Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2096—Heterocyclic compounds

Definitions

• the present invention relates to the field of laundry detergent compositions. More in particular, it relates to a laundry detergent composition comprising one or more surfactants, a furanone compound or lactam analogue thereof, and an enzyme.
• Suitable solutions to prevent microbial activity and or achieve microbial kill have traditionally involved the application of strong chemicals such as bleaches. However, there are many formulations that are bleach free and in some products it is beneficial to remove such chemicals. It is also important to develop laundry detergent systems that have a reduced environmental impact.
• Furanones are heterocyclic compounds having a five-membered ring containing an oxygen atom. Some furanones have been reported to possess activity as biofilm blocking substances, see for instance WO-A-2006/117113 (Henkel KGaA) . Further suitable furanone compounds and their lactam analogues are described in WO-A-2008/040097 (Biosignal Ltd.) .
• furanones are particularly compatible with other laundry ingredients such as builders and surfactants and that they can act synergistically with an enzyme against microbes present on fabrics and those encountered in the washing process, which results in a reduction of malodour.
• a laundry detergent composition comprising (i) at least one surfactant, (ii) at least one furanone compound or lactam analogue thereof, and
• a process for laundering textile fabrics by machine or hand characterised in that it comprises the step of immersing the fabrics in a wash liquor comprising water in which the composition according to the invention is dissolved or dispersed.
• a process for manufacturing a laundry detergent composition according to the invention is provided.
• the laundry detergent composition of the invention comprises, as a first ingredient, at least one surface active ingredients or surfactants. Depending on the physical type of detergent, the surfactants are present in an amount of 0.1 to 60 % by weight of the composition.
• an aqueous liquid detergent composition comprises from 5% to 50%, commonly at least 10% and up to 40% by weight of one or more surfactants.
• Fabric washing powders usually comprise from 20% to 45% by weight of one or more surfactants.
• surfactants include alkylbenzene sulphonates, branched or linear alkyl benzene sulphonates, primary and secondary alcohol sulphates, particularly C8 ⁇ Ci6 primary alcohol sulphates; alkyl ether sulphates, olefin sulphonates, including alpha olefin sulphonates, alkane sulphonates, alkyl xylene sulphonates, dialkyl sulphosuccinates, and alkyl carboxylates . These may be present as sodium, potassium, calcium or magnesium salts or mixtures of these. Sodium salts are generally preferred.
• the surfactant is preferably a sulphonate or sulphate anionic surfactant or a combination thereof. More preferably, the anionic surfactant is linear alkylbenzene sulphonate or primary alkyl sulphate. Most preferably the other surfactant is linear alkylbenzene sulphonate.
• the linear alkyl benzene sulphonate may be present as sodium, potassium, or alkaline earth metal salts, or mixtures of these salts. Sodium salts are generally preferred.
• the surfactant may also comprise a nonionic surfactant, preferably an ethoxylated alcohol nonionic surfactant with an average degree of ethoxylation ranging from about 3 to 9, preferably from about 3 to 7.
• the alcohol may be derived from natural or synthetic feedstock. Preferred alcohol feedstocks are coconut and palm kernel, predominantly C 12 -C 14 , and oxo C ⁇ 2 ⁇ C 15 alcohols.
• the nonionic surfactant is suitably present in an amount of from 1 to 20 wt.%, preferably from 1 to 10, more preferably from 2 to 6 wt.%, most preferably from 3 to 5 wt.%, based on the weight of the total composition.
• Additional surfactants may comprise other nonionics such as alkylpolyglucosides, polyhydroxyamides (glucamide) , methyl ester ethoxylates and glycerol monoethers .
• cationic, amphoteric surfactants and/or zwitterionic surfactants may be present.
• Preferred cationic surfactants are quaternary ammonium salts of the general formula R 1 R 2 R3R 4 N + X-, for example where Ri is a C 12 -C 14 alkyl group, R 2 and R3 are methyl groups, R 4 is a
• Preferred amphoteric surfactants are amine oxides, for example coco dimethyl amine oxide.
• Preferred zwitterionic surfactants are betaines, and especially amidobetaines .
• Preferred betaines are C8 to C18 alkyl amidoalkyl betaines, for example coco amido betaine. These may be included as co-surfactants, preferably present in an amount of from 0 to 10 wt.%, more preferably 1 to 5 wt.%, based on the weight of the total composition.
• the laundry detergent may also contain a biological based surfactant, as sourced and generated via microbial fermentation.
• a biological based surfactant as sourced and generated via microbial fermentation.
• biosurfactants that could be used are described in Pattanathu et al . Biotechnology 7 (2) 360-370 (2008) and Muthusamy et al . Current Science Vol. 94 N°6 736-747 (2008) .
• the laundry detergent composition of the invention comprises, as a second ingredient, one or more furanone compounds or their lactam analogues.
• furanones are heterocyclic compounds having a five-membered ring containing an oxygen atom. Suitable furanone compounds and their lactam analogues are described in WO-A-2008/040097 (Biosignal Ltd.) .
• the furanone compound has the general formula
• X is selected from -O- or -N(R5)-; wherein R5 is selected from H, alkyl, aryl and arylalkyl; Rl is selected from H, halo, alkyl, aryl and heteroaryl; R2 and R4 are each independently selected from hydrogen, aryl and heteroaryl with the proviso that both R2 and R4 cannot be hydrogen; and R3 is selected from H, alkyl, heteroaryl and aryl. R4 and R3 are preferably H. It is preferred that wherein R2 is aryl or heteroaryl.
• the aryl is preferably a phenyl group, optionally substituted with one or more substituents selected from the group consisting of CF3, OCF3, cyano (CN) , halo, F, alkoxyl and methoxyl .
• the heteroaryl is preferably a five-membered heteroaromatic ring containing one or more heteroatoms selected from O, N and S.
• the five-membered heteroaromatic ring is a thiophene.
• Rl is preferably aryl, heteroaryl or halo, wherein halo is Br.
• the aryl is preferably a phenyl group optionally substituted with one or more substituents selected from the group consisting of CF3, OCF3, cyano (CN), halo and F.
• the heteroaryl is preferably a five-membered heteroaromatic ring containing one or more heteroatoms selected from 0, N and S. In an especially preferred embodiment the five-membered heteroaromatic ring is a thiophene.
• each of Rl and R2 are preferably the same substituent selected from aryl and heteroaryl .
• the furanone compound or its lactam analogue would generally be present in an amount of 0.0001 to 20 wt . % of the composition.
• the desired in use concentration of the furanone is generally from 0.1 to lOOOppm, more preferably from 0.5 to 500ppm, most preferably from 1 to 50ppm.
• the laundry detergent composition of the invention comprises, as a third ingredient, one or more other microbial cell wall degrading enzymes.
• microbial cell wall degrading enzyme we mean in the context of the present invention, any enzyme that can effect or assist in the degradation of microbial cell walls.
• the enzymes are capable, directly or indirectly through their activity, of modifying the surrounding matrix or environment around the microbial entity or of modifying the cell wall of the microbe itself.
• the enzymes are suitably selected from the group consisting of glycosyl hydrolases (mannanase, glucanase, hemicellulase, cellulase, amylase, glycosidase, lysozyme, exopolysaccharidase, chitinase, ligninase) , lactonase, transferase, amidase, protease, lipase, phospholipase, esterase, cutinase, polyesterase, oxidoreductases (laccase, peroxidase, pyranose oxidase, haloperoxidase) , lysostaphin, perhydrolase .
• glycosyl hydrolases mannanase, glucanase, hemicellulase, cellulase, amylase, glycosidase, lysozyme, exopolysacc
• Preferred microbial cell wall degrading enzymes are protease, lipase, esterase (cutinase and polyesterase) and glycosyl hydrolases such as mannanase and amylase.
• compositions may also contain a lipase variant of the Humicola lanuginosa lipase with substitutions T231R + N233R, commercially available as LipexTM from Novozymes or another variant as described in WO-A-00/60063.
• Examples of commercially available bacterial lipase, cutinase or esterase are LumafastTM and LipomaxTM or variants thereof.
• the composition may contain commercial enzymes such as the new enzymes from Novozymes: MannawayTM, NatalaseTM, RenozymeTM, OvozymeTM, CelluCleanTM, PolarzymeTM, StainzymeTM, CoronaseTM, PectaawayTM, PectawashTM, Termamyl UltraTM. And the new enzymes from Genencor: FN-3, FN-4, Purafect PrimeTM, Properase 2 ⁇ TM
• compositions of the invention may also contain maltogenic ⁇ -amylases as described in WO-A-02/02726 page 5, line 14 to page 11 line 29.
• maltogenic ⁇ -amylases are NovamylTM and MaltogenaseTM from Novozymes.
• Enzymes capable of hydrolysing or removing biofilms are known in the art, e.g. Amylase WO2006031554 (Novozymes), Oxidoreductases EP946207 (Novozymes), Endogalactonase
• WO2001023534 VTT Biotechnology
• Enzyme libraries for biofilm control WO20040606945 Verenium Corp
• Mannanases EP871596 Exopolysaccharidases
• EP820516 Boetzadearborn
• Carbohydrase / protease WO2001053010 Universality Madrid
• the enzyme may be a single enzyme or a mixture of enzymes.
• the laundry detergent composition of the invention may additionally comprise a number of the following optional ingredients which provide cleaning performance, fabric care and/or sanitation benefits.
• compositions of the invention may contain a detergency builder.
• the builder is present in an amount of from 1 to less than 80 wt . % based on the weight of the total composition. More preferably the amount of builder is from 1 to 60 wt . % .
• Builders are well-known to those skilled in the art. Many suitable builder compounds are available. Examples are zeolites, sodium tripolyphosphate, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, sodium silicate and mixtures thereof.
• the optional builder may be selected from strong builders such as phosphate builders, aluminosilicate builders and mixtures thereof. However, strong builders are preferably present in an amount not exceeding 5 wt.%, and most preferably strong builders are absent. One or more weak builders such as calcite/carbonate, beryllium/carbonate, citrate or polymer builders may be additionally or alternatively present.
• the phosphate builder (if present) may for example be selected from alkali metal, preferably sodium, pyrophosphate, orthophosphate and tripolyphosphate, and mixtures thereof.
• the aluminosilicate may be, for example, selected from one or more crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel) , amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble) ; and layered silicates as disclosed in EP 164 514B (Hoechst)
• the alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8 1.5 Na2O. A12O3. 0.8 6 SiO2. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
• the preferred sodium aluminosilicates contain 1.5 3.5 SiO2 units (in the formula above) . Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble) .
• the preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, and mixtures thereof.
• the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
• the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever) .
• Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
• zeolite MAP may be used, having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
• the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
• Bleaches Detergent compositions according to the invention may suitably contain a bleach system.
• the bleach system is preferably based on peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
• Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates .
• Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate .
• sodium percarbonate having a protective coating against destabilisation by moisture Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao) .
• the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt.%, preferably from 10 to 25 wt . % .
• the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
• the bleach precursor is suitably present in an amount of from 1 to 8 wt.%, preferably from 2 to 5 wt.%.
• Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
• An especially preferred bleach precursor suitable for use in the present invention is N, N, N ' , N ' -tetracetyl ethylenediamine (TAED) .
• peroxybenzoic acid precursors in particular, N, N, N-trimethylammonium toluoyloxy benzene sulphonate.
• a bleach stabiliser may also be present.
• Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark) , EDTMP.
• EDTA ethylenediamine tetraacetate
• Dequest Trade Mark
• the present invention may be used in a formulation that is used to bleach via air, or an air bleach catalyst system.
• the bleaching composition substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system.
• the term "substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system” should be construed within spirit of the invention. It is preferred that the composition has as low a content of peroxyl species present as possible. It is preferred that the bleaching formulation contains less that 1 % wt . /wt . total concentration of peracid or hydrogen peroxide or source thereof, preferably the bleaching formulation contains less that 0.3 % wt . /wt . total concentration of peracid or hydrogen peroxide or source thereof, most preferably the bleaching composition is devoid of peracid or hydrogen peroxide or source thereof. In addition, it is preferred that the presence of alkyl hydroperoxides is kept to a minimum in a bleaching composition comprising the ligand or complex of the present invention.
• the bleaching composition comprises an organic substance that forms a complex with a transition metal for bleaching a substrate with atmospheric oxygen.
• the bleach catalyst per se may be selected from a wide range of transition metal complexes of organic molecules (ligands) .
• the level of the organic substance is such that the in-use level is from 0.05 ⁇ M to 50 mM, with preferred in-use levels for domestic laundry operations falling in the range 1 to 100 ⁇ M. Higher levels may be desired and applied in industrial textile bleaching processes.
• Suitable organic molecules (ligands) for forming complexes and complexes thereof are found, for example in: WO-A-98/39098 ; WO- A-98/39406, WO 9748787, WO 0029537; WO 0052124, and WO0060045 the complexes and organic molecule (ligand) precursors of which are herein incorporated by reference.
• An example of a preferred catalyst is a transition metal complex of MeN4Py ligand (N, N- bis (pyridin- 2 -yl-methyl) -1, 1-bis (pyridin-2-yl) -1-aminoethane) .
• the laundry detergent composition of the invention may comprise one or more further enzymes other than microbial cell wall degrading enzymes, which provide cleaning performance, fabric care and/or sanitation benefits.
• all enzymes are usually employed in granular form in amounts of from about 0.1 to about 10.0 wt. %, preferably from about 0.2 to about 3% by weight, more preferably from about 0.2 to about 1% by weight.
• the detergent compositions of the invention may further comprise one or more of the following optional ingredients selected from soap, sequestrants, cellulose ethers and esters, cellulosic polymers, other antiredeposition agents, sodium chloride, calcium chloride, sodium bicarbonate, other inorganic salts, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, acrylic and acrylic/maleic polymers, citric acid, soil release polymers, silicone, fabric conditioning compounds, coloured speckles such as blue speckles, and perfume.
• soap sequestrants
• cellulose ethers and esters cellulosic polymers
• other antiredeposition agents sodium chloride, calcium chloride, sodium bicarbonate, other inorganic salts, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, acrylic and acrylic/maleic polymers, citric acid, soil release polymers, silicone,
• Suitable lather boosters for use in the present invention include cocamidopropyl betaine (CAPB) , cocomonoethanolamide (CMEA) and amine oxides.
• CAPB cocamidopropyl betaine
• CMEA cocomonoethanolamide
• Preferred amine oxides are of the general form:
• n is from 7 to 17.
• a suitable amine oxide is Admox (Trademark) 12, supplied by Albemarle.
• compositions of the invention may optionally contain other active ingredients to enhance performance and properties.
• compositions of the invention may contain from 0 to 85 wt .% of an inorganic non-builder salt, such as sodium sulphate, sodium sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite, preferably from 0 to 60 wt. %, preferably from 0 to 40 wt.%, based on the weight of the total composition.
• an inorganic non-builder salt such as sodium sulphate, sodium sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite
• compositions of the invention may contain a polycarboxylate polymer.
• polycarboxylate polymer include homopolymers and copolymers of acrylic acid, maleic acid and acrylic/maleic acids.
• the publication ⁇ Polymeric Dispersing Agents, Sokalan' a printed publication of BASF Aktiengesellschaft, D-6700 Ludwigshaven, Germany describes organic polymers which are useful.
• the polycarboxylate polymer is selected from the group consisting of sodium polyacrylate, sodium acrylate maleate and mixtures thereof.
• suitable polymers include Sokalan CP5, ex BASF polyacrylate, namely maleic acid-acrylic acid copolymer, with a sodium salt.
• the laundry detergent composition of the invention may be in any convenient dry form, e.g., a bar, a tablet, a powder, a particle or a paste. It may also be a liquid detergent, in particular low-content aqueous (less than 70% by weight) or non-aqueous liquid detergent. If it is in a powder form, it preferably has a mean particle size between 200 and 800 micrometer. Alternatively, the compositions may be in tablet form. The compositions can be formulated for use as hand wash or machine wash detergents.
• the granular compositions of the invention may be prepared by any suitable process. Powders of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosing (dry-mixing) further ingredients. “Concentrated” or “compact” powders may be prepared by mixing and granulating processes, for example, using a high-speed mixer/granulator, or other non-tower processes.
• Tablets may be prepared by compacting powders, especially "concentrated" powders.
• the choice of processing route may be in part dictated by the stability or heat-sensitivity of the surfactants involved, and the form in which they are available. In all cases, all ingredients may be added separately.
• Figure 1 shows a two-day biofilm treated with furanone compounds, with and without one of two enzymes (polyesterase or protease), in a laundry detergent base formulation.
• Figure 2 shows a two-day biofilm treated with furanone compounds, with and without one of two enzymes (polyesterase or protease), in sterile distilled water.
• Figure 3 shows Images obtained after treatment of attached bacterial cells with a dilute laundry liquid base (LLB) .
• Figure 4 shows the darkness (%) levels assigned to each image of Figure 3.
• Bacteria were established as overnight cultures on tryptone soya agar (TSA) at 37°C. Colonies from these agar plates were suspended in tryptone diluent. The optical density (measured in McFarland units) was established using a Densimat (BioMeriux) . The resulting bacterial suspension should read between 1.5 - 1.7 which equates to a suspension containing 1-5 x 10 8 cfu/ml.
• Biofilm Development A 1:10 dilution of the bacterial suspension was prepared in 25% Tryptone Soya Broth (TSB) . This bacteria and media solution was then added (lOO ⁇ l) to the wells of a PreSens microplate and incubated at 28°C for 48h in static, moist conditions.
• TLB Tryptone Soya Broth
• the Liquid Laundry Base (LLB) had the following composition:
• Furanone compounds were:
• Enzymes Supplied as lmg/ml or 1000 ppm in PBS (phosphate buffered saline) .
• the wells were rinsed three times with PBS (120 ⁇ l) using a multi-channel pipette.
• the test samples were then added (lOO ⁇ l) for 2h (static at room temperature) then removed.
• the wells were rinsed again three times with PBS (120 ⁇ l) using a multi-channel pipette.
• TSB sterile, gas permeable sheet was placed on top of the plate. Plates were then incubated at 37°C for 2Oh. Bacterial respiration within each well was determined using a Genios plate reader and the Tecan workstation was employed to transfer the plates between the plate reader and the incubator. The data generated was represented as time required to detect bacterial respiration (mid way through the exponential phase of the "growth" curve for the control i.e. no treatment) .
• the level of bacterial removal was established after treating attached bacterial cells with a dilute laundry liquid base (LLB) with and without an enzyme, with and without a furanone compound.
• LLC dilute laundry liquid base

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