GB2411177A - Liquid bleaching - Google Patents

Abstract

A liquid bleaching comprising: ```a first compartment containing a first aqueous composition comprising a source of active oxygen, such as hydrogen peroxide ```a second compartment containing a second aqueous composition having a pH of 2 to 6 and comprising a compound having the structural Formula I, such as methyl morpholinium acetonitrile methyl sulphate <EMI ID=1.1 HE=19 WI=50 LX=637 LY=1175 TI=CF> <PC>wherein A is a saturated ring formed of four carbon atoms and a heteroatom in addition to the N1 atom, <DL TSIZE=10> <DT>R1<DD>is selected from the group consisting of alkyl, aryl, alkoxy, alcohol and acetonitrile, <DT>R2 and R3<DD>are each selected from the group consisting of hydrogen, alkyl, aryl, alkoxy and alcohol, <DT>Y<DD>is an anionic counterion, and <DT>Z<DD>is in the range of 0 to 10. Also disclosed is a process for treating a surface using the liquid bleach. </DL>

Description

241 1 1 77 - 1 Liquid Composition The present invention relates to a

liquid bleaching composition.

Bleaching compositions containing a source of active oxygen are well known. For example, peroxygen compounds are often included in cleaning compositions to improve their stain- removing properties. Peroxygen compounds, however, are relatively unstable and tend to decompose on storage. Thus, bleaching compositions containing such compounds tend to lose their bleaching power during storage.

To alleviate this problem, bleach activators have been included in peroxygen-containing compositions. In US 6,046,150, for example, a N-methylmorpholinium acetonitrile salt (MMA), such as N-methylmorpholinium acetonitrile methyleulphate (MMAM) is identified as being an effective activator for hydrogen peroxide. Alkaline buffers and surfactants are also included in the composition. In a preferred embodiment, the composition is contained in a dual chamber container. The hydrogen peroxygen and MMA are stored in one chamber at acidic pH, whilst the alkaline buffers and surfactant(s) are contained in the other chamber. The contents of the two chambers may be blended prior to delivering the combined solutions, for example, as a spray.

It has now been found that the combination of MMA and hydrogen peroxide has to be kept at a pH of 1.5 or less for the resulting mixture to be stable under storage. Whilst not wishing to be bound by theory, we believe that the MMA is oxidised by hydrogen peroxide and forms the "active" perimidic acid. Once formed, perimidic acid is relatively unstable and degrades. At very low pHs (less than 1.5), the rate of reaction or oxidation is quite low and therefore the MMA is relatively stable.

Compositions having pHs of 1.5 or less may be hazardous, as they can cause irritation and/or damage upon contact with the skin and/or eyes. Thus, such compositions have to be handled with care, often using protective clothing. In many countries, such compositions have to be labelled with warning symbols and detailed instructions as to how to avoid or minimise damage caused by mishandling the product.

We have found that peroxygen-containing compositions may be stored in a less hazardous manner by storing the peroxygen compound separately from MMA and which are mixed prior to or during use.

Thus, according to the present invention, there is provided a multicompartment dispenser comprising: a first compartment containing a first aqueous composition comprising a source of active oxygen, and, preferably, a pH buffer, a second compartment containing a second aqueous composition having a pH of 2 to 6 and comprising a compound having the structural Formula I A:!_CR2R3C-N-Ye-ZH2O wherein A is a saturated ring formed of four carbon atoms and an O or S heteroatom in addition to the Nl atom, Rl is an alkyl, R2 and R3 are each selected from hydrogen or alkyl, Y is an anionic counterion, and Z is in the range of O to lo.

The contents of the dispenser may be used to treat surfaces, for example, for stain-removal. Thus, according to a further aspect of the present invention, there is provided a process for treating a surface, said process comprising applying to the surface i) a first aqueous composition comprising a source of active oxygen, and ii) a second aqueous composition having a pH of 2 to 6 and comprising a compound having the structural Formula I above.

In one embodiment, the contents of the dispenser is used as a hard surface cleaning composition suitable, for example, for cleaning kitchen and/or bathroom surfaces. In another embodiment, the contents of the dispenser is used as a fabric cleaning composition.

The first aqueous composition and the second aqueous composition may be dispensed as a mixture. Preferably, the first aqueous composition and the second aqueous composition are mixed not more than one hour before being applied to the surface, preferably, not more than five minutes before being applied to the surface, more preferably, not more than one minute before being applied to the surface. Ideally the first and second aqueous compositions are mixed during application to a surface.

The pH of the second aqueous composition is preferably less than 6, ideally less than 5.5, 5.0, 4.5, 4.0, 3.5 or 3.0.

Ideally the pH is at least 2.5, 3.0 or 3.5.

The pH of the first aqueous composition is preferably greater than 5.5 or 6.0, ideally greater than 7.0, 7.5, 8.0, or 8.5, and ideally less than 9. 5.

Ideally sufficient buffer is present so that the mixed solution pH ends up between 6.5 and 9.5 ideally a pH near 7.5-9 will work best.

The pH of each aqueous composition can be adjusted by the addition of a suitable acid or base.

pH Adjusting Agent Preferably the first aqueous composition contains a pH adjusting agent. A pH adjusting agent is a compound or mixture of compounds that can change the pH of the resultant mixture of both aqueous compositions after mixture to a pH of >6.0, ideally >7.0, >7.5 or >8.0. Preferably the pH adjusting agent produces a pH of <9.5 or c9.0 or <8.5 or <8.0. The pH adjusting agent ideally comprises a base.

Suitable bases are selected from hydroxides, carbonates, bicarbonates, sequicarbonates, hydroxides, and silicates.

Certain solvents, like ethanolamine, and certain surfactants, like alkyldimethylamine oxides, may also contribute alkalinity. The pH adjusting agent is present in an amount of from O to 15 weight %, 2 to 8 weight %, 0.5 to weight % of the first aqueous composition.

The pH of the first aqueous composition is preferably higher than the pH of the second aqueous composition.

Ideally, an alkaline buffering means is also present in the first aqueous composition. An alkaline buffering means at a level of from 0.1% to 10% by weight of the first aqueous composition. Preferably, the first aqueous composition herein comprise from 0.2% to 8% by weight of the total composition of a pH buffering means or a mixture thereof, most preferably from 0.3% to 5% by weight By "alkaline buffering means", it is meant herein any compound or mixture of compounds which makes the resulting solution able to resist an increase in hydrogen ion concentration when mixed with the second aqueous composition.

In addition the alkaline buffering means helps to stabilise the source of active oxygen in the aqueous first composition by preventing the pH in the alkaline portion from drifting to higher levels, that accelerate decomposition of peroxides.

Preferred alkaline buffering means for use herein comprise an acid having its pK (if only one) or at least one of its pKs in the range from 7.5 to 10.5, preferably from 8 to 10, and its conjugated base.

pK is defined according to the following equation: pK = - log K where K is the Dissocation Constant of the weak acid in water and corresponds to the following equation: [A] [H] / [ HA] =K where HA is the acid and A is the conjugated base.

The weak acid (HA) and its conjugate base (A) are in equilibrium in the compositions of the present according to the equation: HA<A + H (hydrogen ions).

Preferably the alkaline buffering means herein consists of the weak acid as defined herein and its conjugate base at a weight ratio of the weak acid to its conjugate base of preferably O.l:l to lO:l, more preferably 0. 2:1 to 5:l.

Highly preferred ratio of the weak acid to its conjugate base is l since this is the best combination to achieve optimum buffering capacity.

Preferably a given pH buffering means herein will be used to buffer compositions having a pH between pH = pK - l and pH = pK +l of each of its pK.

Suitable buffering systems are selected from: carbonate/bicarbonate, borate/boric acid or phosphates/phosphoric acid or any other buffer systems described in literature.

Preferably the second aqueous composition does not have a significant amount of pH buffer present. Ideally only the first aqueous composition has a pH buffer.

In order to achieve the target pH after mixing the composition of the acidic second composition with the first composition, it is necessary that the first composition be of a higher pH, and preferably buffered at or slightly above the ultimate target pH.

An advantage of the present invention is that extreme pH conditions are not required to store the contents of the dispenser, especially for stabilising the compound of formula I. Thus, the overall composition of the dispenser may be stored in a non-hazardous manner.

Compound of Formula I The Rl alkyl group may be a straight chain alkyl, a branched chain alkyl or a cyclic alkyl group. The alkyl substituent may comprise l to 12 carbon atoms, preferably, l to 8 carbon atoms, more preferably, l to 6 carbon atoms and, most preferably, l to 4 carbon atoms. In one embodiment, the alkyl substituent is selected from methyl, ethyl, propyl and butyl, preferably the alkyl group is methyl.

Y is an anionic counterion. Suitable counterions include alkyl sulphate ions, especially methyl sulphate ions. Nitrate and/or sulphate counterions may also be employed. Preferably, Y is selected from alkyleulphate, bisulphate, monosulphate, tosylate and mixtures thereof.

Monosulphate and bisulphate salts may exist in equilibrium, the predominance of one over the other being dependent on pH. In a preferred embodiment, Y is an alkyleulphate, such as a Cl to C20 alkyleulphate, for example, methylsulphate, ethylsulphate and propylsulphate.

Preferably, Z is in the range of O to lO, more preferably, l to 6.

In a preferred embodiment, the compound of structural Formula I has the structural Formula II, wherein n is 0 to 24. Preferably, n is 0 to lo, for example, 0. In a preferred embodiment, the compound of the Formula I is a methyl morpholinium acetonitrile (MMA) salt, such as methyl morpholinium acetonitrile methylsulphate. In one preferred embodiment, the MMA methyleulfate compound of the Formula I is a commercially available product sold by BASE, currently in a concentrated aqueous solution under the name Sokalan BM.

(CH2\CH3 o 1,-CH2C-N BY ZH2O Formula II Other preferred salts are illustrated by Formulas III A, III B and III C. mA 7: CH3 CH2CN

MMABS mB

i: CH3: /CH3 O N. O Nl csoG CH2CN

MMAS

IIIC

CH3 CH3 CH2CN

MMATS

The compound of the Formula I, II or III may be included in the first aqueous composition, such that it forms 0.01 to 20 weight %, preferably, 0.1 to 10 weight %, more preferably, 0.25 to 5 weight %, and most preferably 0.5 to 3 weight % of the overall composition contained in the dispenser (e.g. the sum of both the first aqueous composition and second aqueous composition). The compound of the Formula I may form 0.2 to 20 weight %, more preferably, 0.5 to 10 weight %, most preferably, 1 to 6 weight % of the first aqueous composition.

Suitable compounds of the Formula I, II and III are described in US 6,046, 150, the contents of which is incorporated herein by reference.

Two or more compounds of the Formula I, II or III may be included in the same first aqueous composition.

Source of Active Oxygen Any suitable source of active oxygen may be employed in the second aqueous composition. Suitable sources of active oxygen are described in US 6,046,150, the contents of which are incorporated herein by reference. Preferably, a peroxide source, such as hydrogen peroxide, is employed. If desired, two or more sources of active oxygen may be employed in the same second aqueous composition.

The source of active oxygen may be included in the second aqueous composition such that it forms greater than 0 to 8 weight %, preferably, 0.1% to 6 weight %, and more preferably, 0.5 % to 3% weight of the overall composition contained in the dispenser (e.g. the sum of the first aqueous composition and the second aqueous composition).

The ratio of the source of active oxygen (preferably peroxide) to the compound of Formula I may be determined as a molar ratio of peroxide to the compound I. For example, the molar ratio may be 1:1 to 1000:1, more preferably, 1:1 to 300:1 and most preferably 1:1 to 100:1.

Alternatively the above percentages may be expressed as active oxygen concentrations.

The active oxygen concentration refers to the percentage concentration of elemental oxygen, with an oxidation number zero, that could be formed by decomposition of the active oxygen source. For hydrogen peroxide as an example, the amount of elemental oxygen that could be formed from H2O2 is 47%.

Therefore, from 68 g of H2O2 we can get 32g oxygen formed.

The active oxygen concentration can be determined by methods known in the art, such as the iodimetric method, the permanganometric method and the cerimetric method. These methods and the criteria for the choice of the appropriate method are described, for example, in "Hydrogen Peroxide", W. C. Schumo, C.N. Statterfield and R.L. Wentworth, Reinhold Publishing Corporation, New York, 1955 and "Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970.

Preferably, the active oxygen sources according to the present invention are capable of increasing the ability of the compositions to remove oxidisable stains, to destroy malodorous molecules and to kill germs.

Surfactants Whether the first or second aqueous composition, or both, contains surfactant is at the discretion of the formulator. In many instances there is a wide choice available and the choice into which composition the surfactant is placed may not be critical. However, in certain cases, it will be preferable to take into account the pH of the composition when deciding whether to place a particular surfactant in the first or second aqueous composition, i.e. due to chemical stability. In addition the other ingredients in the aqueous chamber will have to be taken into account.

The surfactant may be included in the first aqueous composition and/or the second aqueous composition.

Surfactants may be included such that they form from O.l to weight%, ideally from l.O to lO weight % of the overall composition contained in the dispenser. In one embodiment, the surfactant forms 0.5 to 20 weight %, preferably, from 1.0 to lo weight % of the first and/or second aqueous composition.

The surfactant may be a betaine surfactant. Betaine surfactants may be included such that they form O.l to 20 weight %, preferably, 0.5 to lo weight % of the overall composition contained in the dispenser.

Preferred betaine surfactants herein are according to the formula (R1)(R2)(R3)N -(CH2)n-Y wherein R1 is a hydrocarbon chain containing from 1 to 24 carbon atoms, preferably from 6 to 18 more preferably from to 14 wherein R2 and R3 are hydrocarbon chains containing from 1 to 3 carbon atoms, preferably 1 carbon atom, wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is 1, Y is selected from the group consisting of carboxyl and sulfonyl radicals and wherein the sum of R1, R2 and R3 hydrocarbon chains is from 14 to 24 carbon atoms.

Examples of particularly suitable betaine surfactants include C12-C18 alkyl dimethyl betaine such as coconut- betaine or C10-C16 alkyl dimethyl betaine such as laurylbetaine. Coconutbetaine is commercially available from Seppic under the trade name of Amonyl 2659. Laurylbetaine is commercially available from Albright & Wilson under the trade name Empigen.

Preferred specific betaines include; coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, cetyl dimethyl betaine (available as Lonzaine 16SP from Lonza Corp.), lauryl bis(2-hydroxyethyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl 15 bis-(2- hydroxypropyl)alpha- carboxyethyl betaine, coco dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine, amidobetaines and amidosulfobetaines (wherein the RCONH(CH2)3 radical is attached to the nitrogen atom of the betaine), oleyl betaine (available as amphoteric Velvetex OLB-50 from Henkel), and cocamidopropyl betaine (available as Velvetex BK-35 and BA-35 from Henkel) .

Mixtures of two or more betaine surfactants may be employed, including as examples are mixtures comprising one or more of the following: octyl betaine, cetyl betaine and oleylbetaine.

The surfactants may alternatively or additionally include non-ionic surfactants. Such surfactants may be included such that they form 0.5 to 15 weight%, ideally from 0.5 to 10 weight % of the overall composition contained in the dispenser.

Examples of non-ionic surfactants are fatty acid alkoxylates, such as fatty acid ethoxylates, especially those of formula R(C2H4O)nOH, wherein R is a straight or branched C8-C16 alkyl group, preferably a C'-Cl5 alkyl group, for example, a Cl0-Cl4, alkyl group. n is at least 1, for example, from 1 to 16, preferably 2 to 12, more preferably 3 to 10.

The non-ionic surfactant preferably has a hydrophilic- lipophilic balance (HLB) of 3 to 17, more preferably 6 to 15, and most preferably from 7 to 13.

Examples of suitable fatty alcohol ethoxylates are those made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials are commercially marketed under the trademarks Neodol 25-7 and Neodol 23-6,5 by the Shell Chemical Company. Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary Cl2-Cl3 alcohol having about 9 moles of ethylene oxide; and Neodol 91-10, an ethoxylated C,-Cll primary alcohol having about 10 moles of ethylene oxide.

Other suitable alcohol ethoxylated non-ionic surfactants are Neodol 45-11, which is a similar ethylene oxide condensation products of a fatty alcohol having 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also available from Shell Chemical Company.

Alcohol ethoxylated have also been marketed by the Shell Chemical Company under the Dobanol trademark. Dobanol 91-5 is an ethoxylated C,-Cll fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated Cl2-Cls fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

Other examples of suitable ethoxylated alcohol non ionic surfactants include Tergitol 15-S-7 and Tergitol 15-S 9, both of which are linear secondary alcohol ethoxylated available from Union Carbide Corporation. Tergitol 15-S-7 is a mixed ethoxylated product of a Cll-Cl5 linear secondary alkanol with 7 moles of ethylene oxide and Tergitol 15-S-9 is the same but with 9 moles of ethylene oxide.

Further non-ionic surfactants are, for example, C1O-cl8 alkyl polyglycosides, such as C12-Cl6 alkyl polyglycosides, especially the polyglucosides. These are especially useful when high foaming compositions are desired. Further surfactants are polyhydroxy fatty acid amixes, such as C1O- C18 N-(3methoxypropyl) glycamides and ethylene oxide- propylene oxide block polymers of the Pluronic type.

Further non-ionic surfactants are amine oxides. Amine oxides according to the present invention are those having the formula: RlR2R3NO wherein each of Rl, R2 and R3 is independently a saturated or unsaturated, substituted or unsubstituted, linear or branched hydrocarbon chains of from 1 to 30 carbon atoms.

Preferred amine oxides to be used according to the present invention are amine oxides having the following formula: R1 R2R3NO wherein R is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 18, most preferably from 12 to 14; and wherein R2 and R3 are independently saturated or unsaturated, substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups or 2-hydroxyethyl groups. Rl may be a saturated or unsaturated, substituted or unsubstituted linear or branched hydrocarbon chain.

By substituted it is meant, substituted by any suitable substituent, such as chloride, bromide, iodide, and hydroxy, preferably hydroxy.

Exemplary of the preferred amine oxides are the N hexyldimethylamine oxide, N- octyldimethylamine oxide, N decyldimethylamine oxide, N-dodecyl dimethylamine oxide, N- tetradecyidimethylamine oxide, N-hexadecyl dimethylamine oxide, N- octadecyidimethylamine oxide, Neicosyldimethylamine oxide, and the corresponding amine oxides in which one or both of the methyl groups are replaced with ethyl or 2hydroxyethyl groups and mixtures thereof. The most preferred amine oxides for use herein are N-dodecyldimethylamine oxide and Ntetradecyidimethylmethylamine oxide or a mixture thereof.

Suitable amine oxides for use herein are for instance natural blend C8C10 amine oxides as well as C12-C16 amine oxides commercially available from Hoechst, preferred amine oxide is C12-C14 dimethyl amine oxide commercially available from Alright & Wilson, C12-C14 amine oxides commercially available under the trade name Genaminox from Hoechst or AROMOXO from AKZO.

Alternatively or additionally, an anionic surfactant may also be included in the overall composition contained in the dispenser. The overall composition may contain 0.5 to weight %, preferably, 0.5 to 10 weight % of at least one anionic surfactant.

Anionic surface active agents are frequently provided in a salt form, such as alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or magnesium salts.

Contemplated as useful are one or more sulphate or sulfonate compounds including: alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyleulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarcosinates, acyl isethionates, and N-acyl taurates. Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.

Particularly preferred among the anionic group are alkyl sulphate anionic surfactants. Most preferred are the non-ethoxylated Cl2-ls primary and secondary alkyl sulphates, especially sodium lauryl sulphate.

In addition to their normal purpose of providing detergency and soil removal from surfaces, surfactants may be chosen to also provide suitable viscosity and thickening of either solution or for the solution resulting from combination of the two. For example, a water thin solution of an anionic surfactant when combined with a similar low viscosity solution of an amine oxide can form a solution of appreciably higher viscosity than either of the others.

Enzymes The overall composition contained in the dispenser may or may not include an enzyme. When an enzyme is present in the overall composition, the enzyme may be present in an amount of O to lo weight %, preferably, O to 5 weight % of the composition. The enzyme may be contained in the first aqueous composition and/or the second aqueous composition, preferably the second aqueous composition. Alternatively, the enzyme is contained in a separate compartment of the multi-compartment dispenser.

Where present said enzymes are preferably selected from cellulases, hemicellulases, peroxidases, proteases, gluco- amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.

Preferred enzymes include protease, amylase, lipase, peroxidase cutinase and/or cellulose.

The cellulases usable in the present invention include both bacterial or fungal cellulose. Preferably, they will have a pH optimum of between 5 and 12 and an activity above CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in US-A-4,435,307, JP-A-61078384 and WO-A96/02653 which disclose fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.

EP-A-739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,095,275, DE-OS-2,247,832 and WO-A- 95/26398.

If present, cellulases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the overall composition contained in the dispenser.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching.', i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase.

Peroxidase-containing detergent compositions are disclosed, for example, in WO-A-89/099813, WO-A-89/09813 and in EP-A 540784. Also suitable is the laccase enzyme.

If present, peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the overall composition contained in the dispenser.

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB-A-1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano- CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 Lipase TM and Lipomax TM (Gist-Brocades) and Lipolase TM and Lipolase Ultra TM (Novo) which have found to be very effective when used in combination with the compositions of the present invention.

Also suitable are the lipolytic enzymes described in EP-A- 258068, WO-A-92/05249, WO-A-95/22615, WO-A-94/03578, WO-A- 95/35381 and WO-A-96/00292.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interracial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367, WO-A-90/09446, WO-A-94/14963 and WO-A94/14964.

The lipases and/or cutinases are normally incorporated in either or both composition at a level from 0.0001% to 2% of active enzyme by weight of the overall composition contained in the dispenser.

Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 9-12, developed and sold as ESPERASE TM by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB-A-1, 243,784 to Novo.

Other suitable proteases include ALCALASE TM, DURAZYM TM and SAVINASE TM from Novo and MAXATASE TM, MAXACAL TM, PROPERASE TM and MAXAPEM TM (protein engineered Maxacal) from Gist Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in EP-A- 292623 (particularly pages 17, 24 and 98), and which is calledherein "Protease B", and in EP-A-199,404, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A" herein. Also suitable is what is called herein "Protease C", which is a variant of an alkaline serine Protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagines at position 123, and alanine replaced threonine at position 274.

Protease C is described in WO-A-91/06637. Genetically modified variants, particularly of Protease C, are also included herein.

The proteolytic enzymes are incorporated in either or both compositions at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the overall composition contained in the dispenser.

Amylases (alpha and/or beta) can be included for removal of carbohydratebased stains. WO-A-94/02597 describes cleaning compositions which incorporate mutant amylases (see also WO-A-95/10603). Other amylases known for use in cleaning compositions include both alpha - and beta - amylases. Alpha-amylases are known in the art and include those disclosed in US-A-5,003,257, EP-A-252, 666, WO-A- /91/00353, FR-A-2,676,456, EP-A-285,123, EP-A-525,610, EP-A- 368,341 and GB-A-1,296,839. Other suitable amylases are stability- enhanced amylases described in WO-A-94/18314 and WO-A-96/05295 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO-A-95/10603. Also suitable are amylases described in EP-A-277,216, WO-A-95/26397 and WO-A- 96/23873.

The amylolytic enzymes are incorporated in either or both compositions at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the overall composition contained in the dispenser.

Polymer optionally, the dispenser contains a polymer,which can provide utility, for example, in building viscosity or solids dispersant properties of the formulations. The polymer may be included in the first aqueous composition and/or the second aqueous composition.

Suitable polymers are those that are water-soluble and include polycarboxylate polymers (such as those than can be purchased by Rohm and Haas under the Acusol 445N name) and polycarboxylic acid copolymers (such as can be purchased under the Sokalan CP9 name by BASF).

The polymer may be included in an amount of O to 5 weight %, preferably 0. 01 to 2 weight % of the overall composition contained in the dispenser.

Stabilising Agent Suitable stabilising agents include chelating agents, radical scavengers, antioxidants and mixtures of any thereof.

Chelating Agent The compositions of the present invention may comprise a chelating agent or a mixture thereof as a preferred optional ingredient. Suitable chelating agents may be any of those known to those skilled in the art such as the ones selected from the group comprising phosphonate chelating agents, amino carboxylate chelating agents, other carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'-disuccinic acids, or mixtures thereof. The chelating agents inactivate the metal ions present on the surface of the fabrics and/or in the cleaning compositions (neat or diluted) that otherwise would contribute to the radical decomposition of any peroxygen bleach.

Suitable phosphonate chelating agents to be used herein may include alkali metal ethane 1-hydroxy diphosphonates (HEDP) also known as ethydronic acid, alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphoric acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).

The phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP or ethydronic acid). Such phosphonate chelating agents are commercially available from Monsanto under the trade name BEQUEST.

Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5 disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'-disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins. Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS from Palmer Research Laboratories.

Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA) ,N- hydroxyethylethylenediamine triacetates, nitrilotri- acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa- acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine all-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.

Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASE under the trade name Trilon FSO and methyl glycine all-acetic acid (MGDA).

Further carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.

Particularly preferred chelating agents to be used herein are amino aminotri(methylene phosphoric acid), di- ethylene-triamino-pentaacetic acid, diethylene triamine penta methylene phosphonate, 1-hydroxy ethane diphosphonate, ethylenediamine N,N'- disuccinic acid, and mixtures thereof.

Typically, the compositions according to the present invention comprise up to 5% by weight of the total composition of a chelating agent, or mixtures thereof, preferably from 0.01% to 1.5% by weight and more preferably from 0.01% to 0.5%.

2. Radical Scavenger The compositions of the present invention may comprise a radical scavenger or a mixture thereof. Suitable radical scavengers for use herein include the well-known substituted mono and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures thereof. Preferred such radical scavengers for use herein include di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono- tert-butyl hydroquinone, tert-butyl hydroxy anysole, benzoic acid, toluic acid, catechol, t- butyl catechol, benzylamine, 1,1,3-tris(2-methyl-4- hydroxy- 5-t-butylphenyl) butane, n-propyl-gallate or mixtures thereof and highly preferred is di-tert-butyl hydroxy toluene. Such radical scavengers like N-propyl-gallate may be commercially available from Nipa Laboratories under the trade name Nipanox Sib. Radical scavengers when used, are typically present herein in amounts ranging from up to 10% by weight of the total composition and preferably from 0.001% to 0.5% by weight.

3. Antioxidant The compositions according to the present invention may further comprise an antioxidant or mixtures thereof.

Typically, the compositions herein comprise up to 10% by weight of the total composition of an antioxidant or mixtures thereof, preferably from 0.002% to 5%, more preferably from 0.005% to 2%, and most preferably from 0.01% to 1%.

Suitable antioxidants to be used herein include organic acids like citric acid, ascorbic acid, tartaric acid, adipic acid and sorbic acid, or amines like lecithin, or aminoacids like glutamine, methionine and cysteine, or esters like ascorbil paimitate, ascorbil stearate and triethylcitrate, or mixtures thereof. Preferred antioxidants for use herein are citric acid, ascorbic acid, ascorbil palmitate, lecithin or mixtures thereof.

Such stabilizing agent(s) may be present typically in an amount of 0 to 8 weight %, ideally 0.5 to 6 weight %, of the first aqueous composition.

Other components The overall composition of the dispenser or each of the first and/or second aqueous compositions may further contain up to 10, 5 or 1 weight % of at least one component selected from a fragrance, dye, germicide, preservative and corrosion inhibitor. Mixtures of two or more of such components may also be included. Such components may be contained in the first aqueous composition and/or the second aqueous composition. Alternatively, such compositions may be contained in a separate compartment of the dispenser, as described in further detail below. Water

Water may be present in the overall composition of the dispenser in an amount of O to up to lOO weight %, preferably, l to 99 or 50 to 99 weight %, more preferably, to 98 or 75 to 98 weight %, for example, 80 to 97 weight % of the composition.

Dispensers As mentioned above, the first aqueous composition and the second aqueous composition may be dispensed as a mixture. Preferably, the first aqueous composition and second aqueous composition are mixed immediately prior to or as they are being applied be applied to a surface.

The dispenser of the present invention may optionally comprise means for dispensing a mixture of at least part of the contents of the first compartment and at least part of the contents of the second compartment. Preferably, the two compositions are pre-mixed prior to being delivered onto a surface.

In an alternative embodiment, the two compositions may be directed to a common target. Thus, the dispenser preferably comprises means for directing the first aqueous composition and the second aqueous composition to a common target. The two compositions may be mixed as they are being delivered to the target. Alternatively, the user may be required to mix the compositions once the two compositions have been delivered to the target surface.

Suitable multi-component dispensers include squeezy dispensers, gravity driven dispensers and spray dispensers.

Examples of such dispensers are described in US 5,765,725, WO 01/85595 and EP 0,479,451, respectively.

The dispenser of the present invention contains at least two compartments. The dispenser may contain at least one further compartment.

Example

Claims (20)

1. l. A multi-compartment dispenser comprising: a first compartment containing a first aqueous composition comprising a source of active oxygen, a second compartment containing a second aqueous composition having a pH of 2 to 6 and comprising a compound having the structural Formula I At!-CR2R3C-N-Y ZH2O wherein A is a saturated ring formed of four carbon atoms and a heteroatom in addition to the Nl atom, Rl is selected from the group consisting of alkyl, aryl, alkoxy, alcohol and acetonitrile, R2 and R3 are each selected from the group consisting of hydrogen, alkyl, aryl, alkoxy and alcohol, Y is an anionic counterion, and Z is in the range of O to lo.
2. 2. A dispenser as claimed in claim l, wherein Rl is a Cl to C4 alkyl.
3. 3. A dispenser as claimed in claim 2, wherein Rl is methyl.
4. 4. A dispenser as claimed in any one of the preceding claims, wherein R2 and R3 are both hydrogen.
5. 5. A dispenser as claimed in any one of the preceding claims, wherein the heteroatom of A is oxygen.
6. 6. A dispenser as claimed in any one of the preceding claims, wherein Y is selected from alkyleulphate, bisulphate, monosulphate, tosylate and mixtures thereof.
7. 7. A dispenser as claimed in any one of the preceding claims, wherein the compound is a methyl morpholinium acetonitrile salt.
8. 8. A dispenser as claimed in claim 7, wherein the compound is methyl morpholinium acetonitrile methylsulphate.
9. 9. A dispenser as claimed in any one of the preceding claims, wherein the source of active oxygen is selected from percarbonates, organic peroxides, inorganic peroxides, perborates and peroxymonosulphuric acid.
10. 10. A dispenser as claimed in claim 9, wherein the source of active oxygen is hydrogen peroxide.
11. 11. A dispenser as claimed in any one of the preceding claims, wherein the first aqueous composition and/or the second aqueous composition additionally comprises at least one surfactant and/or water soluble polymer.
12. 12. A dispenser as claimed in claim 11, wherein the surfactant and/or water soluble polymer is present in the second aqueous composition.
13. 13. A dispenser as claimed in any one of the preceding claims, wherein the pH of the second aqueous composition is 2 to 4.
14. 14. A dispenser as claimed in any one of the preceding claims, wherein the pH of the first aqueous composition is 6 to 10. (actually, H202 stability drops off between 9 and 9.5, so 10 is high, but may be a decent number for a claim)
15. 15. A dispenser as claimed in any one of the preceding claims, which comprises means for dispensing a mixture of at least part of the contents of the first compartment and at least part of the contents of the second compartment.
16. 16. A process for treating a surface, said process comprising applying to the surface i) a first aqueous composition comprising a source of active oxygen, and ii) a second aqueous composition having a pH of 2 to 6 and comprising a compound having the structural Formula I A Nl. CR2R3C_ N-Ye 0 wherein A is a saturated ring formed of four carbon atoms and a heteroatom in addition to the N1 atom, R1 is selected from the group consisting of alkyl, aryl, alkoxy, alcohol and acetonitrile, R2 and R3 are each selected from the group consisting of hydrogen, alkyl, aryl, alkoxy and alcohol, Y is an anionic counterion, and Z is in the range of O to 10.
17. 17. A process as claimed in claim 16, wherein the surface is a hard surface or a fabric.
18. 18. A process as claimed in claim 16 or 17, which is a stain-removal process.
19. 19. A process as claimed in any one of claims 16 to 18, wherein the first aqueous composition and the second aqueous composition are applied to the surface as a mixture.
20. 20. A process as claimed in claim 19, wherein the first aqueous composition and the second aqueous composition are mixed not more than two hours before being applied to the surface.