EP2596087B1 - Combinations of rhamnolipids and enzymes for improved cleaning - Google Patents

Combinations of rhamnolipids and enzymes for improved cleaning Download PDF

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Publication number
EP2596087B1
EP2596087B1 EP11728878.7A EP11728878A EP2596087B1 EP 2596087 B1 EP2596087 B1 EP 2596087B1 EP 11728878 A EP11728878 A EP 11728878A EP 2596087 B1 EP2596087 B1 EP 2596087B1
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Prior art keywords
rhamnolipid
rhamnolipids
composition according
mono
rha
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German (de)
English (en)
French (fr)
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EP2596087A1 (en
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Alyn James Parry
Neil James Parry
Anne Cynthia Peilow
Paul Simon Stevenson
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • This invention relates to cleaning compositions comprising mono-rhamnolipids in combination with enzymes.
  • Rhamnolipids are a class of glycolipid. They are constructed of rhamnose combined with beta-hydroxy fatty acids. Rhamnose is a sugar. Fatty acids are ubiquitous in animals and plants. The carboxyl end of the fatty acid end is connected to the rhamnose. Rhamnolipids are compounds of only three common elements; carbon, hydrogen, and oxygen. They are a crystalline acid. Rhamnolipids may be produced by strains of the bacteria Pseudomonas aeruginosa. There are two major groups of rhamnolipids; mono-rhamnolipids and di-rhamnolipids.
  • Mono-rhamnolipids have a single rhamnose sugar ring.
  • a typical mono-rhamnolipid produced by P. aeruginosa is L-rhamnosyl- ⁇ -hydroxydecanoyl- ⁇ -hydroxydecanoate (RhaC 10 C 10 ). It may be referred to as Rha-C 10 -C 10 , with a formula of C 26 H 48 O 9 .
  • Mono-rhamnolipids have a single rhamnose sugar ring.
  • the IUPAC Name is 3-[3-[(2R,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxydecanoyloxy]decanoic acid.
  • Di-rhamnolipids have two rhamnose sugar rings.
  • a typical di-rhamnolipid is L-rhamnosyl-L-rhamnosyl- ⁇ -hydroxydecanoyl- ⁇ -hydroxydecanoate (Rha2C 10 C 10 ). It may be referred to as Rha-Rha-C 10 -C 10 , with a formula of C 32 H 58 O 13 .
  • the IUPAC name is 3-[3-[4,5-dihydroxy-6-methyl-3-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid.
  • Rhamnolipids produced by P. aeruginosa (unidentified as either mono- or di-rhamnolipids):
  • rhamnolipids are produced in various chemical formulas, each with a different HLB, it is known that rhamnolipids can be produced or mixed to have a range of foaming properties.
  • Rhamnolipids are an anionic surfactant with both hydrophilic end and a lipophilic end. When their concentration increases to a certain level it is known that the rhamnolipids join together inside a liquid in a micelle.
  • rhamnolipids with two shorter fatty acids are more active in reducing surface tension and as an emulsifier. Those rare rhamnolipids with a single fatty acid chain are not as effective.
  • Pseudomonas aeruginosa The bacterium Pseudomonas aeruginosa is found naturally in soils, in water, and on plants. Metabolically, P . aeruginosa is chemoheterotrophic, generally aerobic, utilizing a wide range of organic compounds for sources of carbon and nitrogen.
  • strains of P . aeruginosa can be isolated to produce rhamnolipids at higher concentrations and more efficiently. Strains can also be selected to produce less byproduct and to metabolize different feedstock or pollutants. This production is greatly affected by the environment in which the bacterium is grown.
  • US 5417879 A1 suggests a mixed micellar Glycolipid and lamellar surfactant composition, that can be either glycolipid, or not. Compositions are proposed for use at 0.5 to 50 g/l. Examples using Rhamnolipid did not use any enzyme. In column 12 lines 24 to 25, it is mentioned as possible to combine the biosurfactants with an undisclosed amount of enzyme. To arrive at a combination of enzyme with Rhamnolipid it is necessary to make several selections from this document.
  • US2006106120 describes a mixture of micro-organism, biosurfactant and a plastic degrading enzyme for the bioremediation of man-made materials.
  • the biosurfactant may be a rhamnolipid (para 62).
  • the enzyme may be a lipase (para 64). No preference is given for any components of the rhamnolipid. Neither rhamnolipids nor lipases are exemplified and rhamnolipids are not specifically claimed.
  • US2004072713A discloses an article for use in an enzymatic fabric cleaning process, said article containing one or more types of harmless micro-organisms capable of excreting enzymes useful in said fabric cleaning process. It is especially useful if, in addition to enzymes, the micro-organisms are also capable of producing other chemical entities that contribute to the cleaning process, e.g. biosurfactants, for example lipopolysaccharides as described in EP924221 . These biosurfactants are not Rhamnolipids. The levels of biosurfactants generated were very low indeed and certainly would not have exceeded 0.5g/l.
  • the micro-organisms are said to be capable of producing and secreting useful laundry enzymes such as Oxidoreductases, Carbohydrases, Proteases, Lipases, Transferases and Glycosidases.
  • a detergent composition with a novel ratio of mono to di rhamnolipids in combination with lipase.
  • the amount of mono-rhamnolipid present is more than the amount of di-rhamnolipid present (if any).
  • at least 80 wt%, more preferably at least 90 wt% or even 100 wt% of the rhamnolipid in the composition is mono-Rhamnolipid.
  • the lipase is preferably derived from either fungal or bacterial sources.
  • bacterial sources we include expression from other microbes, such as yeast, of genes that have been cloned from bacteria.
  • the rhamnolipid is preferably present in an amount of from 0.5 to 40 wt%.
  • the lipase is preferably present in an amount of from 0.0001 to 5 wt%.
  • the detergent composition is preferably unbuilt. That is zeolite, phosphate or silicate builders are absent.
  • the detergent composition is preferably a liquid detergent composition and if citric acid builder is present, it is limited to a maximum level of 2 wt%.
  • the composition is especially useful as a laundry detergent and may be used with advantage for washing in water with a low water hardness of less than 15°F. A process whereby the laundry and the composition are washed in presoftened water is particularly advantageously used with the compositions of the invention.
  • compositions are used to remove fatty soils from laundry, especially from cotton cloths. Removal of soils from cotton is of increasing concern because many of the sophisticated soil removal and soil release technologies included in modern laundry detergents work best on polyester cloths. Accordingly, it is advantageous to combine the detergent system of the present invention with a polyester soil release polymer.
  • Using mono-rhamnolipids and lipase in a detergent composition according to the invention leads to enhanced cleaning benefits and possibly synergies with synthetic anionic surfactants, for example C12-14 alkyl benzene sulphonate synthetic anionic surfactant.
  • This surfactant is commonly employed in laundry detergent compositions and is typically used with a nonionic surfactant, such as the ethoxylated nonionic surfactant used in US5417879 .
  • a nonionic surfactant such as the ethoxylated nonionic surfactant used in US5417879 .
  • the rhamnolipids with mono to di rhamnolipid ratio claimed provide a suitable substitute for the nonionic surfactant component, especially when used to remove fatty soils and particularly when used to remove soils from cotton cloth.
  • the compositions are suited to low wash temperatures and fast wash times, which support energy and time savings.
  • a preferred fatty soil is beef fat.
  • Rhamnolipids formed by the degradation of oils and fats by Pseudomonas Aeg, show poor cleaning benefits when used at concentrations of components generated by the bacterial breakdown process.
  • mono and di rhamnolipid components of the expressed rhamnolipids are extracted and the mono-rhamnolipid is used with lipase superior cleaning results.
  • further enhancement in detergency may be achieved.
  • the detergent composition may comprise other ingredients commonly found in laundry liquids. Especially polyester substantive soil release polymers, hydrotropes, opacifiers, colorants, perfumes, other enzymes, other surfactants, microcapsules of ingredients such as perfume or care additives, softeners, polymers for anti redeposition of soil, bleach, bleach activators and bleach catalysts, antioxidants, pH control agents and buffers, thickeners, external structurants for rheology modification, visual cues, either with or without functional ingredients embedded therein and other ingredients known to those skilled in the art.
  • the composition is preferably a liquid and is advantageously packaged in either a multidose bottle or in a unit dose soluble pouch.
  • Suitable lipases for use in the compositions of the invention include those of bacterial, fungal or yeast origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces ), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P .
  • lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 , WO 97/07202 , US2008004186 , US2006205628 , US5869438 , US6017866 , US2002110854 , US6939702 , US2009221034 , US200802425 , US2004053360 , US2005281912 , US2006075518 , US2005059130 , US20041542180 , US2003199069 , WO98106215 and WO08088489 .
  • lipases are described and referenced but not limited to those in Juardo et al J Surfact Deterg (2007) 10: 61-70 , Horchani et al J Molecular Catalysis: Enzymatic 56 (2009) 237-245 , Aloulou et al Biochimica et Biophysica acta 1771 (2007) 1446-1456 , Mogensen et al Biochemistry (2005) 44: 1719-1730 , Nicanuzia dos Prazeres et al Brazilian J of Microbiology (2006) 37: 505-509 , Fernandez-Lorente et al Biotechnology and Bioengineering, 97: vol2 242-250 , Gilbert (1993) Enzyme Microb. Technol.
  • Preferred commercially available lipase enzymes include LipolaseTM and Lipolase UltraTM, LipexTM, Novozym 525L (Novozymes A/S).
  • the composition may comprise a cutinase. classified in EC 3.1.1.74.
  • the cutinase used according to the invention may be of any origin.
  • cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
  • Cutinases are enzymes that are able to degrade cutin.
  • the cutinase is derived from a strain of Aspergillus, in particular Aspergillus oryzae, a strain of Alternaria, in particular Alternaria brassiciola, a strain of Fusarium, in particular Fusarium solani, Fusarium solani pisi, Fusarium roseum culmorum, or Fusarium roseum sambucium, a strain of Helminthosporum, in particular Helminthosporum sativum, a strain of Humicola, in particular Humicola insolens, a strain of Pseudomonas, in particular Pseudomonas mendocina, or Pseudomonas putida, a strain of Rhizoctonia, in particular Rhizoctonia solani, a strain of Streptomyces, in particular Streptomyces scabies
  • the cutinase is derived from a strain of Humicola insolens, in particular the strain Humicola insolens DSM 1800.
  • Humicola insolens cutinase is described in WO 96/13580 .
  • the cutinase may be a variant, such as one of the variants disclosed in WO 00/34450 and WO 01/92502 , which are hereby incorporated by reference.
  • Preferred cutinase variants include variants listed in Example 2 of WO 01/92502 , which is hereby specifically incorporated by reference.
  • esterases are those described in US2002012959 , WO09085743 , WO09002480 , US2002137177 , US2003024009 , US2010151542 , US2003032161 , US2002007518 and US2007167344 . This also includes the Transferase enzyme class.
  • Preferred commercial cutinases include NOVOZYMTM 51032 (available from Novozymes A/S, Denmark).
  • the composition may also comprise phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32.
  • phospholipase is an enzyme which has activity towards phospholipids.
  • Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
  • Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
  • phospholipases A 1 and A 2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
  • lysophospholipase or phospholipase B
  • Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
  • phospholipase includes enzymes with phospholipase activity, e.g., phospholipase A (A 1 or A 2 ), phospholipase B activity, phospholipase C activity or phospholipase D activity.
  • phospholipase A used herein in connection with an enzyme of the invention is intended to cover an enzyme with Phospholipase A 1 and/or Phospholipase A 2 activity.
  • the phospholipase activity may be provided by enzymes having other activities as well, such as, e.g., a lipase with phospholipase activity.
  • the phospholipase activity may, e.g., be from a lipase with phospholipase side activity.
  • the phospholipase enzyme activity is provided by an enzyme having essentially only phospholipase activity and wherein the phospholipase enzyme activity is not a side activity.
  • the phospholipase may be of any origin, e.g., of animal origin (such as, e.g., mammalian), e.g. from pancreas (e.g., bovine or porcine pancreas), or snake venom or bee venom.
  • animal origin such as, e.g., mammalian
  • pancreas e.g., bovine or porcine pancreas
  • snake venom or bee venom e.g., from snake venom or bee venom.
  • the phospholipase may be of microbial origin, e.g., from filamentous fungi, yeast or bacteria, such as the genus or species Aspergillus, e.g., A . niger, Dictyostelium, e.g., D. discoideum; Mucor, e.g. M. javanicus, M. mucedo, M.
  • subtilissimus Neurospora, e.g. N. crassa; Rhizomucor, e.g., R. pusillus; Rhizopus, e.g. R. arrhizus, R. japonicus, R. stolonifer, Sclerotinia, e.g., S . libertiana; Trichophyton, e.g. T . rubrum; Whetzelinia, e.g., W. sclerotiorum; Bacillus, e.g., B. megaterium, B. subtilis; Citrobacter, e.g., C . freundii; Enterobacter, e.g., E.
  • aerogenes E. cloacae Edwardsiella, E. tarda; Erwinia, e.g., E. herbicola; Escherichia, e.g., E. coli; Klebsiella, e.g., K . pneumoniae; Proteus, e.g., P. vulgaris; Providencia, e.g., P. stuartii; Salmonella, e.g. S . typhimurium; Serratia, e.g., S . liquefasciens, S. marcescens; Shigella, e.g., S . flexneri; Streptomyces, e.g., S .
  • the phospholipase may be fungal, e.g., from the class Pyrenomycetes, such as the genus Fusarium, such as a strain of F. culmorum, F. heterosporum, F. solani, or a strain of F. oxysporum.
  • the phospholipase may also be from a filamentous fungus strain within the genus Aspergillus, such as a strain of Aspergillus awamori, Aspergillus foetidus, Aspergillus japonicus, Aspergillus niger or Aspergillus oryzae.
  • Preferred phospholipases are derived from a strain of Humicola, especially Humicola lanuginosa.
  • the phospholipase may be a variant, such as one of the variants disclosed in WO 00/32758 , which are hereby incorporated by reference.
  • Preferred phospholipase variants include variants listed in Example 5 of WO 00/32758 , which is hereby specifically incorporated by reference.
  • the phospholipase is one described in WO 04/111216 , especially the variants listed in the table in Example 1.
  • the phospholipase is derived from a strain of Fusarium, especially Fusarium oxysporum.
  • the phospholipase may be the one concerned in WO 98/026057 displayed in SEQ ID NO: 2 derived from Fusarium oxysporum DSM 2672, or variants thereof.
  • the phospholipase is a phospholipase A 1 (EC. 3.1.1.32). In another preferred embodiment of the invention the phospholipase is a phospholipase A 2 (EC.3.1.1.4.).
  • Examples of commercial phospholipases include LECITASETM and LECITASETM ULTRA, YIELSMAX, or LIPOPAN F (available from Novozymes A/S, Denmark).
  • the composition may further comprise other enzymes enhancing the detergency of the composition such as softening agents, an amylase (e.g. Fungamyl(R) from Novo Nordisk A/S, Denmark), a lipase (e.g. Novocor(R) AD from Novo Nordisk A/S, Denmark), a cellulase (e.g. Celluzyme(R), Carezyme(R), and/or Celluclast(R), all from Novo Nordisk A/S, Denmark), a xylanase (e.g. Biofeed(R) PLUS or Shearzyme(TM) from Novo Nordisk A/S, Denmark), a beta-glucanase (e.g.
  • an amylase e.g. Fungamyl(R) from Novo Nordisk A/S, Denmark
  • a lipase e.g. Novocor(R) AD from Novo Nordisk A/S, Denmark
  • a cellulase e.g. Cellu
  • a pectinase e.g. Pectinex(TM) Ultra from Novo Nordisk A/S, Denmark
  • a peroxidase e.g. Guardzyme(TM) from Novo Nordisk A/S, Denmark
  • a laccase e.g. obtained from Myceliophthora or Polyporus
  • Wash solutions were prepared by dispersing lipase at a concentration of 4mg protein per litre together with detergent surfactant at the required concentration in phosphate buffered saline (PBS) adjusted to pH 8 and 12° FH water hardness. 10 mls of the wash solution were mixed in 25 ml plastic vials at 37 °C with agitation at 200 rpm in an orbital incubator for 30 minutes. Swatches (approximately 1 cm 2 ) of cotton cloth stained with Sudan Red coloured Beef fat were then added and the vials returned to the shaking incubator. Swatches were removed at timed intervals, rinsed in cold water and dried at 37 °C. The residual colour was monitored using a Macbeth Colour Eye, and compared with untreated stained cloths.
  • PBS phosphate buffered saline
  • Bacterial enzyme is "Lipomax", a bacterially derived Lipase variant M21 L of the lipase of Pseudomonas alcaligenes as described in WO 94/25578 to Gist-Brocades (M.M.M.J. Cox, H.B.M. Lenting, L.J.S.M. Mulleners and J.M. van der Laan).
  • Fungal enzyme is "Lipolase”, derived from Humicola languginosa as described in EP 0 258 068 and available from NovoZymes A/S.
  • the process of separating and characterising the mixture was carried out using an HPLC connected to an Ion Trap Electrospray ionisation Mass Spectrometer.
  • the mode of ionisation was in negative mode with a scanning range of 50-1200Da.
  • the column used to separate was a Phenomenex luna C18 250 x 4.6mm 5 ⁇ m column.
  • the mobile phase water (mobile phase A) and acetonitrile (mobile phase B) were used to separate via a gradient of 60:40 (A:B) changing to 30:70 (A:B) over 30 minutes.
  • the system was then held for 5 minutes before returning to the start conditions all at a flow rate of 0.5ml/min.
  • the injection volume was 10 ⁇ l.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP11728878.7A 2010-07-22 2011-07-04 Combinations of rhamnolipids and enzymes for improved cleaning Active EP2596087B1 (en)

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Application Number Priority Date Filing Date Title
EP11728878.7A EP2596087B1 (en) 2010-07-22 2011-07-04 Combinations of rhamnolipids and enzymes for improved cleaning

Applications Claiming Priority (3)

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EP10170403 2010-07-22
PCT/EP2011/061214 WO2012010406A1 (en) 2010-07-22 2011-07-04 Combinations of rhamnolipids and enzymes for improved cleaning
EP11728878.7A EP2596087B1 (en) 2010-07-22 2011-07-04 Combinations of rhamnolipids and enzymes for improved cleaning

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EP2596087A1 EP2596087A1 (en) 2013-05-29
EP2596087B1 true EP2596087B1 (en) 2015-12-16

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EP (1) EP2596087B1 (pt)
CN (2) CN103052704A (pt)
BR (1) BR112013000108B1 (pt)
ES (1) ES2561553T3 (pt)
WO (1) WO2012010406A1 (pt)
ZA (1) ZA201300377B (pt)

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WO2022229069A1 (en) * 2021-04-29 2022-11-03 Unilever Ip Holdings B.V. Process to produce mono-rhamnolipids

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US8957129B2 (en) 2012-05-07 2015-02-17 Rhodia Operations Aqueous coatings and paints incorporating one or more antimicrobial biosurfactants and methods for using same
DE102013205755A1 (de) * 2013-04-02 2014-10-02 Evonik Industries Ag Waschmittelformulierung für Textilien enthaltend Rhamnolipide mit einem überwiegenden Gehalt an di-Rhamnolipiden
DE102013205756A1 (de) * 2013-04-02 2014-10-02 Evonik Industries Ag Mischungszusammensetzung enthaltend Rhamnolipide
WO2015091294A1 (en) * 2013-12-18 2015-06-25 Unilever Plc Mono-rhamnolipid based compositions.
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