EP2139978B1

EP2139978B1 - Improvements relating to laundry cleaning compositions

Info

Publication number: EP2139978B1
Application number: EP08749624A
Authority: EP
Inventors: Jeremy Jonathan Francis Coen; Kenneth Metcalfe; Joanne Clare O'keeffe
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2007-04-24
Filing date: 2008-04-21
Publication date: 2010-12-22
Anticipated expiration: 2028-04-21
Also published as: EP2139978A1; WO2008129026A1; BRPI0810460A2; ZA200906773B; DE602008004126D1; ATE492621T1

Abstract

The invention provides a laundry cleaning composition comprising: a) at least one laundry adjunct selected from: builder, enzyme, fluorescer, perfume, anti-redeposition polymer, soil release polymer, source of alkalinity, chelating agents other than for hardness ions, bleach or precursor thereof, and, b)a surfactant system comprising: i)at least 1%wt on total surfactantof one or more anionic surfactants, ii)at least 1%wton total surfactant of one or more nonionic surfactants, and, iii)0.5-30%wt on total surfactant of, a mixed cationic surfactant system consisting of a 9:1-1:9 weight ratio of one or more first cationic surfactant of general type(I) and one or more second cationic surfactant of general type (II), wherein: cationic surfactants of type I are quaternary ammonium compounds of the general formula: C4539 (C) CPL -53- [R1 -N+ ( R2 ) 2-CH 2-R3 ] Z- (Type I): in which: Z- is an anionic counter-ion, R1 is a straight or branched C 6to C 20alkyl or alkenyl group, R2 is, independently, a C 1to C4 alkyl group, R3 is H, phenyl, benzyl or C 1to C 20alkyl benzyl, and, cationic surfactants of type II which are quaternary ammonium compounds of the general formula: [R1 -(A) n-N+ ( R4 )((A) lR5 )-(A) mR4 ] Z- (Type II) in which:Z, R1 are as defined above, A is the same or a different C 1-C 4alkoxy group and n, m and l are independently 0 to 30, R4 is, independently, R2 or a C 2-C 4hydroxy-alkyl group, and, R5 is R2 or H with the proviso that should the structure of a type II cationic surfactant be such that it falls within the definition of type I cationic surfactants it shall be counted only as a type I cationic surfactant. Preferably the Type I surfactant is benzalkonium chloride and preferably the Type II surfactant is selected from the group comprising fatty dialkyl dimethyl hydroxy-ethyl ammonium chloride, fatty monoalkyl tri-ethoxy trimethyl ammonium chloride and mixtures thereof. Preferably the ratio of the type I to type II surfactant is in the range 1:1-5:1, more preferably 2:1-4:1.

Description

Technical Field:

The present invention relates to laundry cleaning compositions which comprise cationic surfactants.

Background of the Invention:

Laundry detergent products are characterised by the presence of one or more of builder, enzyme, fluorescer, perfume, anti-redeposition polymer, soil release polymer, source of alkalinity, chelating agents other than for hardness ions and bleach or precursor thereof.
Such compositions also contain surfactant. Typical surfactants in general use include both anionic and nonionic surfactants. The anionic surfactants are generally sulphated or sulphonated materials. Linear alkyl benzene sulfonate (LAS), for example, is a widely used type of anionic surfactant. The nonionic surfactants are generally ethoxylated materials. There has been some lesser use of other surfactant types. The role of these surfactants is to assist in the removal of soil from textile articles and to maintain the soil in suspension so that it can be separated from the articles by rinsing.
One major consumer concern relevant to the formulation of laundry products is malodour. One possible source of malodour is bacterial activity (although there are several others). It is believed that the trend towards lower wash temperatures, increasing use of bleach-free detergents (e.g. colour-care powders or liquid detergents) lower water usage and shorter wash times leads to much greater numbers of bacteria surviving the laundering process than in previously commonplace 'boil-wash' conditions.
Cationic surfactants are a broad range of surfactants that are used as textile softeners, hair conditioners, biocides, antistatic agents, corrosion inhibitors and emulsifiers. Cationic biocide materials have been proposed for use in detergent compositions as a means of reducing malodour. These are typically quaternary ammonium compounds with a mixture of long and short alkyl chains and may contain aryl or alk-aryl groups. A well known example of this class of materials is benzalkonium chloride (alkyl dimethyl benzyl ammonium chloride) Benzalkonium chloride is a mixture of alkylbenzyl dimethylammonium chlorides of various alkyl chain lengths. The greatest anti-microbial activity is believed to be associated with the C12-C14 alkyl derivatives. The biocidal activity of cationic surfactants has long been believed to occur by a complex mechanism including the steps of (i) adsorption onto the bacterial cell surface; (ii) diffusion through the cell wall; (iii) binding with the cytoplasmic membrane, (iv) disruption of the cytoplasmic membrane; (v) leakage of cytoplasmic constituents; (vi) cell lysis leading to cell death.
Cationic surfactant materials have also been proposed for use to improve cleaning in laundry detergent products. Typical cationic surfactants proposed for such use are fatty dimethyl hydroxy ethyl or fatty trimethyl ammonium salts. EP 0008829 discloses the use of a broad range of cationic surfactants including C12-14 alkyl methyl dihydroxyethyl ammonium chloride and tallow alkyl trimethyl ammonium chloride. US 2004/058835 discloses quaternary methyl/dihydroxyethyl, dimethyl/hydroxyethyl or trimethyl ammonium salts in which the fatty chain is C8-18 alkyl. Suitable examples of these materials are Praepagen HY^™ (a fatty alkyl dimethyl hydroxy-ethyl ammonium chloride, ex Clariant) and Servamine KAC^™ (dodecyl trimethyl ammonium chloride, ex Condea). Many of these materials have less pronounced biocidal properties.
WO 00/34423 (Unilever, published 2000) discloses how the incorporation of cationic materials can lead to difficulties due to the formation of complexes between the anionic detergent and the cationic materials. The cationic materials proposed in WO 00/34423 include didecyl methyl benzyl ammonium chloride, didecyl dimethyl ammonium chloride, didecyl methyl propyl ammonium chloride and 'numerous' other such compounds. WO 00/34423 states that the biocidal cationic compounds can be used either singly or in combination with one another.
The present invention is concerned with the incorporation of the biocidal cationic materials in laundry detergent products without loss of overall cleaning performance.

Brief Description of the Invention:

We have determined that when specific mixtures of structurally different cationic surfactants are employed together with anionic/nonionic surfactant systems, effective biocidal activity can be obtained against microbes involved in malodour production whilst maintaining acceptable cleaning performance.
Accordingly the present invention provides laundry cleaning composition comprising:

a) at least one of builder, enzyme, fluorescer, perfume, anti-redeposition polymer, soil release polymer, source of alkalinity, chelating agents other than for hardness ions, bleach or precursor thereof, and,
b) a surfactant system comprising:
1. i) at least 1%wt on total surfactant of one or more anionic surfactants,
2. ii) optionally at least 1%wt on total surfactant of one or more nonionic surfactants, and,
3. iii) 0.5-30%wt on total surfactant of, a mixed cationic surfactant system consisting of a 9:1-1:9 weight ratio of one or more first cationic surfactant of general type (I) and one or more second cationic surfactant of general type (II), wherein:
  - cationic surfactants of type I are quaternary ammonium
  - compounds of the general formula
    in which:
    - Z^- is an anionic counter-ion,
    - R¹ is a straight or branched C₆ to C₂₀ alkyl or alkenyl group,
    - R² is, independently, a C₁ to C₄ alkyl group,
    - R³ is H, phenyl, benzyl or C₁ to C₄ alkyl benzyl, and, cationic surfactants of type II which are quaternary ammonium compounds of the general formula:

Z, R¹ are as defined above,
A is the same or a different C₁-C₄ alkoxy group and n, m and 1 are independently 0 to 30,
R⁴ is, independently, R² or a C₂-C₄ hydroxy-alkyl group, and,
R is R² or H

In general the cationic surfactants of type I are believed to be more effective biocides than those of type II. Cationic surfactants of type II are believed to be more tolerant to precipitation by anionic surfactants, such as LAS, than those of type I. It will be noted that type II surfactants comprise either alkoxy groups or hydroxyl-alkyl groups. These oxygen-containing species are located either between the quaternary nitrogen atom and the relatively long chain alkyl group, or in part replace or extend the lower alkyl substituents. As noted above the compositions of the invention must always contain both a Type I (believed to be more biocidal) cationic and a Type II (believed to assist in cleaning) cationic. If the Type II cationic is present which also falls within the description of a Type I cationic then a further Type II cationic must be present so that there is always some Type II but non-Type I cationic present.
The preferred weight ratio of Type I to Type II surfactant is preferably in the range 1:1 to 5:1, more preferably 2:1 to 4:1, with ratio's around 3:1 being particularly preferred. It is believed that the most preferred combinations show not only no significant reduction in cleaning performance but also a synergistic benefit as regards microbial kill.
Any suitable counter-ion may be used in the cationic surfactant. Preferred counter-ions for the cationic surfactants include halogens (especially chlorides), methosulphate, ethosulphate, tosylate, phosphate and nitrate. Chlorides are preferred. It is preferable that no further cationic surfactants are present other than the up to 30% forming the mixed cationic system.
In order that the present invention may be further understood, it is described below with reference to various preferred features.

Detailed Description of the Invention:

Cationic Materials:

In the formulae given above it is preferred that the longer chain R¹ is an unbranched, linear chain. The preferred chain length of R¹ is C₈-C₂₀, more preferably C₁₂-C₁₈ and the carbon-carbon bonds are preferably saturated. The shorter chain R² is preferably methyl or ethyl. The aromatic group R³ is preferably phenyl (such that the quaternary nitrogen is effectively substituted with a benzyl group). R⁴ is preferably methyl, ethyl or hydroxyl-ethyl. Where present, A is preferably ethoxy (-CH₂-CH₂-O-). Where, for example a substituent appears more than once in a formula the two or more groups substituted need not be the same.
A preferred class of Type I surfactant has R¹ as fatty (preferably C₁₂-C₁₈) alkyl. This is believed to give optimal biocidal properties. Preferably, R² is methyl and R³ is phenyl. A particularly preferred Type 1 surfactant is benzalkonium chloride (which is a fatty (C10-C18) alkyl dimethyl benzyl ammonium chloride). various grades of this material are available, and ones rich in the C12-C16 fatty residues are preferred. Other Type I surfactants envisaged for use in the present invention include Cetyl trimethyl ammonium chloride (CTAC).
A preferred class of Type II surfactant is:
wherein: Z^-, R¹, R² and R⁴ are as defined above, A is a C₁-C₄ alkoxy and n is an integer from 0 to 20. It is particularly preferred that A is an ethoxy (O-CH₂-CH₂) group. The number of equivalent moles of alkylene oxide present ('n') can be zero provided that at least one of the R⁴ groups is a hydroxy alkyl. Praepagen HY^™ (fatty alkyl dimethyl hydroxy-ethyl ammonium chloride, ex Clariant) is an example in which R¹ is a fatty residue, n=0, R² is methyl and the R⁴ groups consist of one methyl and one hydroxy-ethyl.
A further preferred class of type II surfactant is:
wherein: Z^-, R¹ and R² are as defined in claim 1, A is a C₁-C₄ alkoxy group (preferably an ethoxy group) and n is an integer from 2 to 30. More preferably, R¹ is a C₈ to C₁₈ alkyl group. More preferably, R² is a C₁ to C₃ alkyl group. Suitable materials of these alkoxylated quaternary ammonium type IIb surfactants are disclosed by P&G in WO9 43364 , 43365 , 43371 , 43387 , 43389 , 43390 , 43391 and 43393A .
A further preferred class of type II surfactant is:
wherein: Z^-, R¹ and R² are as defined in claim 1, A is a C₁-C₄ alkoxy group, x and y are each 1 to 8 and x+y is from 2 to 9. Ethoxylated amine cationic surfactants of Type IIc have been disclosed by Colgate Palmolive in US5994285
The type IIa surfactant is preferably selected from the group comprising fatty alkyl dimethyl hydroxy-ethyl ammonium chloride, fatty alkyl tri-ethoxy trimethyl ammonium chloride and mixtures thereof.

Anionic and Nonionic surfactants:

In general, the surfactants of the surfactant system may be chosen from the surfactants described in "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & 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.
Levels of total surfactant in powder and tablet products are preferably from 5 to 65%wt on product. Preferred are levels of 30-60%wt. For liquid products the levels of total surfactant is generally between 10 and 50%wt. Preferred are levels of 28-50%wt. In this paragraph total surfactant includes cationic surfactant and the anionic and non-ionic present.

• Anionic Surfactants:

Suitable anionic surfactants for the detergent compounds which may be used are usually 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 being used to include the alkyl portion of higher acyl radicals, including alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, N-alkoyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulphonates and acyl methyl taurates, especially their sodium, magnesium ammonium and mono-, di- and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms, still more preferably 12 to 15 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether phosphates and alkyl ether carboxylates may contain from one to 10 ethylene oxide or propylene oxide units per molecule, and preferably contain 1 to 3 ethylene oxide units per molecule.
Another preferred group of anionic surfactants are the methyl ester sulphonates (MES or FAES). These have a preferred alkyl chain length of 8-18 carbons.
The preferred surfactants for powders and tablets are salts of linear alkylbenzene sulphonate (LAS) and primarily alcohol suphate (PAS) and mixtures thereof. These all typically have a preferred alkyl chain length of 8-18 carbons, and are more preferably C12-C16.
The preferred surfactants for liquids are fatty acids, linear alkylbenzene sulphonate (LAS), alkyl ether sulphates (AES), methyl ester sulphonates (MES or FAES) and mixtures thereof. These all typically have a preferred alkyl chain length of 8-18 carbons.
While the role of the anionic surfactant is generally as a cleaning agent, anionic surfactant particularly in the form of fatty acid (soap), may be present with the principal objective of acting as an antifoam. Fatty acid is not counted towards the total of anionic surfactant in determining the levels present.

• Nonionic Surfactants:

Nonionic detergent surfactants are well-known in the art. They normally consist of a water-solubilizing polyalkoxylene or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived, for example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof), preferably having from 8 to 20 carbon atoms, monocarboxylic acids having, from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylene. Also common are fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms. In any of the mono- and di-alkanolamide derivatives, optionally, there may be a polyoxyalkylene moiety joining the latter groups and the hydrophobic part of the molecule. In all polyalkoxylene containing surfactants, the polyalkoxylene moiety preferably consists of from 2 to 20 groups of ethylene oxide or of ethylene oxide and propylene oxide groups. Amongst the latter class, particularly preferred are those described in European specification EP-A-225,654 .
Also preferred are those ethoxylated nonionics which are the condensation products of fatty alcohols with from 9 to 18 carbon atoms condensed with from 1 to 35, preferably 3 to 11 moles of ethylene oxide. Examples of these are the condensation products of C9-18 alcohols with on average 3 to 9 moles of ethylene oxide.
Preferably the nonionic surfactant of the present inventions is a C - ethoxylated alcohol, comprising 3 to 9 ethylene oxide units per molecule. More preferred are C_12-15 primary, linear ethoxylated alcohols with on average 5 to 9 ethylene oxide groups, more preferably on average 7 ethylene oxide groups. Neodol^™ 25-7, a C12-C15 alcohol ethoxylate (with 7 moles of ethoxylation) is a suitable non-ionic surfactant.
Alkyl poly-glucoside surfactants may replace some or all of the non-ionic surfactant.
While it preferred that some relatively low level of nonionic surfactant is present, it can be omitted completely to save cost. However the presence of nonionic improves oily soil cleaning and is believed to assist in the solubilisation of the cationic surfactants in the mixture. This is believed to improve the efficacy of the antimicrobial cationics and/or overall product stability

Other surfactants:

In addition to the non-ionic, anionic and cationic present in the compositions of the invention, the composition may comprise relatively small amounts (preferably less than 10%wt on product, more preferably less than 5%wt) of zwitterionic and/or amphoteric surfactants. Suitable zwitterionics include carbobetains and suitable amphoterics include amine-oxides. These additional surfactants are generally present as foam and/or detergency boosters.

Other Materials:

As noted above, the compositions of the invention are intended for use in laundering clothes and consequently will comprise one or more of: builder, enzyme, fluorescer, perfume, anti-redeposition polymer, soil release polymer, source of alkalinity, chelating agents other than for hardness ions, bleach or precursor thereof. Preferred compositions comprise builder and perfume and will be free of bleach or precursors thereof.

Builders and Salts:

Builder materials may be selected from 1) calcium sequestrant materials, 2) calcium precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof. Examples of commonly used calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid. Examples of commonly used precipitating builder materials include sodium orthophosphate, sodium carbonate and sodium soaps. Examples of commonly used calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. 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-0,384,070 .
The composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
Preferably the builder is present in an amount of from 0 to less than 60 wt % based on the weight of the total composition. More preferably, the amount of builder is from 0 to 25 wt %, although for carbonate builders higher levels may be used.

• Phosphate Builders:

Alternatively, or additionally phosphate builders may be used. In this art the term 'phosphate' embraces diphosphate, triphosphate, and phosphonate species. The phosphate builder (if present) may for example be selected from alkali metal, preferably sodium, pyrophosphate, orthophosphate and tripolyphosphate (STP), and mixtures thereof.

• Carbonate Builders:

For low cost formulations carbonate (including bicarbonate and sesquicarbonate) and/or citrate may be employed as builders. These builders also have environmental benefits as compared with phosphates. A particularly important class non-phosphorus builders are the alkali metal carbonates, e.g. sodium carbonate. These carbonates counteract calcium water hardness reacting with the calcium ions to form insoluble calcium carbonate. Unfortunately, calcium carbonate deposits tend to adhere to fabrics in the wash liquor, causing the well-known "ashing" phenomenon.
It is possible avoid ashing by including a seed crystal substance such as calcite for the precipitated calcium carbonate to grow on. Calcite is a particular crystalline form of calcium carbonate. The seed crystals with a grown layer of calcium carbonate readily remain dispersed in the wash liquor.
It is also possible to reduce the impact of ashing by using a combination of carbonate and a low level of STP.
The sodium carbonate may be present in a dense or light form. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt %, preferably from 10 to 50 wt %, more preferably from 20 to 40 wt %, based on the weight of the total composition. These amounts are most relevant when a spray drying process is used to make the formulation. If a non-tower processing route is used to make the formulation the sodium carbonate may be present in an amount of from 30 to 80 wt %, preferably 40 to 70 wt %, based on the weight of the total composition. However, compositions containing little or no sodium carbonate are also within the scope of the invention.

● Aluminosilicate Builders:

The aluminosilicate (if present) 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 for example as disclosed in GB 1 473 202 (Henkel ) and mixed crystalline/amorphous aluminosilicates for example as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates for example as disclosed in EP 164 514B (Hoechst ).
Preferred aluminosilicates have the general formula: 0.8-1.5 Na₂O.Al₂O₃ 0.8-6SiO₂. 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. The ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1. 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. However, according to a preferred embodiment of the invention, 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. Suitably 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.
Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
The compositions of the invention may contain from 0 to 85 wt % of an inorganic salt, preferably from 1 to 80 wt %, more preferably from 10 to 75 wt %, most preferably from 20 to 65 wt %, based on the weight of the total composition. The inorganic salt may be present in an amount of from 0 to 60 wt %, preferably from 1 to 40 wt %, based on the weight of the total composition.
Suitable inorganic salts include alkaline agents such as alkali metal, preferably sodium, carbonates, sulphates, silicates, metasilicates as independent salts or as double salts etc. Preferably the inorganic salt is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sulphate, burkeite, sodium silicate and mixtures thereof. A preferred alkali metal carbonate is sodium carbonate.
Sodium sulphate may suitably be present in an amount of from 10 to 50 wt -, preferably from 15 to 40 wt %, based on the weight of the total composition. Compositions containing little or none of the independent solid sodium sulphate are also within the scope of the invention. The composition according to the invention preferably may comprise sodium carbonate and sodium sulphate, wherein the total amount of sodium carbonate and sodium sulphate is of from 40 to 80 wt -, and preferably from 60 to 70 wt %, based on the weight of the total composition.
The composition according to the invention may comprise a ratio of sodium carbonate to sodium sulphate within the range of from 0.1:1 to 5:1, preferably 0.5:1 to 1.5:1, most preferably from 1:1. Burkeite may suitably be present in an amount of from 40 to 80 wt %, preferably from 60 to 70 wt %, based en the weight of the total composition. Compositions containing burkeite as the only non-builder salt are within the scope of the invention, as are compositions containing little or no burkeite. Burkeite is of the formula Na.CO .2Na.SO₄, and this is different from sodium carbonate and sodium sulphate as previously described as it is a double salt comprised of the combination of sodium carbonate and sodium sulphate.
In addition to the inorganic salts listed above the detergent composition according to the invention may further comprise sodium silicate, the sodium silicate may be present at levels of from 0 to 20 wt %, preferably from 1 to 10 wt %, based on the weight of the total composition. Preferably the total amount of sodium carbonate, sodium sulphate, burkeite and sodium silicate is from 50 to 85 wt %, most preferably from 65 to 80 wt %, based on the weight of the total composition.
Inorganic soluble salts, when present are believed to further improve the biocidal activity of the compositions of the present invention by increasing the stress on the microbes present in the wash liquor, thus the use of carbonate built or phosphate built compositions is preferred.

Enzymes:

One or more enzymes may be present in a composition of the invention.
Especially contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases, oxidases, pectate lyases, and mannanases, or mixtures thereof. Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included. The protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Preferred commercially available protease enzymes include Alcalase^™, Savinase^™, Primase^™, Duralase^™, Dyrazym^™, Esperase^™, Everlase^™, Polarzyme^™, and Kannase^™, (Novozymes A/S), Maxatase^™, Maxacal^™, Maxapem^™, Properase^™, Purafect^™, Purafect OxP^™, FN2^™, and FN3^™ (Genencor International Inc.).
Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839 , or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060 . Commercially available amylases are Duramyl^™, Termamyl^™, Termamyl Ultra^™, Natalase^™, Stainzyme^™, Fungamyl^™ and BAN^™ (Novozymes A/S), Rapidase^™ and Purastar^™ (from Genencor International Inc.).
Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 , and WO 98/012307 . Commercially available cellulases include Celluzyme^™, Carezyme^™, Endolase^™, Renozyme^™ (Novozymes A/S), Clazinase^™ and Puradax HA^™ (Genencor International Inc.), and KAC-500(B)^™ (Kao Corporation).
Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P. fluorescens, Pseudomonas sp. strain SD 705 ( WO 95/06720 and WO 96/27002 ), P. wisconsinensis ( WO 96/12012 ), a Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus ( JP 64/744992 ) or B. pumilus ( WO 91/16422 ).
Other examples are lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 and WO 97/07202 .
Preferred commercially available lipase enzymes include Lipolase^™ and Lipolase Ultra^™, Lipex^™ (Novozymes A/S). Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618 , WO 95/10602 , and WO 98/15257 . Commercially available peroxidases include Guardzyme^™ and Novozym^™ 51004 (Novozymes A/S).
Composition may comprise a phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32 and/or a cutinase classified in EC 3.1.1.74.
Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
The presence of enzymes allows less surfactant to be used for cleaning and it is believed that this can assist in the antimicrobial benefit of the invention as some microbes are believed to metabolize residual surfactants.

Fluorescers:

In order to further improve whiteness, the composition preferably comprises a fluorescent agent (optical brightener).
Fluorescent agents are well known and many such fluorescent agents are available commercially. 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 classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine 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: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]trazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1, 3, 5-triazin-2-yl)] amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.

Perfumes:

Compositions according to the present invention will preferably comprise perfume. Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
Some or all of the perfume may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius and pro-fragrances which can produce such components.

Polymers:

The composition may comprise one or more polymers. These can be present for a number of reasons such as dye-transfer inhibition (DTI), soil-dispersants, soil-release, anti-redeposition, crystal growth inhibition or physical stabilization of the product form Examples are carboxymethylcellulose, poly(vinylpyrrolidone), poly (ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
Modern detergent compositions typically employ polymers as so-called 'dye-transfer inhibitors'. These prevent migration of dyes, especially during long soak times. Any suitable dye-transfer inhibition agents may be used in accordance with the present invention. Generally, such dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese pthalocyanine, peroxidases, and mixtures thereof. Nitrogen-containing, dye binding, DTI polymers are preferred. Of these polymers and co-polymers of cyclic amines such as vinyl pyrrolidone, and/or vinyl imidazole are preferred. Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (as a class, referred to as "PVPVI") are also preferred. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000, as determined by light scattering as described in Barth, et al., Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization". The preferred PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched. Suitable PVPVI polymers include Sokalan^(™) HP56, available commercially from BASF, Ludwigshafen, Germany. Also preferred as dye transfer inhibition agents are polyvinylpyrrolidone polymers ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 2000,000, and more preferably from about 5,000 to about 50,000. PVP's are disclosed for example in EP-A-262,897 and EP-A-256,696 . Suitable PVP polymers include Sokalan^(™) HP50, available commercially from BASF. Compositions containing PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1. The amount of dye transfer inhibition agent in the composition according to the present invention will be from 0.01 to 10 %, preferably from 0.02 to 5 %, more preferably from 0.03 to 2 %, by weight of the composition. It will be appreciated that the dye transfer inhibition agents will assist in the preservation of whiteness by preventing the migration of dyes from coloured articles to white ones.
Other polymers used in laundry compositions include soil-release and anti-redeposition polymers as well as polymers which improve powder properties.
Polymeric dispersing agents can advantageously be utilized in the compositions herein, especially in the presence of layered silicate builders. Suitable polymeric dispersing agents include polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is also believed that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release, peptization, and anti-redeposition.
Any polymeric soil release agent known to those skilled in the art can optionally be employed in compositions according to the invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures. Generally the soil release polymers will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols), for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokalan (Trade Mark) HP22. Especially preferred soil release polymers are the sulphonated non-end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie).

Other Chelating Agents:

A heavy metal sequestrant may also be present. Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.
Heavy metal sequesterants are known to impede microbial growth by reducing the levels of metal ions available for some enzymic processes.

Bleaches:

Detergent compositions according to the invention may comprise 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.
Especially preferred is 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). Also of interest are peroxybenzoic acid precursors, in particular, N,N,N-trimethylammonium toluoyloxy benzene sulphonate.
Alternatively the present invention may be used in a formulation that is used to bleach via air, or an air bleach catalyst system. In this regard the bleaching composition substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system. 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).
Photobleaches may also be employed In the context of the present invention a "photo-bleach" is any chemical species which forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction. Preferred photo-bleaches include singlet oxygen photo-bleaches and radical photo-bleaches. Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Z1 where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably the phthalocyanin has 1-4 SO₃X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba).
Bleaches, where present, are believed to assist in antimicrobial efficacy of the present formulations.

Further Components, Form and Manufacture:

Other materials that may be present in detergent compositions of the invention lather control agents or lather boosters as appropriate; dyes and decoupling polymers. As noted above, the foam control agent (antifoam) may comprise a fatty acid. Prifac 5908 is a suitable fatty acid. As also noted above, suitable lather boosters for use in the present invention include cocamidopropyl betaine (CAPB), cocomonoethanolamide (CMEA) and amine oxides.
Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate. One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt %, based on the weight of the total composition.
Shading dyes can be used to counteract the tendency of the hue of fabrics to move away from white. Preferred dyes are violet or blue. Direct violet and direct blue dyes are preferred. Particularly preferred dyes are as described in WO2005/003274 (Unilever) and WO2005/003277 (Unilever). The most preferred shading dyes are bis azo direct dyes, particularly those of the direct violet 9, 35 and 99 type and acid azine dyes such as acid violet 50 and acid blue 98. The compositions of the invention may be of any suitable physical form, for example, particulates (powders, granules, tablets), liquids, pastes, gels or bars. According to one especially preferred embodiment of the invention, the detergent composition is in particulate form, preferably powder form. The composition can be formulated for use as hand wash or machine wash detergents. The 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 post-dosing (drymixing) 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.
Preferred solid laundry cleaning composition according to the invention comprise:

a) at least 20-wt of aluminosilicate, phosphate or carbonate builder or mixtures thereof,
b) at least 10-wt of a surfactant system comprising:
1. i) 2-24 parts by weight of AOS, LAS, PAS, soap and mixtures thereof
2. ii) 1-3 parts by weight of 3-7EO ethoxylated alcohol.

Preferably these compositions comprise:

a) less than 40%wt of aluminosilicate, phosphate or carbonate builder or mixtures thereof,
b) less than 20%wt of a surfactant system comprising:
1. i) 2-4 parts by weight of LAS, PAS, soap and mixtures thereof
2. ii) 1-3 parts by weight of 3-7EO ethoxylated alcohol.

Liquid detergent compositions may be prepared by admixing the essential and optional ingredients in any desired order to provide compositions containing the ingredients in the requisite concentrations.
Preferred liquid laundry cleaning composition according to the invention comprise:

a) optionally citric acid and/or soap, and
b) a surfactant system comprising at least 12%wt (on product):
1. i) 2-10 parts by weight of MES, AES, LAS, PAS, and mixtures thereof, and
2. ii) 1-3 parts by weight of ethoxylatedalcohol

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, ingredients such as enzymes, bleach ingredients, sequestrants, polymers and perfumes may be added separately.
In order that the invention may be further understood it will be further explained with reference to the following non-limiting examples.

EXAMPLES:

Evaluation Methodology

The method used is a micro-plate suspension test for bactericidal efficacy corresponding to British / European Standard BS EN 1040 conditions. It is used to assess the efficacy of disinfectants against bacteria in suspension. The bacteria used are either skin isolates of Staphylococcus and Corynebacteria or a standard strain of Escherichia Coli (ATCC10536).
Formulations are allowed a contact period with the bacterial cells, then are chemically neutralised. Survivors are enumerated by serial dilution and viable counting in liquid media. The data are then used to calculate the log reduction of the bacterial population elicited by the test disinfectant.

EXAMPLE 1

Liquid formulations were evaluated at 4 g/l surfactant in 40°FH water at 40°C with 30 minutes contact. Compositions were made up as shown in table 1 below. Examples of the invention (with both types of cationic surfactant present) are shown in bold.

Table 1

	A	B	C	D	E	F
Neodol 25-7 (ex. Shell)	13%	11.7%	11.7%	11.7%	11.7%	11.7%
Prifac 5908 (ex. Uniqema)	3%	3%	3%	3%	3%	3%
Praepagen HY (ex. Clariant) TYPE II cationic	0%	1.6%	1.2%	0.8%	0.4%	0.0%
Benzalkonium Chloride (ex. Riedel-de-Haen) TYPE I cationic	0%	0.0%	0.4%	0.8%	1.2%	1.6%
NaOH (ex. Fisher Chemicals)	0.25%
NaCl (ex. Fisher Chemicals)	0.25%
Water	To 100%

Performance of the comparative formulations

	Formulation
LOG (Reduction in Bacteria)	A	B	C	D	E	F
Staphylococcus (Skin Isolate)	0	2.6	3.4	4.8	4.8	5
Escherichia coli (ATCC 10536)	0.2	0	0.8	2	2.4	1.3

EXAMPLE 2

UK Persil Colour powder was used at 8g/l in 6°FH water at 25°C with 30 minutes contact. In examples H to L the concentration of the powder is adjusted to allow for addition of cationic surfactants at the levels shown in the table. Examples of the invention are again shown in bold.

	G	H	I	J	K	L
UK Persil Colour powder	100%	98.7%	98.7%	98.7%	98.7%	98.7%
Praepagen HY TYPE II cationic	0.00%	1.30%	0.98%	0.65%	0.33%	0.00%
Benzalkonium Chloride TYPE I cationic	0.00%	0.00%	0.33%	0.65%	0.98%	1.30%

Performance of the comparative powder formulations

LOG (Reduction in Bacteria)	G	H	I	J	K	L
Staphylococcus (Skin Isolate)	1	0.6	0.4	1.6	2.4	1.3

EXAMPLE 3

Liquid formulations evaluated at 8 g/l in 12°FH water at 40°C with 30 minutes contact. Examples of the invention are shown in bold

	M	N	O	P	Q
Na Linear Alkylbenzene Sulphonate (Petrelab 550 ex. Petresa)	11.7%	11.7%	11.7%	11.7%	11.7%
Neodol 25-7 (ex. Shell)	5.8%	5.8%	5.8%	5.8%	5.8%
Praepagen HY (ex. Clariant) TYPE II cationic	1.5%	1.1%	0.7%	0.4%	0.0%
Benzalkonium Chloride (ex. Riedel de Haen) TYPE I cationic	0.0%	0.4%	0.7%	1.1%	1.5%
NaCl (ex. Fisher Chemicals)	0.25%
Water,	To 100%

Performance of comparative liquid formulations

LOG (Reduction in Bacteria)	M	N	O	P	Q	Persil Bio Liquigel	Ariel Bio Liquid (UK)
Corynebacterium (NCIMB 40928)	1.0	0.3	1.0	3.4	3.0	0.6	0.9
Staphylococcus (Skin Isolate)	2.3	2.0	3.0	1.5	3.0	0.7	2.4

EXAMPLE 4

Liquid formulations evaluated at 8 g/l in 12°FH water at 40°C with 30 minutes contact. Examples of the invention are shown in bold.

	R	S	T	U	V
Na Linear Alkylbenzene Sulphonate (Petrelab 550 ex. Petresa)	2.9%	2.9%	2.9%	2.9%	2.9%
Neodol 25-7 (ex. Shell)	14.6%	14.6%	14.6%	14.6%	14.6%
Praepagen HY (ex. Clariant) TYPE II cationic	1.5%	1.1%	0.7%	0.4%	0.0%
Benzalkonium Chloride (ex. Riedel de Haen) TYPE I cationic	0.0%	0.4%	0.7%	1.1%	1.5%
NaCl (ex. Fisher Chemicals)	0.25%
Water	To 100%

Performance of comparative liquid formulations

LOG (Reduction in Bacteria)	R	S	T	U	V	Persil Bio Liquigel	Ariel Bio Liquid (UK)
Corynebacterium (NCIMB 40928)	1.0	0.7	2.0	1.7	0.4	0.6	0.9

EXAMPLE 5

Examples of the present invention are shown in bold.

	W	X	Y	Z	AA	AB	AC	AD	AE
Na LAS (Petrelab 550 ex Petresa)	12	12	12	12	12	12	12	12	12
Na Coco PAS Emal 10 ex Kao Corporation)	5	5	5	5	5	5	5	5	5
Neodol 25-7EO (ex. Shell)	1	1	1	1	1	1	1	1	1
C₁₂-₁₆ tri-ethoxy TAC (GVS-Nr.12320 ex. Clariant) TYPE II cationic	0	0	0	0	1	0.75	0.5	0.25	0
Praepagen HY (ex.Clariant) TYPE II cationic	1	0.75	0.5	0.25	0	0	0	0	0
BKC (ex.Riedel de Haen) TYPE I cationic	0	0.25	0.5	0.75	0	0.25	0.5	0.75	1
STP	2	2	2	2	2	2	2	2	2
Na Carbonate (ex Fisher)	20	20	20	20	20	20	20	20	20
Na Sulphate (ex Fischer)	45	45	45	45	45	45	45	45	45
Water	To 100%

The compositions in Example 5 were evaluated using product concentrations of 5 g/l in 12°FH water at 25°C at a contact time of 60 minutes. The resulting performance is summarised in the table below: -

LOG (Red. in Bacteria) W X Y Z AA AB AC AD AE

Corynebacterium (NCIMB 40928) 2.7 3.0 3.3 4.0 3.0 4.0 4.3 4.0 3.7

EXAMPLE 6

Examples of the present invention are shown in bold.

	AF	AG	AH	AI	AJ	AK
Neodol 25-7EO (ex Shell)	20	18	18	18	18	18
Lauric Acid (Uniquema)	1.5	1.5	1.5	1.5	1.5	1.5
Praepagen HY (ex. Clariant) TYPE II cationic	0	2	1.5	1	0.5	0
BKC (ex. Riedel de Haen) TYPE I cationic	0	0	0.5	1	1.5	2
Sodium Tripolyphosphate	2	2	2	2	2	2
Zeolite 4A	15	15	15	15	15	15
Sodium Carbonate (ex Fisher)	35	35	35	35	35	35
Sodium Sulphate (ex. Fisher)	15	15	15	15	15	15
Water	To 100%

The compositions in Example 6 were evaluated using product concentrations of 5 g/l in 12°FH water at 25°C at a contact time of 60 minutes. The resulting performance is summarised in the table below: -

LOG (Reduction in Bacteria) AF AG AH AI AJ AK

Corynebacterium (NCIMB 40928) 0.0 2.7 3.0 3.3 4.0 3.7

EXAMPLE 7:

Examples of the present invention are shown in bold.

	AL	AM	AN	AO	AP
Na LAS (Petrelab 550 ex Petresa)	12	12	12	12	12
Na Coco PAS Emal 10 ex Kao Corporation)	5	5	5	5	5
C₁₂-₁₆ tri-ethoxy TAC (GVS-Nr.12320 ex. Clariant) TYPE II cationic	0	0.5	1	1.5	2.0
BKC (ex. Riedel de Haen) TYPE I cationic	2	1.5	1	0.5	0
STP	2	2	2	2	2
Sodium Carbonate (ex Fisher)	20	20	20	20	20
Sodium Sulphate (ex Fischer)	45	45	45	45	45
Water and minors to 100%

The compositions in Example 7 were evaluated using product concentrations of 5 g/l in 12°FH water at 25°C at a contact time of 60 minutes. The resulting performance is summarised in the table below: -

LOG (Reduction in Bacteria) AL AM AN AO AP

Corynebacterium (NCIMB 40928) 4.0 4.7 3.7 2.7 2.7

Claims

A laundry cleaning composition comprising:
a) at least one of builder, enzyme, fluorescer, perfume, anti-redeposition polymer, soil release polymer, source of alkalinity, chelating agents other than for hardness ions, bleach or precursor thereof, and,

b) a surfactant system comprising:
i) at least 1%wt on total surfactant of one or more anionic surfactants,

ii) optionally at least 1%wt on total surfactant of one or more nonionic surfactants, and,

iii) 0.5-30%wt on total surfactant of, a mixed cationic surfactant system consisting of a 9:1-1:9 weight ratio of one or more first cationic surfactant of general type (I) and one or more second cationic surfactant of general type (II), wherein: cationic surfactants of type I are quaternary ammonium compounds of the general formula
in which:
Z^- is an anionic counter-ion,

R¹ is a straight or branched C₆ to C₂₀ alkyl or alkenyl group,

R² is, independently, a C₁ to C₄ alkyl group, R³ is H, phenyl, benzyl or C₁ to C₂₀ alkyl benzyl, and, cationic surfactants of type II which are quaternary ammonium compounds of the general formula:

in which:
Z, R¹ are as defined above,

A is the same or a different C₁-C₄ alkoxy group and n, m and 1 are independently 0 to 30,

R⁴ is, independently, R² or a C₂-C₄ hydroxy-alkyl group, and,

R⁵ is R² or H with the proviso that should the structure of a type II cationic surfactant be such that it falls within the definition of type I cationic surfactants it shall be counted only as a type I cationic surfactant.
A laundry cleaning composition according to claim 1, wherein part or all of the type II surfactant is:
wherein: Z^-, R¹, R² and R⁴ are as defined in claim 1, A is a C₁-C₄ alkoxy group and n is an integer from 0 to 20
A laundry cleaning composition as claimed in claim 1, wherein part or all of the type II surfactant is:
wherein: Z^-, R¹ and R² are as defined in claim 1, A is a C₁-C₄ alkoxy group and n is an integer from 2 to 30.
A laundry cleaning composition as claimed in claim 1, wherein part or all of the type II surfactant is:
wherein: Z^-, R¹ and R² are as defined in claim 1, A is a C₁-C₄ alkoxy group, x and y are each 1 to 8 and x+y is from 2 to 9.
A laundry cleaning composition as claimed in any one of claims 1-4 wherein the ratio of the type I to type II surfactant is in the range 1:1-5:1, preferably 2:1-4:1.
A laundry cleaning composition as claimed in any one of claims 1-5 wherein the type I surfactant is benzalkonium chloride.
A laundry cleaning composition according to claim 2 wherein the type IIa surfactant is selected from the group comprising fatty alkyl dimethyl hydroxy-ethyl ammonium chloride, fatty monoalkyl tri-ethoxy trimethyl ammonium chloride and mixtures thereof.
A laundry cleaning composition according to any of claims 1-7 which is a solid and which comprises:
a) at least 20%wt of aluminosilicate, phosphate or carbonate builder or mixtures thereof,

b) at least 10%wt of a surfactant system comprising:
i) 2-24 parts by weight of AOS, LAS, PAS, soap and mixtures thereof

ii) 1-3 parts by weight of 3-7EO ethoxylated alcohol.
A composition according to claim 8 which comprises:
a) less than 40%wt of aluminosilicate, phosphate or carbonate builder or mixtures thereof,

b) less than 20%wt of a surfactant system comprising:
i) 2-4 parts by weight of LAS, PAS, soap and mixtures thereof

ii) 1-3 parts by weight of 3-7EO ethoxylated alcohol.
A laundry cleaning composition according to any of claims 1-7 which is a liquid and which comprises:
a) optionally citric acid and/or soap, and

b) a surfactant system comprising at least 12%wt on product:
i) 2-10 parts by weight of MES, AES, LAS, PAS, and mixtures thereof

ii) 1-3 parts by weight of ethoxylated alcohol