CN103052703A - Detergent compositions comprising biosurfactant and lipase - Google Patents

Detergent compositions comprising biosurfactant and lipase Download PDF

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Publication number
CN103052703A
CN103052703A CN2011800357954A CN201180035795A CN103052703A CN 103052703 A CN103052703 A CN 103052703A CN 2011800357954 A CN2011800357954 A CN 2011800357954A CN 201180035795 A CN201180035795 A CN 201180035795A CN 103052703 A CN103052703 A CN 103052703A
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Prior art keywords
surfactant
bio
lipase
enzyme
composition
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A·J·帕里
N·J·帕里
A·C·佩洛
P·S·斯特文森
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Unilever PLC
Unilever NV
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Unilever NV
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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
    • C11D3/38627Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/06Ether- or thioether carboxylic acids

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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)
  • Enzymes And Modification Thereof (AREA)

Abstract

A cleaning composition comprising an effective amount of surfactant system and an enzyme system characterised in that the surfactant system comprises at least 1 wt% (based on the cleaning composition) of a biosurfactant, which is a glycolipid surfactant comprising at least 20 mol% of glycolipid having both disaccharide and acid moieties and at least one lipase enzyme of bacterial origin.

Description

The detergent composition that comprises bio-surfactant and lipase
Technical field
The present invention relates to comprise the detergent composition of bio-surfactant and lipase.
Background
Rahman is at Biotechnology 7 (2): 360-370, the general introduction of bio-surfactant is disclosed among the 2008ISSN 1682-296 X " Production, Characterisation and application of Biosurfactants-review (production of bio-surfactant, sign and application-summary) ".
Enzyme is used for detergent formulations for many years as the cleaning auxiliary.They can be derived from the bacterium in other sources.The most frequently used enzyme is proteolytic enzyme, amylase, mannonase lipase and cellulase.They are derived from fungi or yeast culture usually.
The detergent formulations that lipase is used for containing tensio-active agent is helped the oily dirt on the clean textile.Although they have obtained separating and characterizing before many decades, because there is the competition to target substrates oil between enzyme and the tensio-active agent, these enzymes are difficult to be formulated in the conventional surfactants preparation.Tensio-active agent will win the competition of this effects on surface, and will win or with enzyme from the oil-containing surface replacement out, therefore reduce enzyme to the effect of those dirts.Therefore, the actual effect of lipase in the washing composition cleaning product is restricted, especially with other cleaning enzymes (as, proteolytic enzyme and amylase) effect when comparing.
The promotion of sustainable chemistry has more been strengthened reducing the expectation of tensio-active agent level in the washing.As the biological substitution product, enzyme has represented the selection with weight efficiency, in order to keep oily dirt removal effect in the situation that the surfactant water pancake is low.In many prior art documents, the use bio-surfactant has been proposed.
Relate to bio-surfactant and the combination of originating from the enzyme of bacterium with Publication about Document.
JP5168489A has described a kind of method of using lipase to prepare bio-surfactant.With lipase exist bio-surfactant do not have any acid moieties.The existence of two sugar moieties is chosen wantonly.
" Lipase and biosurfactant production for utilisation in bioremediation of vegetable oils and hydrocarbon (being used for the lipase of biological restoration of vegetables oil and hydrocarbon and the production of bio-surfactant) ", (2008) Quimica Nova the 31st phase the 8th volumes such as Martins VG, 1942-1947.
" Isolation and characterisation of a lipid degrading bacterium and its application to lipid containing wastewater treatment (separation of degradation of lipid bacterium and sign and the application in the processing that contains lipid waste water thereof) ", (2007) Journal of Bioscience and the 103rd phases of Bioengineering such as Matsumiya Y., the 4th volume, 325-330.
US2006106120 has described the mixture of microorganism, bio-surfactant and plastic degradation enzyme, is used for the biological restoration of artificial material.Bio-surfactant can be derived from bacterium or other sources; The preferred enzyme that uses among the embodiment is the at of bacterial origin.It can with amylase and hydrophobin co expression.Said composition is not for cleaning.
Relate to bio-surfactant and be not the specific composition that originates from the enzyme of bacterium with Publication about Document, be used for cleaning.
CN101126052 has described the cleaning compositions that contains bio-surfactant, and it also contains proteolytic enzyme.The source of proteolytic enzyme is the pineapple plant.
US5417879 (Unilever) has described the collaborative duplex surface promoting agent laundry composition that contains sophorolipid (from yeast), cellobiose fat (from fungi) or rhamnolipid (from bacterium) Glycolipids Biosurfactants via.Use the example of these bio-surfactants not comprise any enzyme.At the 12nd hurdle the 24th to 25 row, mentioned possible bio-surfactant is combined with the enzyme in the unexposed source of unexposed amount.
US2004171512A (Igarashi Keisuke; Hirata Yoshihiko; Furuta Taro) disclose the low-sudsing detergent composition that comprises bio-surfactant (from the sophorolipid of yeast), described bio-surfactant can substitute conventional low bubble block polymer nonionic surface active agent.According to overall disclosed content, bio-surfactant can use with the enzyme of unexposed type, and described enzyme is selected from amylase, proteolytic enzyme, cellulase, lipase, Starch debranching enzyme, isopullulanase, isoamylase, catalase, peroxidase etc.Can suitably select to add enzyme according to substrate specificity.For example, for protein contaminants, can select proteolytic enzyme, and for the starch spot, can select amylase.Use sophorolipid to be used for cleaning dish (hard-surface cleaning) in conjunction with Savinase 6.0T (a kind of proteolytic enzyme from Novo Nordisk) and Duramyl 60T (a kind of amylolytic enzyme from Novo Nordisk (amylase)) among the embodiment.Duramyl originates from Bacillus licheniformis (Bacillus licheniformis), and Savinase originates from Bacillus clausii (Bacillus Clsusii)/bacillus lentus (Bacillus lentus), all is bacterial origin.Not instructing these in the document is preferably to originate on the kind.
US2009188055A (Stepan Co) discloses the composition of the sulfonation estolide that comprises lipid acid and other derivatives.Table 20 provides the prophesy example of these tensio-active agents in conjunction with other tensio-active agents (comprising rhamnolipid).In these examples, do not comprise enzyme.In the other places of the document, declared by using lipase, with the collaborative clean-up performance that has improved the unctuousness dirt of estolide.Suitable lipase comprises by those of the microorganisms of Rhodopseudomonas, such as English Patent 1,372, and disclosed pseudomonas stanieri (Pseudomonas stutzeri) ATCC 19.154 in 034.Suitable lipase comprises by those of the positive immunological cross-reaction of having of producing of microorganism Pseudomonas fluorescens IAM1057 and lipase antibody.This lipase can be available from Amano Pharmaceutical Co.Ltd., Nagoya, and Japan, its commodity are called Lipase P " Amano ", hereinafter are called " Amano-P ".Suitable lipase in addition is the lipase as M1 Lipase.RTM and Lipomax.RTM (Gist-Brocades).Highly preferred lipase is the U.S.6 that authorizes such as on January 25th, 2000,017,871 (P﹠amp; The D96L lipolytic enzyme variants of the native lipase that is derived from pubescence detritus enzyme (Humicola lanuginosa) (a kind of fungi) G).The preferred pubescence detritus enzyme strain DSM 4106 that uses.According to this technology, this kind of enzyme is mixed in the composition with the level that 50LU to 8500LU/ rises washings.Preferably, modification D 96L exists with the level that 100LU to 7500LU/ rises washings.The level that more preferably rises washings with 150LU to 5000LU/ exists.
US2006080785A (Nero) has described and has been applied to carpet by the composition that will contain bio-surfactant and enzyme and carries out carpet cleaning; And with justifying the cover cleaning material.Described enzyme is derived from sea-tangle.
One piece of document has proposed the composition of bio-surfactant and the enzyme that is derived from bacterium is used for cleaning.
US2004072713A (Unilever) discloses the goods that are used for enzymatic clean fabric method, and described goods contain the harmless microorganism for the enzyme of described clean fabric method of can secreting of one or more types.In one embodiment, microorganism can be bacterium, but also for example understands fungi microbe.Embodiment all represents bleaching enzymes.Although microorganism is not used for embodiment, the document is inferred except enzyme, if microorganism also can produce other chemical substances that help cleaning method (for example, bio-surfactant, for example lipopolysaccharides), then is particularly useful.In the document, in fact openly do not comprise the bio-surfactant that is derived from bacterium and be derived from scavenging solution or the enriched material of mixture of the enzyme of bacterium.We be sure of that the concentration ratio 0.5g/L of bio-surfactant is much lower.
Summary of the invention
According to the present invention, there be a kind of surfactant system of significant quantity and cleaning compositions of enzyme system of comprising, it is characterized in that this surfactant system comprises at least bio-surfactant of 1wt% (based on cleaning compositions), it is to comprise the glycolipid class tensio-active agent that 20mol% at least has the glycolipid of disaccharides and acid moieties, and the lipase of at least a bacterial origin.
Had been found that the lipase that will be derived from bacterium and the biological tensio-active agent (bio-surfactant) with disaccharides and acid moieties in conjunction with the time, the cleaning of spot and dirt is had surprising synergistic benefits.
Said composition can be used for any biotechnological formulation.Lipase is that a class is for the enzyme of the key of mixing detergent composition (especially laundry detergent), also be used to the enzyme of the composition that is designed for cleaning of hard surfaces such as the key of cleaning dish composition, it is under the tensio-active agent level that reduces, preparation effectively cleans daily dirt and spot, so that can concentrate.
We have tested the combination of bio-surfactant (fungi, bacterium and yeast) with two types the lipase (fungus and bacterium) of three types.For bio-surfactant, bacterial enzyme is better than fungal enzyme all the time.Best result is from the combination of bacteriogenic enzyme and bacteriogenic bio-surfactant, and described bio-surfactant comprises the bio-surfactant (two-rhamnolipid) that 80mol% at least has disaccharides and acid moieties.
According to a second aspect of the invention, there is a kind of method for the cleaning matrix, comprise matrix is immersed in the water, to be added to the water the step that forms scavenging solution and clean matrix according to the composition of each claim before, it is characterized in that time cleaning interval is less than 60 minutes, preferably be less than 30 minutes, and water temperature always is lower than 35 ℃.
Detailed Description Of The Invention
Comprising lipase of bacterial origin
Suitable lipase comprises those of bacterial origin.The mutant that comprises chemically modified or protein engineering.The example of useful comprising lipase of bacterial origin comprises from Pseudomonas alcaligenes (P.alcaligenes) or pseudomonas pseudoalcaligenes (P.pseudoalcaligenes) (EP218272), pseudomonas cepacia (P.cepacia) (EP331376), pseudomonas stanieri (GB1372034), Pseudomonas fluorescens, pseudomonas strain SD 705 (WO95/06720 and WO96/27002), Wisconsin pseudomonas (P.wisconsinensis) lipase (WO96/12012); Genus bacillus lipase, for example, from subtilis (B.subtilis) (Dartois etc. (1993), Biochemica et Biophysica Acta, 1131,253-360), bacillus acidocldarius (B.stearothermophilus) (JP64/744992) or bacillus pumilus (B.pumilus) (WO91/16422).
The bacterial gene of coding comprising lipase of bacterial origin can be transferred among the preferred Expression product host, it is not limited to bacterium and comprises for example other microorganism host.The term comprising lipase of bacterial origin comprises and produces from these expressive hosts but be derived from the lipase of bacterium.
Enzyme can be the Phospholipid hydrolase that classifies as EC 3.1.1.4 and/or EC 3.1.1.32.As used herein, the term Phospholipid hydrolase is to the activated enzyme of phosphatide tool.Phosphatide is such as Yelkin TTS or phosphatidylcholine, by with (sn-1) and middle (sn-2) the position esterification and with the glycerine formation of phosphoric acid the 3rd position esterification in the outside of two lipid acid; Phosphoric acid and then can esterified one-tenth amino-alcohol.Phospholipid hydrolase is the enzyme that participates in the phosphatide hydrolysis.Can distinguish the phospholipase activity of several types, comprise phospholipase A 1And A 2, it is hydrolyzed a fatty acyl group (each comfortable sn-1 and sn-2 position), to form lysophospholipid; And lysophospholipase (or phospholipase B), it can be hydrolyzed remaining fatty acyl group in the lysophospholipid.Phospholipase C and Phospholipase D (phosphodiesterase) discharge DG or phosphatidic acid separately.
The term Phospholipid hydrolase comprises the enzyme with phospholipase activity, for example, and phospholipase A (A 1Or A 2), phospholipase B is active, Phospholipase C is active or Phospholipase D is active.The relevant term " phospholipase A " of enzyme used herein and of the present invention is intended to contain has phospholipase A 1And/or phospholipase A 2Active enzyme.Phospholipase activity can provide by also having other active enzymes, as, for example, have the lipase of phospholipase activity.Phospholipase activity, for example, can be from having the secondary active lipase of Phospholipid hydrolase.In other embodiments of the present invention, phospholipase activity by basically only have phospholipase activity and wherein phospholipase activity be not that secondary active enzyme provides.
Preferably, Phospholipid hydrolase is bacterial origin: bud is the spore Bacillaceae, for example, and bacillus megaterium (B.megaterium), subtilis; Citrobacter (Citrobacter), for example, citrobacter freundii (C.freundii); Enterobacter (Enterobacter), for example, enteroaerogen (E.aerogenes), enterobacter cloacae (E.cloacae); Edwardsiella (Edwardsiella), Wdwardsiella tarda (E.tarda); Erwinia (Erwinia), for example, grass living Erwinia (E.herbicola); Escherichia (Eecherichia), for example, colon bacillus (E.coli); Klebsiella (Klebsiella), for example, Klebsiella pneumonia (K.pneumoniae); Proteus (Proteus), for example, proteus vulgaris (P.vulgaris); Providencia (Providencia), for example, Si Shi Providence bacterium (P.stuartii); Salmonella (Salmonella), for example, Salmonella typhimurium (S.typhimurium); Serratia (Serratia), for example, liquefied Serratia (S.liquefasciens), serratia marcescens (S.marcescens); Shigella (Shigella), for example, shigella flexneri (S.flexneri).
Composition can further comprise the enzyme that is not bacterial origin.Particularly proteolytic enzyme, amylase and cellulase, but also can comprise non-comprising lipase of bacterial origin.
Bio-surfactant
Bio-surfactant is derived from microbial source, comprises bacterium, yeast and fungi.Term bio-surfactant in the patent specification does not comprise the tensio-active agent of plant-derived material, such as alkyl dextran glycosides (APG).
A) bio-surfactant of bacterial origin
They are for example usually from the rhamnolipid of Rhodopseudomonas.About the information of other bacteriogenic bio-surfactants can acquisition from " Mapping of Patents in Bioemulsifiers and biosurfactants-review (the patent collection of illustrative plates of biological emulsifier and bio-surfactant-summary); be disclosed in Journal of Scientific and Industrial Research the 65th volume; 2006, the 91 pages ".In the definition of bacteriogenic bio-surfactant, we comprised that bacterial gene is cloned and obtained by the another kind of organism expressing as manufacturing technology subsequently those.For example, produced rhamnolipid from intestinal bacteria by this way.
B) from the bio-surfactant of non-bacterial origin
Bio-surfactant from non-bacterial micro-organism source comprises those that are derived from fungi and yeast, for example, give birth to candiyeast (Candida apicola), Candida bombicola, separate the sophorolipid of fatty candiyeast (Candida lipolytica), Candida bogoriensis from the honeybee of mycocandida (Candida) and torulopsis (Torulopsis).Referring to: Environmental applications for biosurfactants (environmental applications of bio-surfactant)-Environmental Pullution, the 133rd volume, 2005, the 183-198 pages or leaves, Catherine N.Mulligan.Can also referring to, Towards commercial production of microbial surfactants (commercial production of MICROBIAL SURFACTANT)-Trends in Biotechnology, the 24th volume, 2006,509-515 page or leaf: Soumen Mukherjee, Palashpriya Das, Ramkrishna Sen.
Mannosylerythritol lipid is usually from Pseudozyma (thinking in the past mycocandida) Antarctica.Cellobiose fat is usually from Ustilago maydis (D C.) Corola. (Ustilago maydis).The marine alga glycolipid is usually from Rhod (Rhodococcus sp.).
More information is referring to Production, Characterisation and Application of Biosurfactants Review (production of bio-surfactant, sign and summary of Application)-Biotechnology-the 7th volume, 2008, the 370th page: Pattanathu, Rahman and Gakpe.
Detergent composition can comprise other compositions of usually finding in washing liquid.Especially the spot release polymers of polyester, hydrotropic agent, opalizer, tinting material, spices, other enzymes, other tensio-active agents, such as microcapsule, the tenderizer of the composition of spices or nursing additive, be used for polymkeric substance, SYNTHETIC OPTICAL WHITNER, bleach-activating agent and bleaching catalyst, antioxidant, pH control agent and buffer reagent, the thickening material that the opposing spot deposits again, external structure agent, the visual indicator that is used for the rheology correction, it contains or does not contain the functional ingredient that is embedded in wherein, and other compositions well known by persons skilled in the art.Composition is liquid preferably, and advantageously be packaged in multi-dose vials or the unitary dose solubility sack.
Further describe the present invention now with reference to following non-limiting example.
Embodiment
Embodiment 1
In this embodiment, test various enzymes/bio-surfactant composition, removed the ability of coloured beef spot from cotton to measure them.
By the lipase of 4mg protein/rise concentration is dispersed in preparation cleaning solution in the phosphate buffered saline (PBS) (PBS) that pH regulator to 8 and the water hardness are 12 °F of H with the detergent surfactant of desired concn.Under 37 ℃ the 10ml cleaning solution was being stirred 30 minutes with 200rpm in the 25ml plastic jar and in the track incubator and mixing.Then add and dye cotton sample (about 1cm that the painted beef fat spot of Sudan red is arranged 2) and bottle returned in the Shaking Incubators.Under interval regularly, take out sample, rinsing and lower dry at 37 ℃ in cold water.Use the remaining color of Macbeth Colour Eye monitoring, and have the cloth of spot to compare with untreated dying.30 minutes the results are shown in the table 1,4 hours the results are shown in the table 2.
Bacterial enzyme is " Lipomax ", Gist-Brocades (M.M.M.J.Cox, H.B.M.Lenting, L.J.S.M.Mulleners and J.M.van der Laan) WO94/25578 in the bacteriogenic lipase Variant M21L of the Pseudomonas alcaligenes lipase described.
Fungal enzyme is " Lipolase ", is derived from pubescence humicola lanuginosa (Humicola languginosa) described in EP025068, and can obtain from NovoZymes A/S.
The detailed content of tensio-active agent is as follows:
SL=sophorolipid: the bio-surfactant that comprises the originated from fungus of two sugar moieties and at least 20% acid moieties.
AC=Accell: the bio-surfactant that is derived from yeast.
RL=rhamnolipid: comprise the bio-surfactant of the bacterial origin of acid moieties, and wherein R2 comprises two sugar moieties.RL is the single rhamnolipid of about 70mol% two rhamnolipids and 30mol%.Only have two rhamnolipids to have two required sugar moieties.
Show 1-30 minute
Bio-surfactant Without enzyme Comprising lipase of bacterial origin Fungal enzyme
0.25g/l SL 2.83 8.42 4.29
0.25g/l AC 0.96 2.39 1.25
0.25g/l RL 3.35 5.40 3.29
0.5g/l SL 8.98 11.20 8.44
0.5g/l AC 1.05 1.95 1.00
0.5g/l RL 1.28 10.00 0.82
Show 2-4 hour
Bio-surfactant Without enzyme Comprising lipase of bacterial origin Fungal enzyme
0.25g/l SL 5.52 12.98 8.61
0.25g/l AC 3.67 9.15 3.19
0.25g/l RL 3.12 8.01 3.36
0.5g/l SL 12.23 13.59 11.29
0.5g/l AC 2.22 8.40 3.52
0.5g/l RL 1.38 12.01 2.34
Comprising lipase of bacterial origin is better than fungal lipase all the time on all Strain types.For sophorolipid, to wash under the time at higher concentration and Changqing, the existence of fungal lipase does not provide the effect that is better than using tensio-active agent and does not use lipase.
By Application standard BCA albumen test box (from Pierce), according to the experimental program of manufacturers, measure the content of the organized enzyme albumen in each sample, enzyme is all added with par.
Embodiment 2
In this embodiment, detect various enzymes/bio-surfactant composition, removed the ability of coloured beef spot to measure them.
Carried out identical experiment according to embodiment 1, except rhamnolipid being divided into list-rhamnolipid and two-rhamnolipid composition.Two rhamnolipids have two rhamnosyls at acyl group.We use symbol R1 to represent single rhamnolipid, and R2 represents two rhamnolipid materials.Provided the cleaning result of 1 hour and 4 hours in the table 3 and 4.
Show 3-1 hour
Bio-surfactant Without enzyme Comprising lipase of bacterial origin Fungal lipase
0.5g/l SL 6.34 10.28 9.72
0.5g/l RL 1.15 8.88 1.04
0.5g/l R1 9.85 11.31 12.25
0.5g/l R2 0.80 8.87 1.05
Show 4-4 hour
Bio-surfactant Without enzyme Comprising lipase of bacterial origin Fungal lipase
0.5g/l SL 10.25 12.54 11.17
0.5g/l RL 1.18 10.68 1.89
0.5g/l R1 14.52 12.43 14.19
0.5g/l R2 1.14 11.42 2.85

Claims (6)

1. cleaning compositions, it comprises surfactant system and the enzyme system of significant quantity, it is characterized in that described surfactant system comprises at least 1wt% (based on cleaning compositions) bio-surfactant, described bio-surfactant is glycolipid class tensio-active agent, comprise the glycolipid that 20mol% at least has disaccharides and acid moieties, and the lipase of at least a bacterial origin.
2. according to claim 1 composition, wherein said bio-surfactant is selected from rhamnolipid, sophorolipid and composition thereof.
3. according to claim 1 composition, wherein said bio-surfactant is bacterial origin.
4. according to each composition of aforementioned claim, wherein said bio-surfactant is rhamnolipid.
5. according to claim 4 composition, wherein said rhamnolipid comprises two or more rhamnosyl monomers at acyl chain, and at least 60% is two-rhamnolipid.
6. the method that is used for the cleaning matrix, comprise described matrix is immersed in the water, to add according to each composition of aforementioned claim the step that forms scavenging solution in the described water and clean described matrix, it is characterized in that time cleaning interval is less than 60 minutes, preferably be less than 30 minutes, and water temperature always is lower than 35 ℃.
CN2011800357954A 2010-07-22 2011-07-04 Detergent compositions comprising biosurfactant and lipase Pending CN103052703A (en)

Applications Claiming Priority (3)

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EP10170404.7 2010-07-22
EP10170404 2010-07-22
PCT/EP2011/061216 WO2012010407A1 (en) 2010-07-22 2011-07-04 Detergent compositions comprising biosurfactant and lipase

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