EP2931864B1

EP2931864B1 - Cleaning composition

Info

Publication number: EP2931864B1
Application number: EP13799259.0A
Authority: EP
Inventors: Jayashree Anand; Prachi Makarand DESAI; Amit Deshpande; Shailesh Sadanand NAIK
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2012-12-12
Filing date: 2013-11-26
Publication date: 2016-08-17
Anticipated expiration: 2033-11-26
Also published as: AU2013357709A1; SA515360548B1; BR112015011173A2; EP2931864A1; AU2013357709B2; CL2015001611A1; ZA201504272B; WO2014090573A1; CN104837980A

Description

Field of the invention

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 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

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.
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.
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 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).
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.
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 (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 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.
One such attempt was done in WO11117617A1 (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.
US 2009130224 A1 (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 binders.
US 2008113036 A1 (Reinhardt et al. 2008 ) discloses an improved bleach activator and bleach activator compositions having synergistic effects on difficult to remove stains 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 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 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. 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 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.

Summary of the invention

According to the first aspect, the present invention provides for 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 C₁₁ peroxyacid;

(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 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.

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 aspect for bleaching fruity or sebum stains on fabrics.
The invention will now be explained in more details.

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 aqueous solution, a first bleach activator, a second bleach activator, a protease and a lipase or an amylase or mixtures thereof.

Cleaning composition:

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.
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.
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 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-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.
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.

Peroxygen bleach compound:

Disclosed composition includes a peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution. Hydrogen peroxide sources are well known in 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.
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 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 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 µm, most preferably from about 400 to about 600 µm. If coated percarbonate is used, the preferred coating materials include mixtures of carbonate 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 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 composition the composition has 5 to 20 wt % more preferably 10 to 15 wt% of the peroxygen bleach compound.

Bleach activator:

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.
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.
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:

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).
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:

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 (I)
in which R is C₈-C₁₁ alkyl group.
Preferably the second bleach activator is decanoyloxybenzoic acid (DOBA) and derivatives thereof.

Enzyme:

Disclosed composition includes a protease and a lipase or amylase or a mixture thereof.

Protease:

Disclosed cleaning composition includes a protease. Suitable protease includes those 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 Carlsberg, subtilisin 309, subtilisin147 and subtilisin 168 (described WO8906279A1 ). Examples of trypsin-like proteases are trypsin from porcine or bovine origin and the Fusarium protease described in WO8906270A1 and WO9425583A1 . The protease is preferably from B.subtilis. Preferred commercially available protease includes Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and Kannase™, Maxatase™, Maxacal™, Maxapem™, Properase™, Purfast®, Effectenz®, Purafect™, Purafect OxP™, FN2™, and FN3™ (Genencor International Inc.).
Protease from a strain of Bacillus having maximum activity throughout the pH range of 8 to 12 is highly preferred and includes commercially available Esperase™ and Savinase™.
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:

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.
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 WO9613580A1 or lipases from Pseudomonas species which includes lipase from P. alcaligenes or P. pseudoalcaligenes ( EP0218272 A1 ), P. cepacia ( EP0331376B1 ), P. stutzeri ( GB 1 ,372,034 ), P. fluorescens, Pseudomonas species strain SD 705 ( WO95/06720 and WO96/27002 ), P. wisconsinensis ( WO96/12012 ) or lipases from Bacillus species which includes lipases from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131 , 253-360), B. stearothermophilus ( JP64/744992 ) or B. pumilus ( WO 91/16422 ). Other examples include lipase variants such as those described in WO92/05249 , WO94/01541 , EP407225 , EP260105 , WO95/35381 , WO96/00292 , WO95/30744 , WO94/25578 , WO95/14783 , WO95/22615 , WO97/04079 and WO97/07202 .
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 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 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 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.

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 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 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 International Inc.).

Mannanase:

Preferably the disclosed composition includes mannanase. Examples of suitable 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 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 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 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:

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, 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.
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 sulphating higher C₈ to C₁₈ alcohols for example from tallow or coconut oil. Other preferred anionic surfactant include sodium and potassium alkyl C₉ to C₂₀ benzene sulphonates, particularly sodium linear secondary alkyl C₁₀ to C₁₅ benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the 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 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.
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.
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 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.
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 contribution from soap is preferably from 0 to 30 wt% of the total anionic.
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).
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.
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:

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.
Examples of calcium sequestrant materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetraacetic acid.
Examples of precipitating builder materials include sodium orthophosphate and sodium 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), 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 µm (as measured by The Mastersizer 2000 particle size analyzer using laser diffraction ex Malvern™).
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 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.
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 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 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 include ethylenediamine tetraacetate (EDTA), ethylenediamine disuccinate (EDDS), and the aminopolyphosphonates such as ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphonate (DETPMP).
When present the composition may include one or more polymers. Examples include carboxymethylcellulose, 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 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 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.
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 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 distyryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, diamine stilbene disulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH and pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2- (4-styryl-3-sulfophenyl) -2H-napthol [I,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-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) HP22. Especially preferred soil release polymer are the sulphonated non-end-capped polyesters described and claimed in WO9532997A (Rhodia Chimie).
The invention will now be explained in details with the help of non-limiting exemplary embodiments.

Examples

Evaluation of the preferred and the comparative compositions in removal of blackberry

stain and tomato-sunflower stain:

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 ΔE* for each stain. It is defined as ΔE* and is calculated as: $ΔE = \sqrt{{(L *_{stain - after} - L *_{clean - cloth})}^{2} + {(a *_{stain - after} - a *_{clean - cloth})}^{2} + {(b *_{stain - after} - b *_{clean - cloth})}^{2}}$
L*, a*, and b* are the coordinates of the CIE 1976 (L*, a*, b*) colour space, determined using a standard spectrophotometer. ΔE* can be measured before and after the stain is washed, to give ΔE*bw (before wash) and ΔE*aw (after wash).
ΔE after wash is the difference in L a b colour space between the clean (unwashed) fabric and the stained fabric after wash. So a ΔE after wash of zero means that a stain is completely removed.
SRI is defined as: $SRI = 100 - ΔE *_{aw}$
A SRI of 100 means complete removal of a stain. The higher the SRI value, the greater is the stain removal potential.
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.

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.
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 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.
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.
(c) Colour of the two stains on the cotton swatches were measured before washing to get ΔE*_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 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.
(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.
(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.

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. $Delta SRI = (absolute SRI of stained cotton swatch washed with preferred composition) - (absolute SRI of stained cotton swatch washed with control composition)$
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 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 preferred compositions with the machine wash protocol described above are provided in Table 2.

Table1

	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 and acrylic acid)	0.39	0.39	0.39
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

Table 2

	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 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.

Evaluation of the preferred and the comparative compositions in removal of sebum stains:

Commercially available detergent powder ArielTM Actilift UK (ex Proctor and Gamble) 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 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 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-Ionic 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

Table 4

	SRI	Delta SRI	LSD95p	LSD95n
Sebum stain
Ariel™ 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 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.
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

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 C₁₁ 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-C₁₁ alkyl group.
A cleaning composition as claimed in claim 5 wherein the second bleach activator is decanoyloxybenzoic acid and derivatives thereof.
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.