C over 40 ° C and 60 ° C up to 95 ° for mechanical means or in technical applications.
  • the ingredients of the respective agents are coordinated, in particular in such a way that synergies arise with regard to the cleaning performance. Synergies are particularly preferred which are in a temperature range from 10 ° C to 30 ° C, from 15 ° C to 30 ° C from 10 ° C to 25 ° C, from 15 ° C to 25 ° C and most preferably at 20 ° C are present.
  • an agent useful in the method of the invention further contains the hydrolytic enzyme in an amount of from 2 ⁇ g to 20 mg, preferably from 5 ⁇ g to 17.5 mg, more preferably from 20 ⁇ g to 15 mg and most preferably from 50 ⁇ g to 10 mg per g of the agent.
  • the hydrolytic enzyme contained in the agent in particular a protease, and / or other ingredients of the agent may be coated with a substance impermeable to the enzyme at room temperature or in the absence of water, which becomes permeable to the enzyme under conditions of use of the agent.
  • the washing or cleaning agent itself may be packaged in a container, preferably an air-permeable container, from which it is released shortly before use or during the washing process.
  • inventions of the present invention further include all solid, powdered, liquid, gel or pasty dosage forms of the method according to the invention usable means, which may optionally consist of several phases and may be present in compressed or uncompressed form.
  • the agent can be present as a free-flowing powder, in particular with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l or 600 g / l to 850 g / l.
  • the solid dosage forms of the composition also include extrudates, granules, tablets or pouches.
  • the agent can also be liquid, gelatinous or pasty, for example in the form of a non-aqueous liquid detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or a water-containing paste.
  • the agent may be present as a one-component system. Such means preferably consist of one phase. Alternatively, an agent can also consist of several phases. Such an agent is therefore divided into several components.
  • Detergents or cleaning agents which can be used in the process according to the invention may contain only one protease. Alternatively, however, they may also contain further hydrolytic enzymes or other enzymes in a concentration which is expedient for the effectiveness of the agent, it being possible in principle to use all enzymes established for this purpose in the prior art.
  • enzymes preferably used are all enzymes that can develop catalytic activity in the agent, in particular amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, ⁇ -glucosidases, carrageenases, oxidases, perhydrolases, oxidoreductases or lipases, and preferably their mixtures.
  • These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly.
  • the use described herein is advantageous for eliminating contaminants from textiles or hard surfaces, particularly proteinaceous contaminants.
  • Embodiments of this subject invention include, for example, hand washing, manual removal of stains from textiles or from hard surfaces or machine processes.
  • the uses in processes for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent , The same applies to methods for cleaning hard surfaces.
  • a hydrolytic enzyme ie component (a)
  • a hydrolytic activity e.g., a hydrolytic activity
  • a hydrolytic activity e.g., a hydrolytic activity
  • a hydrolytic activity e.g., a hydrolytic activity
  • a hydrolytic activity e.g., a hydrolytic activity
  • a hydrolytic activity e.g., a hydrolytic activity
  • a hydrolytic activity e.g., a hydrolytic activity in media which otherwise have no cleaning power
  • such a method may also merely consist in that apart from the added component (b) the only further component is a hydrolytic enzyme, ie component (a) is applied, preferably in a buffer solution or in water.
  • All uses according to the invention in such processes are carried out in a temperature range from 10 ° C. to 30 ° C.
  • a synergistic interaction of the components (a) and (b) with regard to the cleaning performance is especially at these lower to middle washing temperatures or cleaning temperatures.
  • component (b) is present in the agent from 0.15 to 50% by weight, in particular from 0.9 to 30% by weight.
  • this component advantageously, in particular synergistically, cooperates with a hydrolytic enzyme (component (a)), so that not only the cleaning performance of a washing or cleaning agent (or the wash liquor formed by this agent) is improved, but also the cleaning performance of the hydrolytic Enyzms itself.
  • Preferred embodiments of uses according to the invention are further characterized in that the substances used as component (b) have specific molecular weights.
  • the invention provides a use according to the invention therefore is characterized in that this component has a molecular weight (MW) from 150 to 5x10 6 daltons, in particular from 200 to 1x10 6 daltons, from 220 to 0,75x10 6 Dalton and in particular from 400 to 0.5x10 6 daltons.
  • MW molecular weight
  • Proteases used were the alkaline protease from Bacillus lentus DSM 5483 ( WO 92/21760 , hereinafter referred to as Protease 1) as well as the protease which are shown in FIG. 2 or SEQ ID NO. 3 of the international publication WO 03/057713 (hereinafter referred to as Protease 2).
  • Stock solutions of these substances were prepared with 0.00001-1.5 M substance or 0.0001-55% (weight or volume) in water or buffer (phosphate 0.00001-1.5 M pH 6.5-8.0 or Tris 0.00001-1.5 M pH 7.5-9.0 or Soerensen buffer pH 7.5-9.0 or citrate buffer 0.00001-1.5 M pH 4.5-7.0 or acetate Buffer 0.00001-1.5 M pH 2.5-5.5).
  • buffer phosphate 0.00001-1.5 M pH 6.5-8.0 or Tris 0.00001-1.5 M pH 7.5-9.0 or Soerensen buffer pH 7.5-9.0 or citrate buffer 0.00001-1.5 M pH 4.5-7.0 or acetate Buffer 0.00001-1.5 M pH 2.5-5.5).
  • Tables 4 and 5 show the resulting cleaning performance for each given experimental approaches.
  • the results obtained are the sum of the improvements over all six specified soils and are given as percent power, with the difference of the remission values from the detergent investigated minus the control (detergents without enzyme and no substance) being formed for each value.
  • the increase in performance of the detergent with hydrolytic enzyme (in this case with protease), but without performance-enhancing substance, compared to the detergent without hydrolytic enzyme (protease) and substance was normalized to 100% as a reference. 100% therefore represent the cleaning performance of the detergent with hydrolytic enzyme (protease) alone, ie without performance-enhancing substance. Values greater than 100%, however, therefore show an increased cleaning performance compared to this reference, values less than 100% reduced Cleaning performance against this reference.
  • components used (b) cause a synergistic increase in the washing performance of those detergents containing a hydrolytic enzyme, namely a protease, ie component (a).
  • these components (b) do not synergistically increase the washing performance, so that the enhanced washing performance is due to a beneficial synergistic interaction of components (a) and (b).

Claims (7)

  1. Utilisation d'une substance polyanionique pour réaliser une performance de nettoyage synergique à base d'enzyme en association avec une protéase dans un agent de lavage ou de nettoyage lors de l'utilisation de l'agent de lavage ou de nettoyage, caractérisée en ce qu'elle est mise en oeuvre dans une gamme de températures allant de 10 °C à 30 °C.
  2. Utilisation selon la revendication 1, caractérisée en ce que la substance polyanionique est présente dans l'agent à une concentration de 0,15 à 50 % en poids, en particulier de 0,9 à 30 % en poids.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que l'agent de lavage ou de nettoyage contient la protéase dans une quantité de 2 µg à 20 mg, de préférence de 5 µg à 17,5 mg, de manière particulièrement préférée de 20 µg à 15 mg et de manière tout particulièrement préférée de 50 µg à 10 mg par g d'agent, et/ou en ce que la protéase dans l'agent de lavage ou de nettoyage est enveloppée d'une substance imperméable à l'enzyme à la température ambiante ou en l'absence d'eau.
  4. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que l'agent de lavage ou de nettoyage
    (a) est présent sous forme solide, en particulier sous forme de poudre fluide ayant une densité apparente de 300 g/l à 1200 g/l, en particulier de 500 g/l à 900 g/l, ou
    (b) est présent sous forme pâteuse ou liquide, et/ou
    (c) est présent en tant que système à un composant, ou
    (d) est divisé en plusieurs composants.
  5. Utilisation d'une substance polyanionique pour augmenter le pouvoir nettoyant à base d'enzyme d'une protéase dans un processus de lavage ou de nettoyage, caractérisée en ce qu'elle est mise en oeuvre dans une gamme de températures allant de 10 °C à 30 °C.
  6. Utilisation selon l'une des revendications 1 à 5, caractérisée en ce que la substance polyanionique a un poids moléculaire (MW) de 150 à 5 x 106 daltons, en particulier de 200 à 1 x 106 daltons, de 220 à 0,75 x 106 daltons et notamment de 400 à 0,5 x 106 daltons.
  7. Utilisation selon l'une des revendications 1 à 6, caractérisée en ce que la substance polyanionique est présente dans le bain de lavage ou de nettoyage à une concentration de 0,00025 à 0,6 % en poids, en particulier de 0,0003 à 0,5 % en poids.
EP09780409.0A 2008-08-20 2009-07-10 Procédé pour améliorer le pouvoir de nettoyage d'un produit détergent ou nettoyant Revoked EP2313483B1 (fr)

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PL2727988T3 (pl) 2020-02-28
ES2744829T5 (es) 2022-10-19
WO2010020476A3 (fr) 2010-06-17
US20110136720A1 (en) 2011-06-09
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PL2313482T3 (pl) 2019-11-29
EP2313482B2 (fr) 2022-07-27
EP2727989A3 (fr) 2016-03-16
EP2313482B1 (fr) 2019-06-12
EP2727990A2 (fr) 2014-05-07
US20110201536A1 (en) 2011-08-18
PL2727989T3 (pl) 2019-12-31
WO2010020476A2 (fr) 2010-02-25
EP2727990A3 (fr) 2016-03-16
EP2727988B1 (fr) 2019-09-04
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ES2744829T3 (es) 2020-02-26
ES2753240T3 (es) 2020-04-07
EP2727989A2 (fr) 2014-05-07
EP2313483A2 (fr) 2011-04-27
EP2727989B1 (fr) 2019-06-26
PL2313482T5 (pl) 2023-02-27
WO2010020475A2 (fr) 2010-02-25
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