AU2013357709A1 - Cleaning composition - Google Patents

Abstract

The present invention relates to a cleaning composition for providing effective stain removal. It is thus an object of the present invention to provide a cleaning composition which is effective against fruity stains which are otherwise considered to be difficult to remove. It is another object of the present invention to provide a cleaning composition which can be used at lower wash temperatures. It is yet another object of the present invention to provide a cleaning composition which is effective against sebum stains. It is yet another object of the present invention to provide a cleaning composition which is particularly effective at cleaning fabrics. Surprisingly it has been found that a cleaning composition having a combination of two specific bleach activators and a mixture of specific enzymes removes tough stains, which are otherwise considered to be difficult to be removed, especially fruity stains.

Description

WO 2014/090573 PCT/EP2013/074757 1 CLEANING COMPOSITION Field of the invention 5 The present invention relates to a cleaning composition for providing effective stain removal. The invention has been developed primarily for use in detergent compositions and will 10 be described hereinafter with reference to this application. However, it will be appreciated that the invention is not limited to this particular field of use. Background of the invention 15 Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field. 20 Peroxygen bleach compounds are well known for their ability to remove stains from substrates. Such bleaching agents include hydrogen peroxide, or substances that can generate perhydroxyl radical, such as inorganic or organic peroxides. Generally, the peroxygen bleach compound or hydrogen peroxide must be activated. 25 One method of activation is to employ wash temperatures greater than 60 'C. High temperatures required for activation of the peroxygen bleach compound often damage the fabric dyes, and can also cause premature damage to the substrate or fabric. Another known approach of activation is the use of organic precursor compounds along with peroxygen bleach compound. Addition of the organic precursors, often also 30 referred to as bleach activators, into compositions having peroxygen bleach compound improves bleaching activity at lower wash temperatures, e.g. 40 to 60 'C. Examples of bleach activators are tetraacetylethylenediamine (TAED) and sodium nonanoyloxybenzenesulphonate(NOBS).

WO 2014/090573 PCT/EP2013/074757 2 The bleach activators react with the perhydroxide anion (OOH-) of the hydrogen peroxide released by the peroxygen bleach compound in the aqueous solution to form a peroxyacid which is more reactive as a bleaching agent than the peroxide bleach alone. 5 Using a single bleach activator along with peroxygen bleach compound show limited action on stains depending on whether such stains are hydrophobic or hydrophilic. A hydrophobic bleach activator used with the peroxygen bleach compound is effective on hydrophobic bleachable stains, such as burnt fat (like butter), tomato-sauce, cosmetics 10 (like lipstick), but have limited performance on hydrophilic bleachable stains, such as tea or red wine stains. Similarly, a hydrophilic bleach activator when used with peroxygen bleach compound is effective on hydrophilic bleachable stains, but shows limited performance on hydrophobic bleachable stains. Two or more bleach activators are often used together to activate peroxygen bleach compounds in order to make the 15 bleach composition effective towards hydrophilic as well as hydrophobic stains. Various attempts have been made to improve the overall bleaching performance on fabrics over a wide range of stains by using bleach activator combinations. 20 One such attempt was done in W011117617A1 (Reckitt & Colman, 2011) which discloses a cleaning composition having a dispersion of a particle in acidic aqueous phase for providing stability before use and performance in use. The particle includes an admixture of tetraacetylethylenediamine (TAED) and decanoyloxybenzenecarboxylic acid (DOBA) coated with an acid stable coating. 25 US 2009130224 Al (Borchers et.al., 2009) discloses an improved bleach activator and bleach activator compositions in the form of granules having TAED and DOBA for use in washing, cleaning and disinfectant compositions. The application discloses a granular bleach activating mixture of TAED and DOBA in which the mixture is free of 30 binders. US 2008113036 Al (Reinhardt et al. 2008) discloses an improved bleach activator and bleach activator compositions having synergistic effects on difficult to remove stains WO 2014/090573 PCT/EP2013/074757 3 such as grass and curry. The application discloses a mixture of bleach activators based on hydroxybenzoic acids and particular peracetic acid-releasing activators. This further discloses washing composition, cleaning composition and disinfectant having the activator mixtures in the form of co-granules of bleach component together with 5 hydrogen peroxide-generating substance. However there is still a need for cleaning composition which can provide for effective removal of tough stains like fruity stains, sebum stains, tomato and sunflower oil stains. Especially fruity stains are particularly difficult to remove. Tough stains like fruity stains 10 require a significant amount of bleaching agent for their removal, which might also bleach the colour of the garment. With growing trend towards eating healthier, people consume several servings of fruits or fruit juices and other fruit based products between meals at work as well as at home. 15 As a result, incidents of fruity stains are on the rise. Thus there is a need for cleaning composition providing effective removal of the fruity stains from fabric especially from the white fabrics. It is thus an object of the present invention to provide a cleaning composition which is 20 effective against fruity stains which are otherwise considered to be difficult to remove. It is another object of the present invention to provide a cleaning composition which can be used at lower wash temperatures. 25 It is yet another object of the present invention to provide a cleaning composition which is effective against sebum stains. It is yet another object of the present invention to provide a cleaning composition which is particularly effective at cleaning fabrics. 30 Surprisingly it has been found that a cleaning composition having a combination of two specific bleach activators and a mixture of specific enzymes removes tough stains, which are otherwise considered to be difficult to be removed, especially fruity stains.

WO 2014/090573 PCT/EP2013/074757 4 Summary of the invention According to the first aspect, the present invention provides for a cleaning composition comprising: 5 (i) hydrogen peroxide or a peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution; (ii) a first bleach activator comprising a precursor of peracetic acid; and, (iii) a second bleach activator comprising a precursor of C8 to C11 peroxyacid; 10 wherein the composition comprises: (i) a protease; and, (ii) a lipase or an amylase or mixtures thereof. According to the second aspect, the present invention provides for a method of 15 bleaching a bleachable substrate comprising the steps of: (i) applying to the substrate a neat or diluted form of the composition of the first aspect; (ii) optionally applying to the substrate a detergent composition; and, rinsing the substrate. 20 According to the third aspect disclosed is a use of the cleaning composition of the first aspect for bleaching stains. According to a fourth aspect disclosed is a use of the cleaning composition of the first 25 aspect for bleaching fruity or sebum stains on fabrics. The invention will now be explained in more details. 30 Detailed description of the invention According to the first aspect disclosed cleaning composition includes hydrogen peroxide or a peroxygen bleach compound capable of yielding hydrogen peroxide in WO 2014/090573 PCT/EP2013/074757 5 aqueous solution, a first bleach activator, a second bleach activator, a protease and a lipase or an amylase or mixtures thereof. Cleaning composition: 5 Disclosed cleaning composition may be in different forms including but not limited to powders, tablets, liquids, bars, crystals, gels, capsules or in the form of non-aqueous liquids or carried on sheets or other substrates or in pouches. 10 The cleaning composition described herein can be used to make any cleaning preparation which can be used for the purpose of bleaching any suitable substrate, for example, laundry cleaning, laundry bleaches, bleach pre-treaters, hard surface cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.) or automatic dishwashing compositions. 15 Preferably the disclosed cleaning composition is a granular detergent composition. When the cleaning composition is a granular detergent composition it may be of a low to moderate bulk density. The known methods for manufacturing a granular detergent composition includes spray-drying, drum drying, fluid bed drying, and scraped film 20 drying preferably using the wiped film evaporator. Alternatively, the granular detergent composition may be in a 'concentrated' or 'compact' form. Such detergent composition may be prepared by mixing and granulating process, for example, using a high-speed mixer or granulator, or other non 25 tower process. When the cleaning composition is a granular detergent composition the first bleach activator and the second bleach activator may be post dosed as particulates. 30 Preferably the pH of the aqueous solution on dissolution of the detergent composition is 6 to 12 and more preferably from 7 to 10.5.

WO 2014/090573 PCT/EP2013/074757 6 Peroxyqen bleach compound: Disclosed composition includes a peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution. Hydrogen peroxide sources are well known in 5 the art. Hydrogen peroxide sources are described in details in Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", and include the alkali metal salts of sodium perborates and sodium percarbonates, including various coated and modified forms. 10 Suitable peroxygen bleach compounds include hydrogen peroxide or any of its solid adducts such as organic peroxides example; urea peroxide and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Mixtures of two or more such compounds may also be suitable. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and 15 sodium percarbonate. Hydrogen peroxide is especially preferred in liquid cleaning compositions. Percarbonate is stable during storage and dissolves quickly in the cleaning liquor and is especially preferred. It is believed that such rapid dissolution results in the formation 20 of higher levels of percarboxylic acid and, thus, enhances substrate bleaching performance. Highly preferred percarbonate is in uncoated or coated form. Preferably the average particle size of uncoated and coated percarbonate ranges from about 400 to about 1200 pm, most preferably from about 400 to about 600 pm. If coated percarbonate is used, the preferred coating materials include mixtures of carbonate 25 and sulphate, zeolite, precipitated silica, waxes, borates, polymers, citrates, silicate, borosilicate or fatty acids. Preferably the disclosed cleaning composition has 4 to 35 wt% of the peroxygen bleach compound. When the disclosed cleaning composition is in the form of a bleach additive 30 for addition at the point of use either to wash liquor or to a non-bleaching detergent composition, the peroxygen bleach compound may be present at even higher levels of up to 90wt% of the composition. When the cleaning composition is a detergent WO 2014/090573 PCT/EP2013/074757 7 composition the composition has 5 to 20 wt % more preferably 10 to 15 wt% of the peroxygen bleach compound. Bleach activator: 5 Disclosed composition includes a first bleach activator and a second bleach activator. Preferably the ratio of the first bleach activator to the second bleach activator is from 5:1 to 1:5, preferably from 3:1 to 1:3 and further preferably from 2:1 to 1:2, and most preferably 1:1. 10 The bleach activator may be in the form of a powder or as particulate bodies having the bleach activator, a binder or agglomerating agent. It is preferred for reasons of stability and handling, that bleach activator is in the form of particulate bodies. 15 Preferably the weight ratio of bleach activator to hydrogen peroxide or peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution is from 1:2 to 1:20 more preferably from 1:2 to 1:15 and still preferably from 1:5 to 1:10. First bleach activator: 20 Disclosed cleaning composition includes a first bleach activator having a precursor of peracetic acid. The first bleach activator is preferably a compound from the class of polyacylated alkylenediamines. Preferably the compound from the class of polyacylated alkylenediamines is tetraacetylethylenediamine (TAED). 25 Disclosed cleaning composition include 0.1 wt% to 20 wt%, preferably from 0.5 wt% to 10 wt% and optimal composition include 1 wt% to 5 wt% of the first bleach activator. Second bleach activator: 30 Disclosed cleaning composition includes a second bleach activator having a precursor of C8 to C11 peroxyacid. Preferably the second bleach activator is hydroxybenzoic acid derivative of the formula (1) WO 2014/090573 PCT/EP2013/074757 8 R-COO OOH in which R is C8-C11 alkyl group. Preferably the second bleach activator is decanoyloxybenzoic acid (DOBA) and 5 derivatives thereof. Enzyme: Disclosed composition includes a protease and a lipase or amylase or a mixture 10 thereof. Protease: Disclosed cleaning composition includes a protease. Suitable protease includes those 15 of animal, vegetable or microbial origin. Protease from microbial origin is preferred. Protease may also be chemically modified or protein engineered mutant. Preferably the protease is a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Examples of alkaline proteases are subtilisins, especially those derived from Bacillus, examples include subtilisin Novo, subtilisin 20 Carlsberg, subtilisin 309, subtilisin147 and subtilisin 168 (described W08906279A1). Examples of trypsin-like proteases are trypsin from porcine or bovine origin and the Fusarium protease described in W08906270A1 and W09425583A1. The protease is preferably from B.subtilis. Preferred commercially available protease includes Alcalase T M , Savinase T M , Primase T M , Duralase T M , Dyrazym

TM

, Esperase T M , Everlase T M , 25 Polarzyme T M and Kannase T M , Maxatase T M , Maxaca T M , Maxapem T M , Properase T M Purfast@, Effectenz@, Purafect

TM

, Purafect OXP TM, FN2 TM, and FN3TM (Genencor International Inc.). Protease from a strain of Bacillus having maximum activity throughout the pH range of 30 8 to 12 is highly preferred and includes commercially available Esperase T M and Savinase TM.

WO 2014/090573 PCT/EP2013/074757 9 Preferably the cleaning composition of the present invention include 0.001 wt% to 10 wt% more preferably from 0.01 wt% to wt% of protease depending upon their activity. Lipase: 5 Disclosed cleaning composition includes a lipase. Lipase catalyses hydrolysis of ester bonds of edible fats and oils, i.e. triglycerides, into free fatty acids, mono- and diglycerides and glycerol. 10 Preferred lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola species (incl. Thermomyces. species) which includes lipase from H. lanuginosus (T. lanuginosus) as described in EP0258068B1 and EP0305216B1 or from H. insolens as described in W09613580A1 or lipases from Pseudomonas species 15 which includes lipase from P. alcaligenes or P. pseudoalcaligenes (EP0218272 Al), P. cepacia (EP0331376B1), P. stutzeri (GB 1 ,372,034), P. fluorescens, Pseudomonas species strain SD 705 (W095/06720 and W096/27002), P. wisconsinensis (W096/12012) or lipases from Bacillus species which includes lipases from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131 , 253-360), B. 20 stearothermophilus (JP64/744992) or B. pumilus (WO 91/16422). Other examples include lipase variants such as those described in W092/05249, W094/01541, EP407225, EP260105, W095/35381, W096/00292, W095/30744, W094/25578, W095/14783, W095/22615, W097/04079 and W097/07202. 25 Preferred commercially available lipases are available under the trademarks Lipoclean@, Lipolase@, Lipolase@ Ultra and Lipex @. LIPEX @ is particularly preferred, and LIPEX@ 100 T is further particularly preferred. The activity of commercial lipase is commonly expressed as Lipase Units or LU. Different lipase preparations may have different activities. For fungal lipases these may range from 2,000 to 2,000,000 LU per 30 gram. Preferred compositions include lipase having 5 to 20000LU/g. In order to prevent accidents and to alleviate safety concerns, commercial lipases are always coated with an inert material. Therefore, commercial lipases that are used for WO 2014/090573 PCT/EP2013/074757 10 detergent powders, bars and tablets are in granular form containing very low amount of active lipase and balance of adjunct materials. Such granulates contain lipase concentrate, inorganic salt, binders and coating materials. They are free-flowing so that there is no lumping, and the granulate dissolve faster. Lipases are also available in 5 liquid form, example LIPEX @ 100 L. Preferred cleaning composition has 0.0001wt% to 0.3wt% lipase, more preferably from 0.0001 to 0.1wt% lipase and further preferably 0.0009wt% to 0.00186 wt% lipase. 10 Amylase: Disclosed cleaning composition includes an amylase. Suitable amylases (alpha amylase and/or beta-amylase) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of amylase suitable for 15 the present invention includes alpha-amylase obtained from Bacillus species which includes special strain of B. licheniformis, described in more detail in GB 1,296,839, or the Bacillus species strains disclosed in WO 95/026397 or WO 00/060060. Other suitable examples of amylases are the variants described in WO 94/02597, WO 94/18314, WO 96/23873, WO 97/43424, WO 01/066712, WO 02/010355 and WO 20 02/031124 (which references all incorporated by reference). Commercially available amylases are Duramyl(TM), Termamyl(TM), Termamyl Ultra(TM), Natalase(TM), Stainzyme(TM), Stainzyme Plus(TM), Fungamyl(TM) and BAN(TM) (Novozymes A/S), Rapidase(TM) and Purastar(TM) (from Genencor 25 International Inc.). Mannanase: Preferably the disclosed composition includes mannanase. Examples of suitable 30 mannanase include those of bacterial or fungal origin. Preferably the mannanase is derived from a strain of a filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus (WO 94/25576). WO 93/24622 disclosing a mannanase isolated from Trichoderma reese is also preferred. Mannanases have also been WO 2014/090573 PCT/EP2013/074757 11 isolated from several bacteria, including Bacillus species. For example, Talbot et al.,Appl. Environ. Microbiol., Vol.56, No. 11, pp. 3505-3510 (1990) describes a beta mannanase derived from Bacillus stearothermophilus. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551 -555 (1994) describes a beta-mannanase 5 derived from Bacillus subtilis. JP-A-03047076 discloses a beta-mannanase derived from Bacillus sp. JP-A-63056289 describes the production of an alkaline, thermostable beta- mannanase. JP-A-63036775 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase. JP-A-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001. A purified mannanase 10 from Bacillus amyloliquefaciens is disclosed in WO 97/11164. Examples of preferred commercially available mannanases include Mannaway(TM) available from Novozymes A/S Denmark. Surfactant: 15 Disclosed cleaning composition preferably includes a surfactant. The surfactant may be a soap or an anionic, nonionic, amphoteric, zwitterionic or cationic surfactant or mixtures thereof. In general, the nonionic and anionic surfactant may be chosen from the surfactants described in "Surface Active Agents" Vol. 1, by Schwartz and Perry, 20 Interscience 1949, Vol. 2 by Schwartz, Perry and Berch, Interscience 1958, in the current edition of "McCutcheon ' s Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H.Stache, 2nd Edn., Carl Hauser Verlag, 1981. 25 Suitable anionic surfactant includes water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl includes the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic surfactant are sodium and potassium alkyl sulphates. Especially preferred are the sodium and potassium sulphates obtainable by 30 sulphating higher C 8 to C 1 8 alcohols for example from tallow or coconut oil. Other preferred anionic surfactant include sodium and potassium alkyl C 9 to C 20 benzene sulphonates, particularly sodium linear secondary alkyl C 10 to C 15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the WO 2014/090573 PCT/EP2013/074757 12 higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. Most preferred anionic surfactants are sodium lauryl ether sulfate (SLES), particularly 5 preferred are anionic surfactant with 1 to 3 ethoxy groups, sodium C10 to C15 alkyl benzene sulphonates (LAS) and sodium C12 to C18 alkyl sulphates (PAS). Alkyl ester suphonates such as methyl ester sulphonates (MES) may be preferably used for replacing a portion or completely replacing the anionic surfactant. 10 Other suitable surfactants are those described in EP-A-328 177 (Unilever), which shows resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074 and alkyl monoglycosides. The surfactant chain may be branched or linear. 15 Suitable nonionic surfactants include the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Preferred nonionic surfactants are C6 to C22 alkyl phenol-ethylene oxide condensates, generally having 5 to 25 EO, i.e. 5 to 25 units of 20 ethylene oxide per molecule, and the condensation products of aliphatic C8 to C18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 50 EO. Preferably, the non-ionic is 10 to 50 EO, more preferably 20 to 35 EO. Alkyl ethoxylates are particularly preferred. 25 Soaps may also be present. The fatty acid soap used preferably contains from about 16 to about 22 carbon atoms, preferably in a straight chain configuration. Preferred soap may be derived from saturated and non-saturated fatty acids obtained from natural sources and synthetically prepared. Examples of such fatty acids include capric, lauric, myristic, palmitic, stearic, oleic, linoleic and linolenic acid. The anionic 30 contribution from soap is preferably from 0 to 30 wt% of the total anionic.

WO 2014/090573 PCT/EP2013/074757 13 Preferred surfactant systems are mixtures of anionic with nonionic surfactant, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever). 5 Amounts of amphoteric or zwitterionic surfactants can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic surfactants are used, it is generally in small amounts in combinations with anionic and nonionic surfactants. 10 The compositions according to the invention include 2 wt% to 70wt% of surfactant more preferably 10 to 30wt%. Preferred compositions include anionic or non-ionic surfactants. More preferred compositions include a mixture of the two. Builders and Sesquestrants: 15 Disclosed cleaning composition may include builders. Builders may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof. 20 Examples of calcium sequestrant materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra acetic acid. Examples of precipitating builder materials include sodium orthophosphate and sodium 25 carbonate. Examples of calcium ion-exchange builder materials include the various types of water insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives and includes zeolite A, zeolite B (also known as zeolite P), 30 zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-O, 384, 070. It is preferred that when an insoluble inorganic builder for example zeolite is used, the size is in the range 0.1 to 10 pm (as measured by The Mastersizer 2000 particle size analyzer using laser diffraction ex Malvern T M

).

WO 2014/090573 PCT/EP2013/074757 14 When the cleaning composition is a detergent composition in the form of granular, spray- dried or dry-blended powder, the level of builder is preferably from 1 to 40 wt%. Preferably the detergent composition includes zeolite and carbonate (including 5 bicarbonate and sesquicarbonate) builders. The composition may also contain other builders including crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably sodium aluminosilicate. Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. The term phosphate includes diphosphate, triphosphate, and phosphonate species. 10 Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst). Builders or complexing agent as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid may also be included. Many builders are also 15 bleach- stabilising agents by virtue of their ability to complex metal ions. Other ingredients: Disclosed cleaning composition may include one or more of other ingredients selected 20 from bleach stabiliser, polymers, perfumes, fluorescers, soil release polymers, germicides, colourants and coloured speckles such as blue speckles. This list is not intended to be exhaustive. Disclosed composition may include a bleach stabiliser. Suitable bleach stabilisers 25 include ethylenediamine tetraacetate (EDTA), ethylenediamine disuccinate (EDDS), and the aminopolyphosphonates such as ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphonate (DETPMP). 30 When present the composition may include one or more polymers. Examples include carboxymethylcel lulose, poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers. Suitable commercially available polymer includes Sokalan CP5 (ex WO 2014/090573 PCT/EP2013/074757 15 BASF) which is a polyacrylate, namely maleic acid-acrylic acid copolymer, with a sodium salt. Disclosed cleaning composition may also include perfumes. When present the 5 perfumes could be of natural origin or synthetic. They include single compounds or mixtures of compounds. By perfume in this context is not only meant a fully formulated product delivering fragrance, but includes selected components of that fragrance, particularly those which are prone to loss, such as the so-called top notes. The perfume may be used in the form of neat oil or in an encapsulated form. 10 Disclosed composition may also include fluorescent agent (optical brightener). Fluorescent agents are well known and many fluorescent agents are commercially available. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent 15 agent or agents used in the composition is generally from 0.005 to 2 wt%, more preferably 0.01 to 0.1 wt%. Preferred fluorescent agent includes but not limited to di styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, diamine stilbene di sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH and pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: 20 sodium 2- (4-styryl-3-sulfophenyl) -2H-napthol [1,2-d]triazole, disodium 4, 4 '-bis { [(4 anilino-6- (N methyl-N-2 hydroxyethyl) amino 1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2' disulfonate and disodium 4,4'- bis (2-sulfoslyryl) biphenyl. Tinopal@ DMS is the disodium salt of disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate. Tinopal@ CBS is the disodium salt of disodium 4,4'-bis(2 25 sulfostyryl)biphenyl. Disclosed composition may include a soil release polymer, for example sulphonated and unsulphonated PET/PEOT polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) 30 HP22. Especially preferred soil release polymer are the sulphonated non-end-capped polyesters described and claimed in W09532997A (Rhodia Chimie).

WO 2014/090573 PCT/EP2013/074757 16 The invention will now be explained in details with the help of non-limiting exemplary embodiments. 5 Examples Evaluation of the preferred and the comparative compositions in removal of blackberry stain and tomato-sunflower stain: 10 a) Measurement of Soil Release Index (SRI) Soil release index (SRI) is a measure of the amount of a stain present on fabric that is removed during a washing process. The intensity of any stain after washing is measured by means of a spectrophotometer and expressed in terms of the difference between the stained fabric and a clean fabric giving AE* for each stain. It is defined as 15 AE* and is calculated as: L*, a*, and b* are the coordinates of the CIE 1976 (L*, a*, b*) colour space, determined using a standard spectrophotometer. AE* can be measured before and after the stain is washed, to give AE*bw (before wash) and AE*aw (after wash). 20 AE after wash is the difference in L a b colour space between the clean (unwashed) fabric and the stained fabric after wash. So a AE after wash of zero means that a stain is completely removed. 25 SRI is defined as: SRI = 100 - AE*aw A SRI of 100 means complete removal of a stain. The higher the SRI value, the greater 30 is the stain removal potential.

WO 2014/090573 PCT/EP2013/074757 17 The clean (or virgin) fabric is an "absolute standard" which is not washed. For each experiment, it refers to an identical piece of fabric to that to which the stain is applied. Therefore, its point in L a b colour space stays constant. 5 b) Preparation of the preferred and control detergent composition A control detergent composition (Control) was prepared with a ratio between first bleach activator (TAED) to second bleach activator (DOBA) of 1:1. Control composition was formulated with no enzymes. Other standard laundry detergents were also included. The composition of Control is provided in Table 1. 10 Preferred detergent composition Ex 1 and Ex 2 had a ratio between first bleach activator (TAED) to second bleach activator (DOBA) of 1:1. Ex 1 was formulated with a combination of protease and amylase. Ex 2 was formulated with a combination of protease and lipase. The composition of preferred detergent compositions is provided 15 in Table 1. c) Washing protocol for determining SRI-values For the determination of the SRI-values, a standard protocol was used, called the machine wash protocol. 20 Said machine wash protocol is as follows: (a) A set of 6 cotton swatches were taken. (b) Each cotton swatch was stained at two different and marked locations with a blackberry fruit stain and a Tomato sunflower oil stain. 25 (c) Colour of the two stains on the cotton swatches were measured before washing to get AE*bw (before wash). (d) 7gpl of the control composition was added to a Miele Washing machine Softronic W4165. (e) A normal white wash cotton intensive cycle 1 hour 56 minutes was selected 30 with water temperature of 40'C. The total wash liquor used was 6 liters. The water used had a hardness 24' French hardness. The wash load was 1.5 kg.

WO 2014/090573 PCT/EP2013/074757 18 (f) The wash load included the stained cotton swatches and two SBL soil strips and the liquor to cloth ratio was 4:1. The stained cotton swatches were not soaked before washing. (g) Post washing the cotton swatches was dried overnight. 5 (h) The after wash reading of the stain on the 6 cotton swatches were recorded. Similarly the stained cotton swatches were prepared and washed as described in the above steps (a) to (h) with a preferred composition and the reading of the swatches before and after wash was recorded. 10 d) Measurement of the delta SRI values The delta SRI value after wash was determined as the difference between the absolute SRI value for a stained cotton swatch washed with the preferred composition and absolute SRI value for a stained cotton swatch washed with the control composition. 15 Delta SRI = (absolute SRI of stained cotton swatch washed with preferred composition) - (absolute SRI of stained cotton swatch washed with control composition) A delta SRI value higher than the LSD (Least significant difference) value indicates a statistically significant difference between the absolute SRI values of stained swatch 20 washed with the preferred composition and the absolute SRI value of stained swatch washed with control composition. The SRI and the delta SRI values of the cotton swatches stained with blackberry fruit stain and tomato - sunflower oil stain and thereafter washed with the control or the 25 preferred compositions with the machine wash protocol described above are provided in Table 2. 30 WO 2014/090573 PCT/EP2013/074757 19 Table Control Ex 1 Ex 2 Ingredients (wt%) (wt%) (wt%) Na-LAS 11.69 11.69 11.69 Non-Ionic 7EO 1.17 1.17 1.17 Sodium Soap 0.63 0.63 0.63 Na disilicate 6.60 6.60 6.60 Soda Ash 20.64 20.64 20.64 Sodium Sulphate 34.579 34.129 34.309 SOKLAN CP5 (ex BASF, polymer of maleic acid 0.39 0.39 0.39 and acrylic acid) SCMC(sodium carboxy methyl cellulose) 0.23 0.23 0.23 Tinopal CBSx 0.02 0.02 0.02 Zeolite 2.613 2.613 2.613 TAED 1.35 1.35 1.35 DOBA 1.35 1.35 1.35 Sodium Percarbonate 12.00 12.00 12.00 EDTMP Ca/Na salt (Dequest 2047) 0.369 0.369 0.369 Citric Acid anhydrous 1.90 1.90 1.90 EHDP (Dequest 2016D) 0.246 0.246 0.246 Antifoam 0.40 0.40 0.40 Savinase 24GTT (protease) 0 0.173 0.173 Lipex 100TB (lipase) 0 0 0.10 Stainzyme Plus 12GT (amylase) 0 0.10 0 Repelotex SF2 0.123 0.123 0.123 Dimorpholino Fluorescer Granular 0.20 0.20 0.20 Blue Carbonate Speckles 1.00 1.00 1.00 Moisture, Salts, NDOM 2.87 2.87 2.87 TOTAL 100.00 100.00 100.00 5 Table 2 WO 2014/090573 PCT/EP2013/074757 20 SRI Delta SRI LSD95p LSD95n Tomato-sunflower oil stain Control 88.0292 0.0000 3.9490 -3.9490 Ex 1 92.0873 4.0582 3.9490 -3.9490 Ex 2 89.9515 1.9224 3.9490 -3.9490 Blackberry fruit stain Control 88.9981 0.0000 4.4120 -4.4120 Ex 1 94.6586 4.6605 4.4120 -4.4120 Ex 2 95.1835 5.1854 4.4120 -4.4120 The results in Table 2 clearly shows that the delta SRI of the preferred compositions (Ex 1 and Ex 2) having a combination of TAED, DOBA and enzymes protease and amylase (Ex 1) or protease and lipase (Ex 2) shows statistically significant 5 improvement in removal of blackberry fruit stain when compared to the control composition. It is also clear from Table 2 that preferred composition (Ex2) is comparatively better than control composition in removal of tomato-sunflower oil stain and the preferred composition (Ex 1) shows statistically significant improvement in removal of tomato and sunflower oil stain when compared to the control composition. 10 Evaluation of the preferred and the comparative compositions in removal of sebum stains: Commercially available detergent powder ArielTM Actilift UK (ex Proctor and Gamble) 15 was used as Control. The preferred granular detergent composition Comp 3 was prepared with a ratio between first bleach activator (TAED) to second bleach activator (DOBA) of 1:1 and having the enzymes protease, amylase and lipase. Other standard laundry detergents 20 were also included. The formulation of Comp 3 is provided in Table 3. One set of 6 cotton swatches stained with sebum stain was rinsed in the machine wash protocol as described above. The SRI values for the stained cotton swatch after wash WO 2014/090573 PCT/EP2013/074757 21 were determined with the procedure as described above and the results were provided in Table 3. The Delta SRI value were also determined and provided in Table 4. Table 3 Ingredients Comp 3 (wt%) Na-LAS 11.69 sNon-lonic 7EO 1.17 Sodium Soap 0.63 Na disilicate 6.23 Soda Ash 20.64 Sodium Sulphate 34.129 CP5 0.39 SCMC 0.23 Tinopal CBSx 0.02 Zeolite 4 A 2.613 TAED 1.35 DOBA 1.35 Sodium Percarbonate 12.00 EDTMP Ca/Na salt (Dequest 2047) 0.369 Citric Acid anhydrous 1.90 EHDP (Dequest 2016D) 0.246 GAG 0.40 Savinase 24GTT (protease) 0.173 Lipex 100TB (lipase) 0.10 Mannaway 4T (mannanase) 0.082 Stainzyme Plus 12GT (amylase) 0.100 Repelotex SF2 0.123 Dimorpholino Fluorescer Granular 0.20 Blue Carbonate Speckles 1.00 Moisture, Salts, NDOM 2.87 TOTAL 100.00 5 Table 4 WO 2014/090573 PCT/EP2013/074757 22 SRI Delta SRI LSD95p LSD95n Sebum stain Ariel' m Actilift UK 88.41 0 4.872 -4.872 Comp 3 93.39 4.979 4.872 -4.872 The results in Table 4 clearly shows that the preferred composition (Comp 3) having a combination of bleach activators TAED, DOBA and enzymes protease, lipase and amylase shows statistically significant improvement in removal of sebum stain when 5 compared to the commercially available comparative composition (ArielTM Actilift UK). It will be appreciated that the illustrated examples provide for a detergent compositions having specific bleach activators and enzymes. 10 It should be understood that the specific forms of the invention herein illustrated and described are intended to be representative only as certain changes may be made therein without departing from the clear teachings of the disclosure.

Claims (1)

1. Claims:

   A cleaning composition comprising:

   (i) hydrogen peroxide or a peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution;

   (ii) a first bleach activator comprising a precursor of peracetic acid; and,

   (iii) a second bleach activator comprising a precursor of C₈ to Cn peroxyacid; wherein the composition comprises:

   (i) a protease; and,

   (ii) a lipase or an amylase or a mixture thereof.

   A cleaning composition as claimed in claim 1 wherein the ratio of first bleach activator to second bleach activator is 5:1 to 1 :5.

   A cleaning composition as claimed in claim 1 or 2 wherein the first bleach activator is a compound from the class of polyacylated alkylenediamines.

   A cleaning composition as claimed in claim 3 wherein the compound from the class of polyacylated alkylenediamines is tetraacetylethylenediamine.

   A cleaning composition as claimed in any one of the preceding claims wherein the second bleach activator is hydroxybenzoic acid derivative of the formula (I) in which R is C₈-Cn alkyl group.

   6 A cleaning composition as claimed in claim 5 wherein the second bleach activator is decanoyloxybenzoic acid and derivatives thereof.

   7 A cleaning composition as claimed in any one of the preceding claims wherein the composition further comprises a mannanase. A cleaning composition as claimed in any one of the preceding claims wherein the peroxygen bleach compound is selected from alkali metal salts of perborates or percarbonates. A cleaning composition as claimed in claim 8 wherein the peroxygen bleach compound is sodium percarbonate. A method of bleaching a bleachable substrate comprising the steps of:

   (i) applying to the substrate, a neat or diluted form of the composition as

   claimed in any of the preceding claims 1 to 9;

   (ii) optionally applying to the substrate a detergent composition; and,

   (iii) rinsing the substrate. Use of a cleaning composition as claimed in any one of the preceding claims 1 to 9 for bleaching stains. Use of a cleaning composition as claimed in any one of the preceding claims 1 to 9 for bleaching fruity or sebum stains on fabrics.