CN102257117B - Laundry detergent composition - Google Patents

Laundry detergent composition Download PDF

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Publication number
CN102257117B
CN102257117B CN200980151382.5A CN200980151382A CN102257117B CN 102257117 B CN102257117 B CN 102257117B CN 200980151382 A CN200980151382 A CN 200980151382A CN 102257117 B CN102257117 B CN 102257117B
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Prior art keywords
composition
enzyme
laundry detergent
detergent composition
washing
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CN102257117A (en
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J·奥克费
N·J·帕里
I·K·史密斯
D·泰勒
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Unilever IP Holdings BV
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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
    • C11D3/38645Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2096Heterocyclic compounds

Abstract

Potential malodour problems are reduced in laundry detergent compositions comprising (i) at least one surfactant, (ii) at least one furanone compound or lactam analogue thereof, and (iii) a microbial cell wall degrading enzyme.

Description

Laundry detergent composition
Technical field
The present invention relates to laundry detergent composition field.More specifically, the present invention relates to the laundry detergent composition that contains one or more tensio-active agents, furan ketone compound or its lactam analogs (lactam analogue) and enzyme.
Background technology
Modern laundry detergent composition has become very efficient for the clean fabric of making dirty.Still one of the challenge existing is niff, and it can occur under particular condition, particularly in the time using the washing times of minimizing and lower temperature.It is believed that such condition may be for removing microorganism and finally preventing them on fabric and/or be that metabolism in the part of washing system is invalid at washing process itself.Then microorganism can be retained on fabric or can spread all over clothes at washing process, and they can cause on clothes, producing niff subsequently between dress or staging life.
Prevent from microorganism active and/or realize suitable terms of settlement that microorganism kills generally including and using such as SYNTHETIC OPTICAL WHITNER of extensive chemical product.But many formulas do not contain SYNTHETIC OPTICAL WHITNER and remove such chemical in some products is favourable.It is also important that exploitation has the detergent for washing clothes system of the environmental influence of minimizing.
Exist and continue demand for thering is the new or substituting laundry detergent composition of bad smell trend of reduction and method.Therefore an object of the present invention is to provide this laundry detergent composition and method.Another object of the present invention is to provide the method for the preparation of the laundry detergent composition of this bad smell that minimizing is provided.
Have been surprisingly found that, of the present invention this can be realized by laundry detergent composition of the present invention with other objects, and it contains
(i) at least one tensio-active agent,
(ii) at least one furanone (furanone) compound or its lactam analogs, and
(iii) microorganism cells wall degrading enzyme (microbial cell wall degrading enzyme).
Furanones is to have the pentacyclic heterogeneous ring compound that contains Sauerstoffatom.Some Furanones it is reported to have the activity that stops (blocking) material as microbial film, for example, referring to WO-A-2006/117113 (Henkel KGaA).The furan ketone compound that other is suitable and lactam analogs thereof are disclosed in WO-A-2008/040097 (Biosignal Ltd.).
Have been surprisingly found that, such furanone and other laundry for example washing assistant of composition and tensio-active agent is compatible especially and they can act synergistically on the microorganism existing on fabric and those microorganisms that run in washing process with enzyme, this causes the minimizing of bad smell.
Summary of the invention
According to a first aspect of the invention, provide laundry detergent composition, it contains
(i) at least one tensio-active agent,
(ii) at least one furan ketone compound or its lactam analogs, and
(iii) microorganism cells wall degrading enzyme.
According to a second aspect of the invention, provide the method for wash textile fabric by machine or hand washing, it is characterized in that it comprises described fabric is immersed in and contains water and composition dissolves of the present invention or be dispersed in the step in washing liq wherein.
According to a third aspect of the invention we, provide the method for preparing laundry detergent composition of the present invention.
Embodiment
Laundry detergent composition of the present invention contains at least one surface active ingredient or tensio-active agent as the first composition.Depend on the physical aspect of washing composition, the amount of described tensio-active agent is the 0.1-60% of said composition weight.Typically, aqueous liquid detergent compositions contains 5 % by weight-50 % by weight, and at least 10 % by weight arrive one or more tensio-active agents of 40 % by weight at the most conventionally.Fabric washing powder contains one or more tensio-active agents of 20 % by weight-45 % by weight conventionally.
Tensio-active agent is well known by persons skilled in the art.Many suitable detergent active compounds are available and fully describe in the literature, for example Schwartz, and " the Surface-Active Agents and Detergents " of Perry and Berch writing, in the 1st volume and the 2nd volume.
The example of tensio-active agent comprises alkylbenzene sulfonate, branched-chain or straight-chain alkyl benzene sulfonate, primary alconol and secondary alcohol sulfate, particularly C 8~C 16primary alcohol sulfate; Sulfated alkyl ether, alkene sulfonate, comprise sulfonated α-olefin, alkane sulfonate, alkylxylene sulfonate, dialkyl sulfosuccinates and alkyl carboxylate.These can be used as sodium salt, sylvite, calcium salt or magnesium salts or their mixture exists.Conventionally particular certain cancers.
Described tensio-active agent is preferably sulfonate or sulphate anion surface active agent or its combination.More preferably, described anion surfactant is linear alkylbenzene sulfonate or primary alkyl sulphates.Most preferably, other tensio-active agent is linear alkylbenzene sulfonate.The mixture that described linear alkylbenzene sulfonate can be used as sodium salt, sylvite or alkaline earth salt or these salt exists.Conventionally particular certain cancers.
Described tensio-active agent also can comprise nonionogenic tenside, and the preferably alcohol nonionogenic tenside of ethoxylation has the average degree of ethoxylation of about 3-9, preferably has the average degree of ethoxylation of about 3-7.Described alcohol can be derived from natural or synthesis material.Preferred raw polyol is coconut and palm-kernel, is mainly C 12-C 14alcohol and oxo process C 12-C 15alcohol (oxo C 12-C 15alcohols).
The suitable amount of described nonionogenic tenside is 1-20wt.%, preferably 1-10wt.%, and more preferably 2-6wt.%, most preferably 3-5wt.%, based on the weight of whole composition.
Extra tensio-active agent can comprise other nonionogenic tenside (nonionics) for example alkyl polyglucoside, polyhydroxyamide (glucamide), methyl ester ethoxylate and glycerol monoethers.Also can there is cats product, amphoterics and/or zwitterionics.Preferred cats product is to have general formula R 1r 2r 3r 4n +x -quaternary ammonium salt, for example R wherein 1c 12-C 14alkyl group, R 2and R 3methyl, R 42-hydroxyethyl groups, and X -it is chlorion.This material can be by Clariant GmbH with commercially available the obtaining of Praepagen (trade mark) HY, the aqueous solution that form is 40wt%.
Preferred amphoterics is oxidation amine, for example cocoyl dimethyl oxidation amine.Preferred zwitterionics is betaines, particularly amido betaines class.Preferred betaines is C8-C18 alkyl amido alkyl betaine, for example cocoyl amido betaines.These can be used as cosurfactant and are included, and preferably amount is 0-10wt.%, more preferably 1-5wt.%, and the weight based on whole composition is calculated.
Described detergent for washing clothes also can contain Bio-surfactant, is derived from microorganism fermentation and by the microorganism generation of fermenting.Operable such bio-surfactant is described in Pattanathu etc., Biotechnology 7 (2) 360-370 (2008) and Muthusamy etc., Current Science, in Vol.94 N ° 6736-747 (2008).
Laundry detergent composition of the present invention contains one or more furan ketone compounds or its lactam analogs as the second composition.As mentioned above, Furanones is to have the pentacyclic heterogeneous ring compound that contains Sauerstoffatom.Suitable furan ketone compound and lactam analogs thereof are described in WO-A-2008/040097 (Biosignal Ltd.).
Preferably, described furan ketone compound has general formula I:
Here, be selected from-O-of X or-N (R5)-; Wherein R5 is selected from H, alkyl, aryl and aralkyl; R1 is selected from H, halogen (halo), alkyl, aryl and heteroaryl; R2 and R4 are respectively independently selected from hydrogen, aryl and heteroaryl, and condition is that R2 and R4 can not be hydrogen simultaneously; Be selected from H, alkyl, heteroaryl and aryl with R3.R4 and R3 are preferably H.Preferably, wherein R2 is aryl or heteroaryl.Described aryl is preferably phenyl, optional selected free CF3, and OCF3, cyano group (CN), halogen (halo), F, one or more substituting groups in the group of alkoxyl group and methoxyl group composition replace.Described heteroaryl is preferably to contain and is selected from O, one or more heteroatomic five yuan of hetero-aromatic rings of N and S.Preferably, these five yuan of hetero-aromatic rings are thiophene.
In general formula I, R1 is preferably aryl, heteroaryl or halogen, and wherein halogen is Br.Described aryl is preferably phenyl, optional selected free CF3, and OCF3, cyano group (CN), one or more substituting groups in the group of halogen and F composition replace.Described heteroaryl is preferably to contain and is selected from O, one or more heteroatomic five yuan of hetero-aromatic rings of N and S.In a particularly preferred specific embodiments, these five yuan of hetero-aromatic rings are thiophene.Therefore, R1 and R2 are preferably the identical substituting group that is selected from aryl and heteroaryl separately.
As selection, can use the lactam analogs of such Furanones, it is also disclosed in WO-A-2008/040097.
Highly preferred compound is:
Compound Title
113 The bromo-4-hexyl-5-of 3-(bromine methylene radical)-2 (5H)-furanones
265 4-(4-trifluoromethyl) phenyl)-2 (5H)-furanones
295 5-methylene radical-4-(4`-bromophenyl)-pyrrolin-2-ketone (dihydropyrrol-2-one)
310 5-methylene radical-4-(2`-fluorophenyl)-pyrrolin-2-ketone
313 5-hydroxy-5-methyl base-4-(2`-fluorophenyl)-pyrrolin-2-ketone
350 5-(thiene-3-yl-methylene radical) furans-(2H)-one
Described furan ketone compound or the common amount of its lactam analogs are by the 0.0001-20wt% that is composition.The expectation working concentration of described furanone is generally 0.1-1000ppm, more preferably 0.5-500ppm, most preferably 1-50ppm.
Laundry detergent composition of the present invention contains one or more other microorganism cells wall degrading enzymes as the 3rd composition.Term " microorganism cells wall degrading enzyme " refers to any enzyme that can realize or help microorganism wall degraded in the context of the present invention.Described enzyme can be directly or indirectly by its activity change microorganism entity (entity) around maybe can change the cell walls of microorganism itself around matrix or environment.Free glycosyl hydrolase (the mannase of choosing that described enzyme is suitable, dextranase, hemicellulase, cellulase, amylase, Glycosylase, N,O-Diacetylmuramidase, exo polysaccharides enzyme (exopolysaccharidase), chitinase, lignoenzyme), lactonase, transferring enzyme, Ntn hydrolase, proteolytic enzyme, lipase, Phospholipid hydrolase, esterase, at, polyester enzyme (polyesterase), oxydo-reductase (laccase, peroxidase, pyranose oxidase (pyranose oxidase), haloperoxidase (haloperoxidase)), lysostaphin, the group of Perhydrolase (perhydrolase) composition.
Preferred microorganism cells wall degrading enzyme is proteolytic enzyme, lipase, esterase (at and polyester enzyme) and for example mannase of glycosyl hydrolase and amylase.
The suitable member of these enzymes in is not described in Enzyme nomenclature 1992:recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology on the nomenclature and classification of enzymes, 1992, ISBN 0-12-227165-3, in Academic Press.Nearest information about the name of enzyme can obtain by ExPaSy Molecular Biology Server (http://us.expasy.org/) on the internet.
Described composition can also contain have replace the lipase Variant of Humicola lanuginosa lipase of T231R+N233R (can be by Novozymes with Lipex tMbe purchased) or be disclosed in the another kind of variant in WO-A-00/60063.The example of comprising lipase of bacterial origin, at or the esterase that can commercially availablely obtain is Lumafast tMand Lipomax tMor its variant.
Described composition can contain commercially available enzyme for example from the new enzyme of Novozymes: Mannaway tM, Natalase tM, Renozyme tM, Ovozyme tM, CelluClean tM, Polarzyme tM, Stainzyme tM, Coronase tM, Pectaaway tM, Pectawash tM, Termamyl Ultra tM.And from the new enzyme of Genencor: FN-3, FN-4, Purafect Prime tM, Properase tM.
Composition of the present invention also can contain the maltogenic alpha-amylase enzyme of describing in 11 page of 29 row of WO-A-02/02726 page 5 14 row-.Commercially available maltogenic alpha-amylase enzyme is the Novamyl available from Novozymes tMand Maltogenase tM.
It is as known in the art can being hydrolyzed or removing biomembranous enzyme, for example amylase WO2006031554 (Novozymes), oxydo-reductase EP946207 (Novozymes), Endogalactonase WO2001023534 (VTT Biotechnology), enzyme storehouse WO20040606945 (Verenium Corp), mannase EP871596 for microbial film control, exo polysaccharides enzyme EP820516 (Betzadearborn), carbohydrase/proteolytic enzyme WO2001053010 (University Madrid).Thereby these and other enzyme family can be as described the 3rd composition in the present invention.Described enzyme can be single mixture of planting enzyme or enzyme.
Optional composition
Laundry detergent composition of the present invention can additionally contain many following optional members that clean-up performance, fabric nursing and/or hygienic benefit are provided.
detergent builder compound
Composition of the present invention can contain detergent builder compound.Preferably, the amount of described washing assistant is that 1wt%-is less than 80wt%, and the weight based on whole composition is calculated.More preferably the amount of washing assistant is 1-60wt.%.Washing assistant is well known by persons skilled in the art.Many suitable washing-aid compounds are available.Example is zeolite, tripoly phosphate sodium STPP, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, water glass and composition thereof.
Optional washing assistant for example phosphate builders, the aluminosilicate washing assistant and composition thereof of improving oneself of described optional washing assistant.But the amount of strong washing assistant is preferably and is no more than 5wt.%, and most preferably not containing strong washing assistant.One or more weak washing assistant for example calcite/carbonate, beryllium/carbonate, Citrate trianion or polymkeric substance washing assistants can exist extraly or alternatively.
Described phosphate builders (if existence) for example can be selected from basic metal, preferably na pyrophosphates, orthophosphoric acid salt and tri-polyphosphate and composition thereof.
Described aluminosilicate (if existence) for example can be selected from one or more crystallizations and amorphous aluminosilicate, for example, be disclosed in the zeolite in GB1473 201 (Henkel), be disclosed in the amorphous aluminosilicate in GB1473202 (Henkel) and be disclosed in the mixed crystallization/amorphous aluminosilicate in GB1470250 (Procter & Gamble); With the layered silicate being disclosed in EP164514B (Hoechst).
Alkali metal aluminosilicate can be crystallization or unbodied or its mixture, has general formula: 0.8 1.5 Na2O.Al2O3.0.86 SiO2.
These materials contain some in conjunction with water and need to have at least calcium ion exchange capacity of 50mg CaO/g.Preferred sodium aluminium silicate contains 1.5 3.5 SiO2 unit (in above-mentioned general formula).Amorphous and crystalline material can easily be prepared by the reaction between water glass and sodium aluminate, as describing in detail in document.Suitable crystalline aluminium water glass ion-exchange detergent builder compound is disclosed in for example GB1429143 (Procter & Gamble).Preferred such sodium aluminium silicate is known commercially available Wessalith CS and X zeolite and composition thereof.
Described zeolite can be the commercially available zeolite 4A being widely used at present in washing powder.But; according to a preferred specific embodiments of the present invention; adding the zeolite builder in the present composition is maximum aluminium zeolite (maximum aluminium zeolite) P (zeolite MAP), describes also claimed in EP384070A (Unilever).Zeolite MAP is defined as silicon and aluminum ratio value is no more than 1.33, is preferably 0.90-1.33, more preferably the alkali metal aluminosilicate of the zeolite P type of 0.90-1.20.
Aptly, can use zeolite MAP, it has and is no more than 1.07, more preferably about 1.00 silicon and aluminum ratio value.The calcium-binding capacity of described zeolite MAP is generally at least every gram of anhydrous substances of 150mg CaO.
SYNTHETIC OPTICAL WHITNER
Detergent composition of the present invention can contain bleach system aptly.This bleach system is preferably based on peroxy bleaching compound, and for example inorganic persalt or organic peracid can produce hydrogen peroxide in the aqueous solution.Suitable peroxy bleaching compound comprises for example urea peroxide of organo-peroxide and inorganic persalt for example alkali metal perborate, percarbonate, superphosphate, persilicate and persulphate.Preferred inorganic persalt is Sodium peroxoborate monohydrate and tetrahydrate, and SPC-D.Particularly preferably be and there is the SPC-D of resisting the unsettled supercoat being caused by moisture.The SPC-D with the supercoat that contains sodium metaborate and water glass is disclosed in GB2123044B (Kao).
The suitable amount of described peroxy bleaching compound is 5-35wt.%, preferably 10-25wt.%.Described peroxy bleaching compound can be combined with bleach-activating agent (bleaching precursor) use to improve bleaching action in low wash temperature.The suitable amount of described bleaching precursor is 1-8wt.%, preferably 2-5wt.%.
Preferred bleaching precursor is peroxycarboxylic acid precursors, more preferably peracetic acid precursors and peroxybenzoic acid precursors and peroxycarbonic acid precursors.Being applicable to the particularly preferred bleaching precursor of one of the present invention is N, N, N ', N '-tetra acetyl ethylene diamine (TAED).Also interested is benzoyl hydroperoxide precursor, particularly toluene acyloxy Phenylsulfonic acid N, N, N-trimethyl ammonium.
Also can there is bleaching stibilizer (heavy metal chelant).Suitable bleaching stibilizer comprises edetate (EDTA) and for example Dequest of polyphosphonate (trade mark), EDTMP.
As selection, the present invention can be used in for passing through the formula of air bleaching, or in air bleaching catalysts system.In this, bleaching composition do not basically contain peroxygen bleach or based on peroxide or produce the bleach system of hydrogen peroxide.
Term " do not basically contain peroxygen bleach or based on peroxide or produce the bleach system of hydrogen peroxide " should in spirit of the present invention, explain.Preferably said composition has the hydroperoxide class of the existence of low levels as far as possible.Preferably bleaching formula contains peracid or hydrogen peroxide or its source lower than 1%wt/wt total concn, preferably bleaching formula contains peracid or hydrogen peroxide or its source lower than 0.3%wt/wt total concn, and most preferably bleaching composition is not containing peracid or hydrogen peroxide or its source.In addition, preferably in the bleaching composition that contains part of the present invention or complex compound, the existence of alkyl hydrogen peroxide (alkyl hydroperoxides) remains minimum.
In order to play the function of air bleaching composition, bleaching composition contains the organic substance that forms complex compound with transition metal, for using aerial oxygen bleaching matrix.
Bleaching catalyst itself can be selected from a large amount of organic molecule (part) transition metal complex.In typical cleaning composition, the concentration of described organic substance is 0.05 μ M-50mM for making concentration in use, is 1-100 μ M for concentration in the preferred use of household laundry operation.Higher concentration may be desired and be applied in industrial textile bleaching technique.
The suitable organic molecule (part) and its complex compound that are used to form complex compound are found in for example WO-A-98/39098; WO-A-98/39406, WO 9748787, WO 0029537; In WO 0052124 and WO0060045, its complex compound and organic molecule (part) precursor is incorporated to herein by reference at this.An example of preferred catalyzer is the transition metal complex of MeN4Py part (N, N-bis-(pyridine-2-base-methyl)-1,1-bis-(pyridine-2-yl)-1-ethylamine).
other enzyme
Laundry detergent composition of the present invention can contain one or more other enzymes except microorganism cells wall degrading enzyme, and it provides clean-up performance, fabric nursing and/or hygienic benefit.
In composition of the present invention, all enzymes all use with the form of particle conventionally, measure about 10.0wt.% into about 0.1-, about 3 % by weight of preferably approximately 0.2-, more preferably about about 1 % by weight of 0.2-.
other optional member
Detergent composition of the present invention can further contain the optional member below one or more, is selected from soap, sequestrant, ether of cellulose and ester, cellulose polymer compound, other anti redeposition agent, sodium-chlor, calcium chloride, sodium bicarbonate, other inorganic salt, white dyes, photobleaching agent, Polyvinylpyrolidone (PVP), other dye transfer inhibiting polymers, foam control agent, profoamer, vinylformic acid and vinylformic acid/toxilic acid polymkeric substance, citric acid, soil release polymer, silicone, fabric-conditioning compound, look grain for example blue grain and spices.It is exhaustive that this list is not intended to.
Other material may reside in detergent composition of the present invention comprises suitable Foam Control or suds booster, dyestuff and decoupling polymkeric substance (decoupling polymers).
Comprise cocamidopropyl betaine (CAPB), coconut monoethanol amide (CMEA) and amine oxide for suitable suds booster of the present invention.Preferred amine oxide has general formula:
N is wherein 7-17.A kind of suitable amine oxide is Admox (trade mark) 12, is provided by Albemarle.
Except optional member discussed above, composition of the present invention can optionally contain other activeconstituents of strengthening the property with characteristic.
For example, composition of the present invention can contain the inorganic non-builder salt of 0-85wt%, and for example sodium sulfate, concentrated crystal soda, sodium-chlor, calcium chloride, magnesium chloride and calcite, be preferably 0-60wt.%, more preferably 0-40wt.%, the weight based on whole composition is calculated.
Composition of the present invention can contain polycarboxylate polymer.These comprise homopolymer and the multipolymer of vinylformic acid, toxilic acid and vinylformic acid/toxilic acid.Publication " Polymeric Dispersing Agents, Sokalan ", BASF Aktiengesellschaft, D-6700 Ludwigshaven, the printed publication of Germany, discloses useful organic polymer.Preferably, described polycarboxylate polymer is selected from the group being made up of sodium polyacrylate, sodium acrylate sodium maleate and composition thereof.The example of suitable polymkeric substance comprises Sokalan CP5, available from BASF polyacrylate, i.e. and maleic acid-acrylic acid copolymer, sodium salt.
The form of composition
Laundry detergent composition of the present invention can be any dried forms easily, for example bar, sheet, powder, particle or lotion.It can be also liquid washing agent, particularly low water content (lower than 70 % by weight) or non-aqueous liquid washing composition.If it is the form of powder, its preferred mean particle size is 200-800 micron.As selection, described composition can be in the form of sheets.Described composition can be formulated into as hand washing or machine washing washing composition.
the preparation of composition
Can prepare particulate composition of the present invention by any suitable method.Be low to moderate medium tap density powder can by spray dry slurry and optional after add the preparation of assigning to of (being dry mixed) other one-tenth." concentrate " or " compression " powder can by mix and prilling process, for example use high-speed mixer/tablets press, or prepared by other non-tower methods.
Sheet can particularly " concentrate " powder by compressing powder to be prepared.The selection of machining path can be partly by the stability of the tensio-active agent relating to or thermo-sensitivity with and available form decide.With regard to all situations, all compositions all can add separately.
The present invention now will further illustrate by nonrestrictive embodiment below, and wherein part and per-cent are all by weight, except as otherwise noted.
Brief description of the drawings
In the accompanying drawings:
Fig. 1 has shown the furan ketone compound being used in detergent for washing clothes base-material preparation, the microbial film of two days or do not have with the processing of one of two kinds of enzymes (polyester enzyme or proteolytic enzyme).
Fig. 2 has shown the furan ketone compound being used in sterile distilled water, the microbial film of two days or do not have with the processing of one of two kinds of enzymes (polyester enzyme or proteolytic enzyme).
Fig. 3 has shown the image of processing gained after the bacterial cell adhering to rare laundry liquid base material (laundry liquid base, LLB).
Fig. 4 has shown darkness (%) level that belongs to each image in Fig. 3.
embodiment 1
method and material
microbial culture
As obtaining bacterium at 37 DEG C of incubated overnight things on tryptose soya agar (TSA).To be suspended in Tryptones diluent from the bacterium colony of these agar plates.Determine optical density(OD) (measuring) with Densimat (BioMeriux) in McFarland unit.The bacterial suspension reading of gained should be at 1.5-1.7, and it is equal to suspension and comprises 1-5x 10 8cfu/ml.
microbial film is cultivated
The preparation bacterial suspension dilution of 1: 10 in 25% pancreas peptone soybean broth (TSB).Then this bacterium and culture medium solution are added to that (100 μ l) cultivate 48 hours at 28 DEG C in the hole of PreSens microplate and under static, wet condition.
test formulation
stoste:
Liquid laundry base-material (LLB) has following composition:
It is diluted to 2.3g/L with sterile distilled water.
Furan ketone compound is:
Compound Title
113 The bromo-4-hexyl-5-of 3-(bromine methylene radical)-2 (5H)-furanones
265 4-(4-trifluoromethyl) phenyl)-2 (5H)-furanones
295 5-methylene radical-4-(4`-bromophenyl)-pyrrolin-2-ketone
310 5-methylene radical-4-(2`-fluorophenyl)-pyrrolin-2-ketone
313 5-hydroxy-5-methyl base-4-(2`-fluorophenyl)-pyrrolin-2-ketone
350 5-(thiene-3-yl-methylene radical) furans-(2H)-one
In pure MPG, prepare the stoste of each compound to 500ppm (every kind of 0.01g in 20ml MPG).Enzyme: provide in PBS (salt solution of phosphate buffered) with 1mg/ml or 1000ppm.
mix:
Use the stoste of each compound, prepared 1: 10 dilution in SDW and laundry base-material, thereby cause the each compound of 50ppm in each base-material.Repeat this step, but obtain each compound of 100ppm level in each base-material with dilution in 1: 5.Enzyme was diluted in SDW or rare laundry base-material with 1: 100, obtained 10ppm concentration.If furanone and enzyme mix, the furanone sample of 100ppm sample, for mixing with the enzyme (1: 1 diluent) of 10ppm level, obtains ultimate density 50ppm furanone and 5ppm enzyme in SDW base-material or rare laundry base-material.All test formulation are all preparations in the time evaluating.
process
At biological lamina membranacea, after the cultivation of 48 hours, with PBS, (120 μ l) use multichannel pipettor to rinse hole 3 times.Then (100 μ l) are added into 2 hours, and (room temperature leaves standstill) then removes to test sample.After processing, with PBS, (120 μ l) use multichannel pipettor again to rinse hole 3 times.
detect the respiration of remaining viable cell
After processing and rinsing, pure TSB be added in hole (200 μ l) and aseptic ventail be placed on plate.Plate is cultivated 20 hours at 37 DEG C subsequently.Determine the bacterial respiratory effect in each hole with Genios plate reader, Tecan workstation is for transmission plate between incubator and plate reader.The data that produce are expressed as the required time of bacterial respiratory effect that detects (not processing the mid-way of the exponential phase of growth of " growth " curve for contrast).
The results are shown in Fig. 1 and Fig. 2.The combination of Furanones and microorganism cells wall degrading enzyme (polyester enzyme or proteolytic enzyme) is very effective for postponing bacterial growth.
embodiment 2
After processing with rare laundry liquid base material (LLB) and do not there is enzyme, have or do not have with furan ketone compound the bacterial cell adhering to, measure bacterium and remove level.
Slide glass (2cm 2) clean and be dried with ethanol, then in sterile distilled water (SDW), rinse and keep flat dry at 37 DEG C on pallet.In phosphate buffered saline (PBS), prepare the bacterial suspension (1-1.5x10 of Pseudomonas aeruginosa (P.aeruginosa) and flavobacterium odoratum (F.odoratum) 8cfu/ml), and by the aliquots containig of each suspension (500 μ l) are added in 9ml tryptose soya agar and soft mixing.By the aliquots containig of described bacterial suspension, (100 μ l) are placed on each slide glass and cultivation liquid are extended to edge with pipette tip.Then pallet be placed in large sterile bag (unsealing) and put into the incubator of 37 DEG C and spend the night.Within second day, inoculate slide glass and be back in incubator with fresh bacterial suspension.
process
Rare test soln (3ml) is placed in the hole of 12 hole MTP, in room temperature, slide glass is vertically put into test soln 30 minutes (not stirring).Shift out slide glass and use wash bottle SDW rinsing gently.Then wave carrier piece kept flat on pallet and cultivate (37 DEG C) to dry.By ethanol (70%) be sprayed onto will be fixing slide glass on, then with the crystal violet solution slide glass that dyes.Use x100 oil immersion lens to obtain presentation graphics (Fig. 3).
Image is carried out to rough quantitative analysis as the method for calculating bacterium surface covering level.This demarcates (greyscaling) this image and carries out by open each image gray scale in Irfan View.Then selective enhancement color options and corresponding ratings slide to the rightmost side (maximum).This generates the image being made up of black and white pixel.Then in PaintShop Pro, open described image and select histogram option.This makes it possible to the per-cent on each image " darkness " to measure, and its representative is processed bacterium afterwards and covered level.Referring to Fig. 4 and following table 1.
Table 1: darkness (%) level of distributing to each image

Claims (12)

1. laundry detergent composition, it contains
(i) at least one tensio-active agent,
(ii) the bromo-4-hexyl-5-of 3-(bromine methylene radical)-2 (5H)-furanones, and
(iii) microorganism cells wall degrading enzyme, wherein said microorganism cells wall degrading enzyme selects the group of free glycosyl hydrolase, transferring enzyme, Ntn hydrolase, proteolytic enzyme, lipase, esterase, oxydo-reductase, lysostaphin, Perhydrolase composition.
2. laundry detergent composition as claimed in claim 1, wherein said glycosyl hydrolase selects the group of free mannonase dextranase, hemicellulase, cellulase, amylase, Glycosylase, N,O-Diacetylmuramidase, exo polysaccharides enzyme, chitinase and lignoenzyme composition.
3. laundry detergent composition as claimed in claim 1, wherein said oxydo-reductase selects the group of free laccase, peroxidase, pyranose oxidase and haloperoxidase composition.
4. the laundry detergent composition as described in arbitrary claim in aforementioned claim 1-3, wherein said microorganism cells wall degrading enzyme selects the group of free lactonase, at, polyester enzyme and Phospholipid hydrolase composition.
5. the laundry detergent composition as described in arbitrary claim in aforementioned claim 1-3, wherein said cell wall degrading enzyme selects the group of free proteolytic enzyme, lipase, esterase and glycosyl hydrolase composition.
6. laundry detergent composition as claimed in claim 5, wherein said esterase is selected from and polyester enzyme.
7. laundry detergent composition as claimed in claim 5, wherein said glycosyl hydrolase is selected from mannase and amylase.
8. the laundry detergent composition as described in arbitrary claim in aforementioned claim 1-3, wherein said enzyme can be directly or indirectly by its activity change microorganism entity around around matrix or environment, or change the cell walls of microorganism itself.
9. the laundry detergent composition as described in arbitrary claim in aforementioned claim 1-3, its amount is the washing assistant of 1-60 % by weight.
10. laundry detergent composition as claimed in claim 9, its amount is the washing assistant of 1-40 % by weight.
11. laundry detergent compositions as claimed in claim 9, wherein said washing assistant selects the group of free zeolite, tripoly phosphate sodium STPP, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, water glass and composition thereof composition.
12. by machine-washing or hand-washing the method for washing textile fabric, it is characterized in that it comprises described fabric is immersed in and contains water and according to the composition dissolves of claim 1-11 any one or be dispersed in the step in washing liq wherein.
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