DE69715463T2 - DETERGENTS CONTAINING A MIXTURE OF A QUATERIAL AMMONIUM TENSIDE AND AN ALKYL SULFATE - Google Patents

Description

Technical area

The present invention relates to cleaning compositions or components thereof containing cationic surfactant and long chain anionic surfactants. The cleaning compositions are generally intended for use in laundry and dishwashing processes to provide improved greasy stain removal and cleaning benefits, particularly on hydrophilic fabric surfaces.

Background of the invention

It is known to use cationic surfactants in cleaning compositions. For example, GB 2 040 990 A describes granular detergent compositions comprising cationic surfactants. EP-A-0 495 554 describes cleaning compositions comprising quaternary ammonium surfactants and cellulase enzymes.

Other cleaning components commonly used in cleaning agents are anionic surfactants, which are known to be used in cleaning compositions to assist in the removal of stains.

However, long chain length alkyl sulfate surfactants, although showing good stain removal performance when used under high temperature washing conditions (for example at 60ºC or above), show relatively poor solubility at low washing temperatures, for example around 40ºC. This is particularly a concern as there is an increasing trend to use lower washing temperatures. This leads to inefficient use of such surfactants at lower washing temperatures and poor stain removal. The problem is particularly pronounced at short washing cycle times.

US-A-4 747 977 relates to liquid cleaning compositions which are substantially free of monohydric C₁₋₆ alcohols.

US-A-4 333 862 relates to a liquid cleaning composition comprising anionic surfactant, nonionic surfactant and cationic surfactant.

WO-95 10591-A1 relates to cleaning compositions containing protease enzymes which are carbonyl hydrolase variants with improved proteolytic activity.

EP-0 495 554-A1 relates to a cleaning composition comprising a quaternary ammonium compound and a cellulase.

The present invention aims to improve the efficiency of using these long-chain anionic surfactants. Applicants have found that in combination with a specific class of quaternary ammonium surfactants, the stain removal performance of long-chain anionic surfactants. The invention is particularly useful in cleaning compositions containing high levels of long alkyl chain anionic surfactants.

Without wishing to be bound by theory, Applicant believes that the use of the specific quaternary ammonium surfactants together with the long chain anionic surfactants results in two compounds forming an ion pair which is a pseudo-non-ionic surfactant with improved solubility. It also results in improved cleaning of hydrophilic fabrics since the repulsion between the negatively charged fabric surface and the anionic surfactant is minimized.

Furthermore, it is believed that following the degradation of the oily soil, the cationic surfactants used in the present invention can also form complexes with the fatty acids and any other negatively charged degradation product produced, increasing their solubility and improving the removal of greasy, oily soil and overall cleaning performance.

All references cited in this specification are incorporated herein by reference.

Summary of the invention

The present invention relates to a granular cleaning composition or component thereof comprising:

(a) a mixture of cationic surfactants of formula I:

R¹R²R³R⁴N⁺X⁻ (I)

wherein R¹ is a hydroxyalkyl group having no more than 6 carbon atoms; each of R² and R³ is independently selected from C₁₋₄ alkyl or alkenyl; R⁴ is a C₅₋₁₁ alkyl or alkenyl and wherein for at least 10% by weight of the mixture R⁴ is a C₅₋₉ alkyl or alkenyl; and

X⊃min; is a counterion; and

(b) an anionic surfactant of formula II

R&sup5;OSO&sub3;&supmin;M&spplus; (II)

wherein R⁵ is an alkyl or alkenyl group having at least 14 carbon atoms, or as found in a secondary alkyl sulfate, and M⁺ is a counter ion.

Unless otherwise indicated, alkyl or alkenyl as used herein may be branched, linear or substituted. Substituents may be, for example, aromatic groups, heterocyclic groups containing one or more N, S or O atoms, or halogen substituents.

Detailed description of the invention Cationic surfactant

The cationic surfactant is generally present in the composition or a component thereof in an amount of no more than 60% by weight, preferably no more than 10% by weight, most preferably in an amount of no more than 4.5% by weight or even 3% by weight. The benefits of the invention can be found even with very small amounts of the cationic surfactant of formula I. Generally, at least 0.01% by weight, preferably at least 0.05% by weight or at least 0.1% by weight of the cationic surfactant will be present in the cleaning compositions of the invention.

R¹ in formula I is a hydroxyalkyl group having not more than 6 carbon atoms, and preferably the -OH group is separated from the quaternary ammonium nitrogen atom by not more than 3 carbon atoms. Preferred R¹ groups are -CH₂CH₂OH, -CH₂CH₂CH₂OH, - CH₂CH(CH₃)OH and -CH(CH₃)CH₂OH.

-CH₂CH₂OH, -CH₂CH₂CH₂OH are most preferred, and -CH₂CH₂OH is especially preferred. Preferably, R² and R³ are each selected from ethyl and methyl groups, and most preferably both R² and R³ are methyl groups. Preferred R⁴ groups have at least 6 or even at least 7 carbon atoms. R⁴ must have no more than 9 carbon atoms, or even no more than 8 or 7 carbon atoms. Preferred R⁴ groups are linear alkyl groups. Linear R⁴ groups having 8 to 11 carbon atoms, or 8 to 10 carbon atoms are preferred. Preferably, each of R2 and R3 is selected from C1-4 alkyl and R4 is C6-11 alkyl or alkenyl.

While pure or substantially pure cationic compounds are within the scope of this invention, it has been found that mixtures of the cationic surfactants of formula I can be particularly effective. For example, mixtures of the compounds of formula I may be useful wherein at least 10, preferably at least 20, weight percent of the cationic surfactants have R4 with C5-9. Other suitable examples include, for example, surfactant mixtures in which R4 may be a combination of linear C8 and C10 alkyl groups or C9 and C11 alkyl groups. According to one aspect of the invention, a mixture of cationic surfactants of formula I is present in the composition, the mixture comprising a shorter alkyl chain surfactant of formula I and a longer alkyl chain surfactant of formula I. The cationic surfactant having the longer alkyl chain is preferably selected from the surfactants of formula I wherein R4 is an alkyl group having n carbon atoms, where n is 8 to 11; the surfactant having the shorter alkyl chain is preferably selected from those of formula I wherein R4 is an alkyl group having (n-2) carbon atoms. Such cationic surfactant mixtures preferably comprise from 30 to 90% by weight of the total cationic surfactant of formula I in a longer alkyl chain length, most preferably at least 50% by weight of the mixture. Preferably, the mixtures will contain from 35 to 65% by weight, preferably from 5 to 70% by weight, most preferably at least 40% by weight of the cationic surfactant of formula I having the shorter alkyl chain.

X in formula I can be any counterion which provides electrical neutrality, but is preferably selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, more preferably selected from methyl sulfate, chloride, bromide and iodide. The halide ions, especially chloride, are most preferred.

Anionic surfactant

The anionic surfactant is generally present in the composition in amounts of at least 5% up to 50% by weight of the cleaning composition. Preferably, at least 10% by weight of anionic surfactant of formula II will be present in the composition and the benefit of the invention is even more useful in cleaning compositions comprising one or more surfactants of formula II in amounts of 20% by weight and above.

The anionic surfactants essential for the present invention are linear or branched primary or secondary alkyl sulfates of formula II.

R&sup5;OSO&sub3;&supmin;N&spplus; (II)

wherein R⁵ is alkyl or alkenyl of at least 14 carbon atoms, or as found in secondary alkyl sulfates. Preferably, R⁵ has no more than 22 carbon atoms, more preferably 14 to 20, and most preferably 16 to 18 carbon atoms. The primary alkyl sulfate surfactants are preferred. M⁺ is selected from alkali metals, alkaline earth metals, alkanolammonium, and ammonium.

In preferred embodiments of the cleaning compositions of the invention comprising anionic surfactant, there will be a significant excess of anionic surfactant, preferably a weight ratio of anionic to cationic surfactant of from 50:1 to 2:1, most preferably from 30:1 to 8:1. However, the benefits of the invention will also be achieved if the ratio of cationic surfactant to anionic surfactant is substantially stoichiometric, for example from 3:2 to 4:3.

In a preferred embodiment of the invention, the essential cationic surfactant of Formula I is intimately mixed with one or more anionic surfactants prior to addition to the other cleaning composition components to provide a readily soluble anionic/cationic ion pair. It may be useful to intimately mix substantially stoichiometric amounts of anionic and cationic surfactant prior to addition to any other detergent components, including any additional anionic surfactant.

Additional cleaning components

The cleaning compositions or components thereof according to the present invention may also contain additional detergent components. The precise nature of these additional components, and their incorporation levels, will depend on the physical form of the composition or component thereof and on the precise nature of the washing operation for which it is to be used.

The compositions of the invention, or components thereof, preferably contain one or more additional detergent components selected from additional surfactants, builders, sequestering agents, bleaching agents, bleach precursors, bleach catalysts, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, additional soil suspending and anti-redeposition agents, soil release agents, perfumes and corrosion inhibitors.

Additional surfactant

The cleaning compositions or components thereof according to the invention preferably contain an additional surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

A typical listing of anionic, nonionic, ampholytic and zwitterionic classes and species of these surfactants is given in USP 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Volumes I and II of Schwartz, Perry and Berch). A listing of suitable cationic surfactants is given in USP 4,259,217, issued to Murphy on March 31, 1981.

When present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and/or non-ionic surfactants.

Anionic surfactant

In a particularly preferred embodiment of the invention, the cleaning compositions additionally comprise an anionic surfactant. Any anionic surfactant useful for cleaning purposes is suitable. These may comprise salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Other suitable anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Additional anionic sulfate surfactant

Additional anionic sulfate surfactants suitable for use in the compositions of the invention include alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, the C5-C17 acyl N-(C1-C4 alkyl) and N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkyl polysaccharides such as the sulfates of alkyl polyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C9-C22 alkyl sulfates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C11-C18, most preferably C11-C15 alkyl sulfate which has been ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention uses mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzenesulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkanesulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkylglycerol sulfonates, fatty acylglycerol sulfonates, fatty oleylglycerol sulfonates, and any mixtures thereof.

Particularly preferred compositions of the present invention additionally comprise an alkylbenzenesulfonate surfactant of formula III:

R&sup6;SO&sub3;&supmin;M'&spplus; (III)

wherein R⁶ is C₁₀-C₁₆ alkylbenzene, preferably C₁₁-C₁₃ alkylbenzene; M'⁺ is selected from alkali metals, alkaline earth metals, alkanolammonium and ammonium.

Particularly preferred compositions of the invention comprise an alkylbenzene surfactant, preferably in such weight ratios with the alkyl sulfate of formula II such that the weight ratio of II to III is from 15:1 to 1:2, most preferably from 12:1 to 2:1.

Preferred amounts of the alkyl sulfate surfactant of Formula II are from 3 to 40%, or more preferably 6 to 30%, by weight of the cleaning composition. Preferred amounts of the alkylbenzenesulfonate surfactant of Formula III in the cleaning composition are at least 1%, preferably at least 2%, or even at least 4%. Preferred amounts of the alkylbenzenesulfonate surfactant are up to 23%, more preferably no more than 20%, most preferably up to 15% or even 10%.

Anionic carboxylate surfactant

Suitable anionic carboxyl surfactants include the alkyl ethoxycarboxylates, the alkyl polyethoxypolycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps, as described herein.

Suitable alkyl ethoxycarboxylates include those having the formula RO(CH2CH2O)xCH2COO- M+ , wherein R is a C6 to C18 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material wherein x is 0 is less than 20%, and M is a cation. Suitable alkyl polyethoxypolycarboxylate surfactants include those having the formula R0-(CHR1-CHR2-O)-R3, wherein R is a C6 to C18 alkyl group, x is 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl acid residue, succinic acid residue, hydroxysuccinic acid residue, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl moiety attached to a secondary carbon atom. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid, and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkaline metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R- CON(R¹)CH₂COOM, where R is a linear or branched C₅-C₁₇ alkyl or alkenyl group, R¹ is a C₁-C₄ alkyl group, and M is an alkali metal ion. Preferred examples are the myristyl and oleoylmethyl sarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred. Linear or branched alkoxylated groups are suitable.

Preferred alkoxylated surfactants can be selected from the classes of nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol and the nonionic ethoxylate condensation products with propylene oxide/ethylenediamine adducts.

Nonionic alkoxylated alcohol surfactant

The condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxide, especially ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can be either straight or branched, primary or secondary and generally contains 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols with an alkyl group containing 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic polyhydroxy fatty acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z, wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is C5-C31 hydrocarbyl, preferably straight chain C5-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly linked to the chain, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic fatty acid amide surfactant

Suitable fatty acid amide surfactants include those having the formula: R6CON(R7)2 wherein R6 is an alkyl group having from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl and -(C2H4O)xH, wherein x is in the range of from 1 to 3.

Nonionic alkyl polysaccharide surfactant

Suitable alkyl polysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group of 6 to 30 carbon atoms and a hydrophilic polysaccharide, e.g., a polyglycoside, group of 1.3 to 10 saccharide units.

Preferred alkyl polyglycosides have the formula

R²O(CnH₂nO)t(Glycosyl)x

wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl groups contain 10 to 18 carbon atoms; n is 2 or 3; t is 0 to 10, and · is 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkylamphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R³(OR⁴)xN⁰(R⁵)₂, wherein R³ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkylphenyl group or mixtures thereof containing 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms, or mixtures thereof; x is 0 to 5, preferably 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl group having 1 to 3, or a polyethylene oxide group having 1 to 3 ethylene oxide groups. Preferred are C₁₀-C₁₈-alkyldimethylamine oxide and C₁₀-C₁₋₁₈-acylamidoalkyldimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM)C2M Conc., manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the cleaning compositions or components thereof according to the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are the compounds having the formula R(R')2N+R2COO-, where R is a C6-C18 hydrocarbyl group, each R1 is typically C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group. Preferred betaines are C12-C18 dimethyl ammoniohexanoate and the C10-C18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Additional cationic surfactants

The compositions of the invention are preferably substantially free of quaternary ammonium compounds of formula I but wherein one of R¹, R², R³ or R⁴ represents an alkyl chain group longer than C₁₁. Preferably the composition should contain less than 1% by weight, preferably less than 0.1% by weight or even less than 0.05% by weight and most preferably less than 0.01% by weight of compounds of formula I having a linear (or even branched) alkyl group having 12 or more carbon atoms.

Another suitable group of cationic surfactants which can be used in the cleaning compositions of the invention are cationic ester surfactants. The cationic ester surfactant is a compound having surfactant properties comprising at least one ester bond (ie -COO-) and at least one cationically charged group. Preferred cationic ester surfactants are water dispersible.

Suitable cationic ester surfactants, including choline ester surfactants, have been disclosed, for example, in U.S. Patent Nos. 4,228,042, 4,239,660, and 4,260,529.

In preferred cationic ester surfactants, the ester bond and the cationically charged group in the surfactant molecule are separated by a spacer group consisting of a chain comprising at least three atoms (i.e., a chain length of three atoms), preferably three to eight atoms, more preferably three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixture thereof, provided that any nitrogen or oxygen atoms in the chain are only bonded to carbon atoms in the chain. Thus, spacer groups having, for example, -O-O- (i.e., peroxide), -N-N- and -N-O- bonds are excluded, while spacer groups having, for example, -CH₂-O-CH₂- and -CH₂-NH- CH₂-bonds are included. In a preferred aspect, the spacer chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

alkalinity

An alkalinity system is preferably present in the cleaning compositions of the present invention to achieve optimum cationic surfactant performance. The alkalinity system comprises components capable of providing alkalinity species in solution. Examples of alkalinity species include carbonate, bicarbonate, hydroxide, the various silicate anions, percarbonate, perborates, perphosphates, persulfate and persilicate. Such alkalinity species can be formed, for example, when alkaline salts selected from alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate including crystalline layered silicate salts and percarbonate, perborates, perphosphates, persulfate and persilicate salts and any mixtures thereof are dissolved in water.

Examples of carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and any mixtures thereof with ultrafine calcium carbonate, as disclosed in German Patent Application No. 2 321 001, published on November 15, 1973.

Suitable silicates include the water-soluble sodium silicates having a SiO2:Na2O ratio of 1.0 to 2.8, with ratios of 1.6 to 2.0 being preferred and the ratio of 2.0 being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate having a SiO2:Na2O ratio of 2.0 is the most preferred silicate.

Preferred crystalline layered silicates for use herein have the general formula

NaMSixO2x+1·yH₂O

where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline sodium layered silicates of this type are disclosed in EP-A-0 164 514 and processes for their preparation is disclosed in DE-A-34 17 649 and DE-A-37 42 043. Herein, x in the above general formula preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is -Na₂Si₂O₅, available from Heochst AG as NaSKS-6.

Water soluble builder compound

The cleaning compositions according to the present invention preferably contain a water soluble builder compound, typically present in the cleaning compositions at a level of from 1 to 80%, preferably from 10 to 70%, most preferably from 20 to 60%, by weight of the composition.

Such water-soluble builder compounds include the water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated by not more than two carbon atoms, borates, phosphates and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builder can be of monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for cost and performance reasons.

Suitable carboxylates containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates having three carboxy groups include in particular water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 379 241, lactoxysuccinates described in British Patent No. 1 389 732 and aminosuccinates described in Dutch Application 7 205 873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylates described in British Patent No. 1 387 447.

Polycarboxylates having four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propanetetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates having sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Patent No. 3,936,448 and the sulfonated pyrolyzed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates having up to three carboxy groups per molecule, more specifically citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures, are also considered useful builder components.

Borate builders, as well as builders containing borate-forming materials that can generate borate under detergent storage or washing conditions, are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, Sodium and potassium orthophosphate, sodium polymeta/phosphate, wherein the degree of polymerization is in the range of about 6 to 21, and salts of phytic acid.

Partially soluble or insoluble builder compound

The cleaning compositions of the present invention, or components thereof, may contain a partially soluble or insoluble builder compound, typically present in cleaning compositions at a level of from 1 to 80%, preferably from 10 to 70%, most preferably from 20 to 60%, by weight of the composition.

Examples of largely water soluble builders include sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO₂)z(SiO₂)y]·xH₂O, where z and y are at least 6; the molar ratio of z to y is 1.0 to 0.5, and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, containing 10 to 28%, more preferably 18 to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the names zeolite A, zeolite B, zeolite P, zeolite X, zeolite HS and mixtures thereof. Zeolite A has the formula

Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] xH 2 O

where · is 20 to 30, especially 27. Zeolite X has the formula

Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ]·276H 2 O.

Another preferred aluminosilicate zeolite is zeolite MAP builder. The zeolite MAP can be present at a level of 4 to 80 wt%, more preferably 15 to 40 wt% of the compositions.

Zeolite MAP is described in EP 384070 A (Unilever). It is defined as an alkali metal alumino silicate of the zeolite P type having a silicon to aluminium ratio of not more than 1.33, preferably within the range 0.9 to 1.33, and more preferably within the range 0.9 to 1.2.

Of particular interest is zeolite MAP with a silicon to aluminum ratio of not more than 1.15 and, more precisely, not more than 1.07.

In a preferred aspect, the zeolite MAP detergency builder has a particle size, expressed as d50 value, of 1.0 to 10.0 microns, more preferably 2.0 to 7.0 microns, most preferably 2.5 to 5.0 microns.

The d₅₀ value indicates that 50% by weight of the particles have a diameter smaller than this value. The particle size can be determined in particular by conventional analytical techniques, such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods for determining d₅₀ values are disclosed in EP 384 070 A.

Heavy metal ion sequestrants

The cleaning compositions or components thereof according to the present invention preferably contain a heavy metal ion sequestrant as an optional component. By heavy metal ion sequestrants herein is meant components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating capabilities, but they preferably exhibit selectivity for the binding of heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of 0.005 to 20%, preferably 0.1 to 10%, more preferably 0.25 to 7.5%, and most preferably 0.5 to 5% by weight of the compositions.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates such as the aminoalkylene poly(alkylene phosphonates), alkali metal ethane-1-hydroxy-diphosphonates and nitrilotrimethylene phosphonates.

Among the above species, diethylenetriamine penta(methylenephosphonate), ethylenediamine tri(methylenephosphonate), hexamethylenediamine tetra(methylenephosphonate) and hydroxyethylene-1,1-diphosphonate are preferred.

Other suitable heavy metal ion sequestrants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid or any salts thereof. Particularly preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid described in EP-A- 317 542 and EP-A-399 133. The iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid- N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516 102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509 382 are also suitable.

EP-A-476 257 describes suitable amino-based sequestrants. EP-A-510 331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528 859 describes a suitable alkyliminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Organic peroxyacid bleaching system

A preferred feature of cleaning compositions or components thereof according to the invention is an organic peroxyacid bleaching system. In a preferred embodiment, the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The preparation of the organic peroxyacid takes place by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred embodiment, a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and an organic peroxyacid precursor in combination with a preformed organic peroxyacid are also contemplated.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium, salt at a level of from 1 to 40%, more preferably from 2 to 30%, and most preferably from 5 to 25% by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional estimation. However, for certain perhydrate salts, preferred embodiments of such granular compositions use a coated form of the material which provides better storage stability for the perhydrate salt in the granular product and/or delayed release of the perhydrate salt upon contact of the granular product with water. Suitable coatings include inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures of these or organic materials such as waxes, oils or fatty soaps.

Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBO₂H₂O₂ or the tetrahydrate NaBO₂H₂O₂·3H₂O.

Alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates herein. Sodium percarbonate is an addition compound with a formula corresponding to 2Na₂CO₃·3H₂O₂, and is commercially available as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt for use in the cleaning compositions described herein.

Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. In general, peroxyacid bleach precursors can be represented as

wherein L is a leaving group and X is essentially any functionality such that upon perhydrolysis the structure of the peroxyacid produced

Peroxyacid bleach precursor compounds are preferably incorporated at a level of 0.5 to 20%, more preferably 1 to 15%, most preferably 1.5 to 10% by weight of the cleaning compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, and these precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1 586 789. Suitable esters are disclosed in GB-A-836 988, 864 798, 1 147 871, 2 143 231 and EP-A-0 170 386.

Leaving groups

The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to take place within the optimal time frame (e.g. a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L-groups are selected from the group consisting of:

and Mixtures thereof, wherein R¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R³ is an alkyl chain having 1 to 8 carbon atoms, R⁴ is H or R³, R⁵ is an alkenyl chain having 1 to 8 carbon atoms, and Y is H or a solubilizing group. Each of R¹, R³ and R⁴ may be substituted by essentially any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups.

The preferred solubilizing groups are -SO₃⁻M⁺, -CO₂⁻M⁺, -SO₄⁻M⁺, -N⁺(R³)₄X⁻ and O<--N(R³)₃ and most preferably -SO₃⁻M⁺ and -CO₂⁻M⁺, where R³ is an alkyl chain having 1 to 4 carbon atoms, M is a cation which imparts solubility to the bleach activator and X is an anion which imparts solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Alkylpercarboxylic acid bleach precursors

Alkyl percarboxylic acid precursors form percarboxylic acids upon perhydrolysis. Preferred precursors of this type provide peracetic acid upon perhydrolysis.

Preferred imide-type alkylpercarboxylic acid precursor compounds include the N-,N,N¹N¹-tetraacetylated alkylenediamines wherein the alkylene group contains 1 to 6 carbon atoms, especially those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacelylethylenediamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethyl-hexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS), and pentaacetylglucose.

Amide-substituted alkyl peroxyacid precursors

Amide substituted alkyl peroxyacid precursor compounds are useful herein, including those of the following general formulas:

wherein R¹ is an alkyl group having 1 to 14 carbon atoms, R² is an alkylene group having 1 to 14 carbon atoms, and R⁵ is H or an alkyl group having 1 to 10 carbon atoms, and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0 170 386.

Perbenzoic acid precursors

Perbenzoic acid precursor compounds provide perbenzoic acid upon perhydrolysis. Suitable acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyloxybenzenesulfonates and the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents and those of the imide type including N-benzoylsuccinimide, tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Cationic peroxyacid precursors

Cationic peroxyacid precursors generate cationic peroxyacids upon perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid portion of a suitable peroxyacid precursor compound with a positively charged functional group such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are typically present in the solid cleaning compositions as a salt with a suitable anion such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid precursor compound as described hereinabove or a substituted derivative thereof. Alternatively, the peroxyacid precursor compound may be an alkylpercarboxylic acid precursor compound or an amide-substituted alkylperoxyacid precursor compound as described hereinafter.

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; G.B. 1,382,594; EP 475,512, 458,396 and 284,292; and JP 87-318,332.

Suitable cationic peroxyacid precursors include any of the ammonium or alkylammonium substituted alkyl or benzoyloxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetylglucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylenebenzoylcaprolactams and the trialkylammonium methylenealkylcaprolactams.

Benzoxazine precursor of organic peroxyacid

Also suitable are precursor compounds of the benzoxazine type, as disclosed for example in EP-A-332 294 and EP-A-482 807, in particular those having the formula:

wherein R₁ is H, alkyl, alkaryl, aryl or arylalkyl.

Preformed organic peroxyacid

The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1 to 15%, more preferably from 1 to 10%, by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide-substituted compounds of the following general formulas:

wherein R¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R² is an alkylene, arylene and alkarylene group having 1 to 14 carbon atoms, and R⁵ is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0 170 386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxycaproic acid are also suitable herein.

Bleach catalyst

The compositions of the invention optionally contain a transition metal-containing bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation with little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant with defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Patent 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(PF₆)₂, MnIII₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl- 1,4,7-triazacyclononane)₂-(ClO₄)₂, MnIV₄(u-O)₆(1,4,7-triazacyclononane)₄-(ClO₄)₂, MnIIIMnIV₄(u- O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₃ and mixtures thereof. Others are described in European Patent Application Publication No. 549 272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

For examples of suitable bleach catalysts, see U.S. Patent 4,246,612 and U.S. Patent 5,227,084; see also U.S. Patent 5,194,416, which teaches mononuclear manganese(IV) complexes such as Mn(1,4,7- trimethyl-1,4,7-triazacyclononane)(OCH3)3-(PF6). Yet another type of bleach catalyst, as disclosed in U.S. Patent 5,114,606, is a water-soluble complex of manganese(III) and/or (IV) with a ligand which is a noncarboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+ and [Bipy2MnIII(u-O)2- MnIVbipy2]-(ClO4)3.

Other suitable bleach catalysts are described, for example, in European Patent Application No. 408 131 (cobalt complex catalysts), European Patent Application Publications Nos. 384 503 and 306 089 (metalloporphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European Patent Application Publication No. 224 952 (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (iron(III) complex catalyst), German Patent Specification 2,054,019 (cobalt chelating agent catalyst), Canadian Patent Specification 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelating agents with manganese cations and non-catalytic metal cations) and U.S. 4,728,455 (manganese gluconate catalysts).

Additional enzymes

The compositions of the present invention may comprise one or more additional enzymes.

Preferred additional enzymatic materials include those commercially available enzymes. The enzymes include enzymes selected from lipases, cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.

A preferred combination of additional enzymes in a cleaning composition of the present invention comprises a mixture of conventionally applicable enzymes such as lipase, protease, amylase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading Enzymes. Suitable enzymes are exemplified in US Patents 3,519,570 and 3,533,139.

Suitable proteases are the subtilisins obtained from certain strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN'). A suitable protease is obtained from a Bacillus strain with maximum activity throughout the pH range 8-12, developed and sold as ESPERASE® by Novo Industries A/S, Denmark, hereinafter "Novo". The production of this enzyme and analogous enzymes is described in GB 1 243 784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gisf-Brocades. Proteolytic enzymes also include modified bacterial serine proteases such as those described in European Patent Application Serial No. 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98) and referred to herein as "Protease B" and in European Patent Application 199 404, Venegas, published October 29, 1986, which relates to a modified bacterial serine proteolytic enzyme referred to herein as "Protease A". Suitable is what is called "Protease C" herein, which is a variant of an alkaline serine protease from Bacillus in which lysine replaces arginine at position 27, tyrosine replaces valine at position 104, serine replaces asparagine at position 123, and alanine replaces threonine at position 274. Protease C is described in EP 90 915 958.4, corresponding to WO 91/06637, published on 16 May 1991. Genetically modified variants, in particular of Protease C, are also included herein.

A preferred protease, designated "Protease D", is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in the carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin as described in WO95/10591 and in the patent application of C. Ghosh, et al.; "Bleaching Compositions Comprising Protease Enzymes" with U.S. Serial No. 08/322,677, filed October 13, 1994.

Also suitable for the present invention are proteases described in the patent applications EP 251 446 and WO91/06637, protease BLAP® described in WO91/02792, and its variants described in WO95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO92/03529 A to Novo. If desired, a protease with reduced adsorption and increased hydrolysis is available as described in WO95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents usable herein is described in WO94/25583 to Novo. Other suitable proteases are described in EP 516200 to Unilever.

One or a mixture of proteolytic enzymes may be incorporated into the cleaning compositions of the present invention, generally at a level of 0.0001 to 2 wt%, preferably 0.001 to 0.2 wt%, more preferably 0.005 to 0.1 wt% pure enzyme, based on the weight of the composition.

When present in the cleaning compositions of the present invention, the lipolytic enzyme component is generally present at levels of from 0.00005 to 2% by weight active enzyme, based on the weight of the composition, preferably from 0.001 to 1%, most preferably from 0.0002 to 0.05% by weight active enzyme in the cleaning composition.

Suitable lipolytic enzymes for use in the present invention include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas truncate ATCC 19,154 as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody to lipase produced by the microorganism Pseudomonas Hisorescent M 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 from Chromobacter viscosum, e.g. Chromobacter viscosum var lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A., and Disoynth Co., Netherlands, and lipases from Pseudomonas gladioli. Particularly suitable lipases are lipases such as M1-Lipase® and Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo), which have been 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 258 068, WO92/05249 and WO95/22615 from Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 from Unilever.

Also suitable are cutinases [EC 3.1.1.50], which can be considered as a special type of lipase, namely lipases that do not require interfacial activation. The addition of cutinases to cleaning compositions has been described, for example, in WO-A-88/09367 (Genencor); WO90/09446 (Plant Genetic System) and WO94/14963 and WO94/14964 (Unilever). The LIPOLASE enzyme, which is derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341 947), is a preferred lipase for use in the present invention.

Another preferred lipase for use in the present invention is the lipolytic D96L enzyme variant of the native lipase derived from Humicola lanuginosa. Most preferably the strain Humicola lanuginosa DSM 4106 is used.

By lipolytic D96L enzyme variant is meant the lipase variant as described in patent application WO92/05249, where in the native lipase from Humicola lanuginosa the aspartic acid residue (D) at position 96 has been changed to leucine (L). According to this nomenclature the substitution of aspartic acid to leucine is shown as: D96L. To determine the activity of the enzyme D96L the standard LU assay can be applied (Analytical Method, internal Novo Nordisk number AF 95/6-GB 1991.02.07). A substrate for D96L was prepared by emulsifying glycerol tributyrate (Merck) using gum arabic as an emulsifier. Lipase activity is tested at pH 7 using the pH stat. method.

The cleaning compositions of the invention may also contain one or a mixture of more than one amylase enzyme (α and/or β). WO94/02597, Novo Nordisk A/S, published February 3, 1994, describes cleaning compositions containing mutated amylases; see also WO95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in cleaning compositions include both α and β amylases. α amylases are known in the art and include those disclosed in U.S. Patent No. 5,003,257; EP 252,666; WO/91/00353; FR 2 676 456; EP 285 123; EP 525 610; EP 368 341 and British Patent Specification No. 1 296 839 (Novo). Other suitable amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994, and WO96/05295, Genencor, published February 22, 1996, and amylase variants with additional modification in the immediate parent form available from Novo Nordisk A/S, disclosed in WO95/10603, published April 1995. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all from Novo Nordisk).

Examples of commercially available α-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark. WO95/26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® in a temperature range of 25ºC to 55ºC and at a pH in the range of 8 to 10, measured by the Phadebas® α-amylase activity assay. Suitable variants of the above enzymes are those described in WO96/23873 (Novo Nordisk). Other preferred amylolytic enzymes with improved properties in terms of activity level and the combination of thermal stability and a higher activity level are described in WO95/35382.

The amylolytic enzymes, when present, are generally incorporated into the cleaning compositions of the present invention 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 composition.

The cleaning compositions of the invention may additionally contain one or more cellulase enzymes. Suitable cellulases include both bacterial and fungal cellulases. Preferably they will have a pH optimum between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al. J61078384 and WO96/02653, which disclose fungal cellulases, produced from Humicola insolens, Trichoderma, Thielavia and Sporotrichum, respectively. EP 739 982 describes cellulases isolated from a new Bacillus species. Suitable cellulases are also disclosed in GB-A-2 075 028; GB-A-2 095 275; DE-OS-22 47 832 and WO95/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), in particular the Humicola strain DSM 1800. Other suitable cellulases are cellulases derived from Humicola insolens with a molecular weight of 50 KDa, an isoelectric point of 5.5 and with 415 amino acids; and a ~ 43 kD endoglucanase, derived from Humicola insolens, DSM 1800, which exhibits cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO91/17243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum, described in WO 94/21801; Genencor, published September 29, 1994. Particularly suitable cellulases are the cellulases which have color care benefits. Examples of such cellulases are the cellulases described in European Patent Application No. 91 202 879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are particularly useful; see also WO91/17244 and WO91/21801. Other cellulases suitable with regard to textile care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471.

Peroxidase enzymes can also be incorporated into the cleaning compositions of the invention. Peroxidases 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 the transfer of dyes or pigments removed from substrates during washing operations to other substrates in the washing 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 cleaning compositions are disclosed, for example, in PCT International Application WO89/099813 and WO89/09813.

Preferred enhancers are substituted phenthiazine and phenoxasin, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

The cellulases and/or peroxidases, if present, are normally incorporated into the cleaning composition at levels of 0.0001% to 2% active enzyme by weight of the cleaning composition.

The additional enzymes, if present, are normally incorporated into the cleaning composition at levels of 0.0001 to 2% active enzyme by weight of the cleaning composition. The additional enzymes may be added as separate individual ingredients (prills, granules, stabilized liquids, etc., containing an enzyme) or as mixtures of two or more enzymes (e.g., cogranules).

Enzyme oxidation scavenger

Other suitable detergent ingredients which may be added are enzyme oxidation scavengers, which are described in European Patent EP 0 553 607, filed January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

Enzyme materials

A selection of enzyme materials and methods for their incorporation into synthetic detergent compositions are also described in WO 93 07263 A and WO 93 07260 A by Genencor International, WO 89 08694 A to Novo; and US 3,553,139, January 5, 1971, to McCarty et al. Enzymes are further described in US 4,101,457, Place et al., July 18, 1978, and in US 4,507,219, Hughes, March 26, 1985. Enzyme materials useful in liquid detergent formulations and their incorporation into such formulations are described in US 4,261,868, Hora et al., April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US 3,600,319, August 17, 1971, Gedge et al., EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in US 3,519,570. A useful bacillus, sp. AC13, which yields proteases, xylanases and cellulases is described in WO 94 01532 A to Novo.

Organic polymeric compound

Organic polymeric compounds are preferred additional components of the cleaning compositions of the present invention or components thereof, and are preferably present as components of any particulate components of the cleaning composition where they can act to bind the particulate component together. By organic polymeric compound is meant any polymeric organic compound which is commonly used as a dispersant, antiredeposition or soil suspension agent in cleaning compositions, including any of the high molecular weight organic polymeric compounds described herein as clay flocculants.

Such an organic polymeric compound is generally incorporated in the cleaning compositions of the invention at a level of from 0.1 to 30%, preferably from 0.5 to 15%, most preferably from 1 to 10%, by weight of the compositions.

Examples of organic polymeric compounds include the water-soluble organic homo- or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1 596 756. Examples of such salts are polyacrylic acid or polyacrylates having a molecular weight of 1000-5000 and their copolymers with maleic anhydride, such as copolymers having a molecular weight of 2000 to 100,000, especially 40,000 to 80,000. Polymaleates or polymaleic acid polymers and salts thereof are also suitable examples.

Polyamino compounds useful herein include those derived from aspartic acid, including polyaspartic acid, and those such as those disclosed in EP-A-305 282, EP-A-305 283 and EP-A-351 629.

Terpolymers containing monomer units selected from maleic acid, acrylic acid, aspartic acid and vinyl alcohol or acetate, particularly those having an average molecular weight of 1,000 to 30,000, preferably 3,000 to 10,000, are also suitable for incorporation into the compositions of the present invention.

Other organic polymeric compounds suitable for incorporation into the cleaning compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose and hydroxyethylcellulose.

Other useful organic polymeric compounds are the polyethylene glycols, especially those having a molecular weight of 1,000 to 10,000; more specifically 2,000 to 8,000 and most preferably about 4,000.

Cationic soil removal/anti-redeposition compounds

The cleaning composition of the invention or components thereof may comprise water-soluble cationic ethoxylated amine compounds having particulate soil/clay soil removal properties and/or anti-redeposition properties. These cationic compounds are described in more detail in EP-B-111 965, US 4,659,802 and US 4,664,848. Particularly preferred of these cationic compounds are ethoxylated cationic monoamines, diamines or trimamines. Especially preferred are the ethoxylated cationic monoamines, diamines and triamines of the formula:

wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups and mixtures thereof, a is 0 to 20, preferably 0 to 4 (e.g. ethylene, propylene, hexamethylene), b is 2, 1 or 0; for cationic monoamines (b = 0), n is preferably at least 16, with a typical range of 20 to 35; for cationic diamines or triamines, n is preferably at least about 12, with a typical range of about 12 to about 42.

These compounds, if present in the composition, are generally present in an amount of 0.01 to 30 wt.%, preferably 0.05 to 10 wt.%.

Foam suppression system

The cleaning compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5%, by weight of the composition.

Suitable foam suppressor systems for use herein can comprise essentially any known antifoam compound including, for example, silicone antifoam compounds and 2-alkylalkanol antifoam compounds.

By antifoam compound is meant herein any compound or mixture of compounds which act to suppress the foaming or sudsing produced by a solution of a cleaning composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds, defined herein as any antifoam compound which contains a silicone component Such silicone antifoam compounds typically also contain a silica component. The term "silicone" as used herein and generally throughout the industry includes a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl groups of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl endblocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as foam suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts, such as sodium, potassium and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, C18-C40 aliphatic ketones (e.g., stearone), N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiaminechlorotriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine having 1 to 24 carbon atoms, propylene oxide, bis-stearic acid amide, and monostearyl dialkali metal (e.g., sodium, potassium, lithium) phosphates and phosphate esters.

A preferred foam suppression system comprises

(a) An antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) polydimethylsiloxane at a level of 50 to 99%, preferably 75 to 95%, by weight of the silicone antifoam compound; and

(ii) silica at a level of 1 to 50%, preferably 5 to 25%, by weight of the silicone/silica antifoam compound;

wherein the silica/silicone antifoam compound is incorporated at a level of 5 to 50 wt.%, preferably 10 to 40 wt.%;

(b) A dispersant compound, most preferably comprising a silicone glycol rake copolymer having a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of 1:0.9 to 1:1.1 at a level of 0.5 to 10 wt%, preferably 1 to 10 wt%; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the trade name DCO544;

(c) An inert carrier fluid component, most preferably comprising an ethoxylated C16-C18 alcohol having a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5 to 80 wt%, preferably 10 to 70 wt%;

A highly preferred particulate foam suppressor system is described in EP-A-0 210 731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50°C to 85°C, the organic carrier material comprising a monoester of glycerol and a fatty acid having a carbon chain of 12 to 20 carbon atoms. EP-A-0 210 721 discloses further preferred particulate foam suppressor systems wherein the organic carrier material is a fatty acid or an alcohol having a carbon chain of 12 to 20 carbon atoms, or a mixture thereof, having a melting point of 45°C to 80°C.

Polymeric dye transfer inhibiting agents

The cleaning compositions described herein may also comprise from 0.01 to 10%, preferably from 0.05 to 0.5% by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers can be crosslinked polymers.

a) Polyamine N-oxide polymers

Polyamine N-oxide polymers suitable for use herein contain units having the following structural formula:

where P is a polymerizable unit, and

A

-O-, -S-,

is; x is 0 or 1; R¹ is H

or linear or branched C₁₋₆alkyl; or can form a heterocyclic group with R; R represents aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached, or wherein the nitrogen of the N-O group is part of these groups.

The NO group can be represented by the following general structures:

wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and/or y and/or z is 0 or 1, and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerizable unit (P) or can be attached to the polymeric backbone, or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerizable unit include polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, N-substituted pyrrole, imidazole, N-substituted pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides to which the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R represents an aromatic, heterocyclic or alicyclic group wherein the nitrogen of the N-O functional group is part of the R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, N-substituted pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained at almost any degree of polymerization. The degree of polymerization is not critical provided that the material has the desired water solubility and dye-suspending performance. Typically, the average molecular weight is within the range of 500 to 1,000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are polymers of N-vinylimidazole and N-vinylpyrrolidone having a preferred average molecular weight range of 5,000 to 100,000 or 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1 to 0.2.

c) Polyvinylpyrrolidone

The cleaning compositions described herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY, and Montreal, Canada, under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones commercially available from BASF Corporation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The cleaning compositions described herein may also use polyvinyloxazolidones as polymeric dye transfer inhibiting agents. The polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000.

e) Polyvinylimidazol

The cleaning compositions described herein may also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. The polyvinylimidazoles preferably have an average molecular weight of 2,500 to 400,000.

Optical Auheller

The cleaning compositions described herein optionally also contain from about 0.005 to 5% by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners usable herein include those having the structural formula:

wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chlorine and amino; and M is a salt forming cation such as sodium or potassium.

In the above formula, when R1 is anilino, R2 is N-2-bis-hydroxyethyl, and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbenedisulfonic acid, disodium salt. This particular brightener species is commercially sold under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the cleaning compositions described herein.

In the above formula, when R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is sold commercially under the trade name Tinopal 5BM-GX by Ciba Geigy Corporation.

In the above formula, when R1 is anilino, R2 is morphilino, and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazin-2-yl)amino]-2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is marketed commercially under the trade name Tinopal AMS-GX by Ciba Geigy Corporation.

Polymeric soil repellant

Known polymeric soil release agents, hereinafter "SRA", may optionally be used in the present cleaning compositions. If used, SRA's will generally comprise from 0.01 to 10.0%, typically from 0.1 to 5%, preferably from 0.2 to 3.0%, by weight of the compositions.

Preferred SRAs typically have hydrophilic segments to render the surface of hydrophobic fibers, such as polyester and nylon, hydrophilic, and have hydrophobic segments to deposit on hydrophobic fibers and remain attached thereto until completion of the wash and rinse cycles, thereby serving as an anchor for the hydrophilic segments. This may allow soils that occur subsequent to treatment with the SRA to be more easily cleaned in subsequent washes.

Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium (IV) alkoxide. Such esters can be prepared using additional monomers capable of being incorporated into the ester structure at one, two, three, four or more positions, of course without forming a densely cross-linked overall structure.

Suitable SRA's include a sulfonated product of a substantially linear ester oligomer built up from an oligomeric or polymeric ester backbone of repeating terephthaloyl and oxyalkyleneoxy units and allyl-derived sulfonated terminal units covalently bonded to the backbone, as described, for example, in U.S. 4,968,451, November 6, 1990, by J. J. Scheibel and E. P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-step transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic endcapped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987, to Gosselink et al., for example, those prepared by transesterification/oligomerization of poly(ethylene glycol) methyl ether, DMT, PG, and poly(ethylene glycol) ("PEG"). Other examples of SRA's include: the partially and fully anionic endcapped oligomeric esters of U.S. 4,721,580, January 26, 1988, to Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT, and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomer compounds of U.S. U.S. 4,702,857, October 27, 1987, to Gosselink, for example prepared from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989, to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, one example being an ester composition prepared from m-sulfobenzoic acid monosodium salt, PG and DMT, but which optionally further contains added PEG, e.g. B. PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see US 3,959,230 to Hays, May 25, 1976, and US 3,893,929 to Basadur, July 8, 1975; cellulose derivatives; such as the hydroxyether cellulose polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see US 4,000,093, December 28, 1976 to Nicol et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to about 2.3 and a solution viscosity of about 80 to about 120 centipoise, measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRAs include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al., and U.S. 4,240,918, Lagasse et al.; and (II) carboxylate-terminated SRAs prepared by adding trimellitic anhydride to known SRAs to convert the terminal hydroxyl groups to trimellitate esters. With the appropriate selection of a catalyst, the trimellitic anhydride forms bonds to the ends of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening the anhydride bond. Either nonionic or anionic SRAs can be used as starting materials as long as they have hydroxyl end groups that can be esterified; see U.S. 4,201,824, Violland et al., and U.S. 4,240,918, Lagasse et al. 4,525,524, Tung et al. Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;

Other optional components

Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colors and filler salts, with sodium sulfate being a preferred filler salt.

Detergent formulations with almost neutral washing pH

While the cleaning compositions of the present invention are operative over a wide range of wash pHs (e.g., about 5 to about 12), they are particularly useful when formulated to provide a near neutral wash pH, i.e., an initial pH of about 7.0 to about 10.5 at a concentration of about 0.1 to 2% by weight in water at 20°C. Formulations having near neutral wash pH are better for enzyme stability and for preventing stain hardening. In such formulations, the wash pH is preferably about 7.0 to about 10.5, more preferably about 8.0 to about 10.5, most preferably 8.0 to 9.0.

Preferred detergent formulations having a near neutral wash pH are disclosed in European Patent EP 0 095 205, filed May 16, 1983, J. H. M. Wertz and P. C. E. Goffinet.

Highly preferred compositions of this type preferably also contain from about 2 to about 10 wt% citric acid and minor amounts (e.g., less than about 20 wt%) of neutralizing agents, buffering agents, phase adjusting agents, hydrotropics, enzymes, enzyme stabilizing agents, polyacids, foam controlling agents, opacifiers, antioxidants, bactericides, dyes, fragrances, and brighteners such as those described in U.S. Patent 4,285,841 to Barrat et al., issued August 25, 1981 (incorporated herein by reference).

Form of compositions

The compositions according to the invention may take a variety of physical forms, including granular form. The compositions may be pretreatment compositions or conventional washing detergents. The compositions are particularly the so-called concentrated granular cleaning compositions which are adapted to be dispensed into a washing machine by means of a dispensing device which is introduced into the drum of the machine with the soiled textile load.

Such granular detergent compositions or components thereof according to the present invention can be prepared by a variety of methods including spray drying, dry blending, extrusion, agglomeration and granulation. The cationic quaternized surfactant can be added to the other detergent components by blending, agglomeration (preferably combined with a carrier material), granulation or as a spray dried component.

The compositions according to the present invention can also be used in, or in combination with, bleaching additive compositions comprising, for example, chlorine bleach.

In one aspect of the invention, the mean particle size of the components of granular compositions according to the invention should preferably be such that no more than 15% of the particles have a diameter greater than 1.8 mm and no more than 15% of the particles have a diameter less than 0.25 mm. Preferably, the mean particle size is such that 10% to 50% of the particles have a particle size of diameter from 0.2 mm to 0.7 mm.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of sieves, preferably Tyler sieves. The weight fractions thus obtained are plotted against the opening size of the sieves. The mean particle size is taken as the opening size through which 50% by weight of the sample would pass.

In a further aspect of the invention, at least 80% by weight, preferably at least 90% by weight of the composition comprises particles having an average particle size of at least 0.8 mm, more preferably at least 1.0 mm, and most preferably 1.0 or 1.5 to 2.5 mm. Most preferably, at least 95% of the particles will have such an average particle size. Such particles are preferably produced by an extrusion process.

The bulk density of granular detergent compositions according to the present invention typically amounts to a bulk density of at least 400, preferably at least 600 g/litre, more preferably 650 g/litre to 1200 g/litre. The bulk density is measured using a simple funnel and cup device consisting of a conical funnel rigidly formed on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup located beneath the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its upper and lower extremities respectively. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an inner height of 87 mm and an inner diameter of 84 mm. Its nominal volume is 500 ml.

To make a measurement, the funnel is filled with powder by pouring it by hand, the flap valve is opened and the powder is allowed to overfill the cup. The filled cup is removed from the frame and excess powder is removed from the cup by running a straight-edged tool, such as a knife, across its top edge. The filled cup is then weighed and the value obtained for the weight of the powder is doubled to provide a bulk density in g/litre. Repeat measurements are made as required.

Compacted solids may be prepared using any suitable compaction process such as tabletting, briquetting or extrusion. Preferably, tablets for use in dishwashing processes are prepared using a standard rotary tablet press using compression forces of 5 to 13 KN/cm2, more preferably 5 to 11 KN/cm2, such that the compacted solid has a minimum hardness of 176 N to 275 N, preferably 195 N to 245 N, as measured by a C100 hardness test as supplied by I.Holland Instruments. This process may be used to prepare homogeneous or layered tablets of any size or shape. Preferably, tablets are symmetrical to ensure uniform dissolution of the tablet in the washing solution.

Laundry washing process

Machine laundry processes herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispersed therein an effective amount of a machine laundry cleaning composition according to the invention. By an effective amount of the cleaning composition is meant 10 g to 300 g of product dissolved or dispersed in a wash solution of a volume of 5 to 65 liters, which are typical product dosages and wash solution volumes commonly used in conventional machine laundry processes. The dosage depends on the particular conditions, such as water hardness and the degree of soiling of the soiled laundry.

The cleaning composition can be dispensed, for example, from the drawer dispenser of the washing machine, or can be sprinkled over the soiled laundry placed in the machine.

In one aspect of the application, a dispensing device is used in the washing process. The dispensing device is loaded with the detergent product and is used to introduce the product directly into the drum of the washing machine prior to the start of the washing cycle. Its volume capacity should be such that it is able to contain sufficient detergent product as is normally used in the washing process.

The dispenser containing the detergent product is placed in the drum before the start of the wash, before, at the same time as, or after the washing machine has been loaded with the laundry. At the start of the washing cycle of the washing machine, water is introduced into the drum and the drum rotates periodically. The dispenser should be designed such that it allows the dry detergent product to be contained, but then Release of this product during the washing cycle in response to its movement with the rotation of the drum and also as a result of its contact with the washing water.

To allow release of the detergent product during washing, the device may have a number of apertures through which the product can pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing temporary localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained both in the dry state and during the wash cycle. Particularly preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2 157 717, GB-B-2 157 718, EP-A-0 201 376, EP-A-0 288 345 and EP-A-0 288 346. An article by J. Bland, published in Manufacturing Chemist, November 1989, pages 41-46, also describes particularly preferred dispensing devices for use with granular laundry products which are of a type commonly known as the "granulette". Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO 94/11562.

Particularly preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0 343 069 & 0 343 070. The latter application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining a mouth, the mouth being adapted to admit sufficient product into the bag for one wash cycle in a washing process. A portion of the wash medium flows through the mouth into the bag, dissolving the product, and the solution then passes out through the mouth into the wash medium. The support ring is provided with a masking arrangement to prevent the escape of moistened undissolved product, this arrangement typically comprising radially extending walls extending from a central hub in a spoked wheel configuration, or a similar structure in which the walls assume a helical shape.

Alternatively, the dispensing device may be a flexible container such as a pouch or bag. The pouch may be of fibrous construction coated with a water-impermeable protective material so that the contents are retained, as disclosed in published European Patent Application No. 0 018 678. Alternatively, it may be formed from a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media, as disclosed in published European Patent Application Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of water-rupturable closure comprises a water-soluble adhesive provided along and sealing an edge of a pouch formed from a water-impermeable polymeric film such as polyethylene or polypropylene.

Machine dishwashing process

Any suitable method for machine dishwashing or cleaning of soiled dishes, especially soiled silverware, will be considered.

A preferred method of machine dishwashing comprises treating soiled items selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof with an aqueous liquid in which an effective amount of a machine dishwashing composition according to the invention is dissolved or dispersed. By an effective amount of the machine dishwashing composition is meant that 8 g to 60 g of product is dissolved or dispersed in a wash solution of 3 to 10 liters volume, which are typical product dosages and wash solution volumes commonly used in conventional machine dishwashing processes.

Packaging for the compositions

Commercially distributed embodiments of the bleaching compositions may be packaged in any suitable container, including those constructed from paper, cardboard, plastic materials, and any suitable laminates.

Abbreviations used in the examples

In the cleaning compositions, the abbreviated component details have the following meanings:

LAS: Linear sodium C12 alkybenzene sufonate

TAS 1: Sodium tallow alkyl sulfate

TAS 2: Sodium C20 alkyl sulfate

CxyAS sodium C1x-C1y alkyl sulfate

C46SAS: Sodium C₁₄-C₁₆-secondary (2,3)-alkyl sulfate

CxyEzS: Sodium C1x-C1y alkyl sulfate, condensed with z moles of ethylene oxide

CxyEz: predominantly linear primary C1x-C1y alcohol condensed with an average of z moles of ethylene oxide

QAS 1: R2 ·N+ (CH3 )2 (C2 H4 OH) with R2 = linear C9 -C11 alkyl

QAS 2: R₂·N⁺(CH₃)₂(C₂H₄OH) with approximately 50% R₂ = linear C₈-alkyl; approximately 50% R₂ = C₁₀

QAS 3: R₂·N⁺(CH₃)₂(C₂H₄OH) with approximately 40% R₂ = linear C₁₁-alkyl; approximately 60% R₂ = linear C₉-alkyl

QAS 4: R2 ·N+ (CH3 )2 (C2 H4 OH) with R2 = linear C6 alkyl

QAS 5: R2 ·N+ (CH3 )2 (C2 H4 OH) with R2 = linear C10 alkyl

Soap: Linear sodium alkyl carboxylate derived from an 80/20 blend of tallow and coconut oils

CFAA: C12 -C14 (coconut)alkyl-N-methylglucamide

TFAA: C16 -C18 alkyl-N-methylglucamide

TPKFA: total cut fatty acids topped by C₁₂-C₁₄

STPP: anhydrous sodium tripolyphosphate

TSPP: Tetrasodium pyrophosphate

Zeolite A: Hydrated sodium aluminosilicate of the formula Na₁₂(AlO₂SiO₂)₁₂·27H₂O with a primary particle size in the range of 0.1 to 10 micrometers

Zeolite MAP: hydrated sodium aluminosilicate zeolite MAP with a silicon to aluminum ratio of 1.07

NaSKS-6: crystalline layered silicate of the formula δ-Na₂Si₂O�5

Citric acid: Anhydrous citric acid

Borate: Sodium borate

Carbonate: Anhydrous sodium carbonate with a particle size between 200 um and 900 um

Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400 um and 1200 um

Silicate: Amorphous sodium silicate (SiO2 :Na2O ratio = 2.0:1)

Sodium sulfate: Anhydrous sodium sulfate

Citrate: Tri-sodium citrate dihydrate with an activity of 86.4% with a particle size distribution between 425 um and 850 um

MA/AA: Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000

AA: Sodium polyacrylate polymer with average molecular weight 4500

CMC: sodium carboxymethyl cellulose

Cellulose ether: Methyl cellulose ether with a degree of polymerization of 850, available from Shin Etsu Chemicals

Protease: Proteolytic enzyme with an activity of 4 KNPU/g, sold by NOVO Industries A/S under the trade name Savinase

Alcalase: Proteolytic enzyme with an activity of 3 AU/g, distributed by NOVO Industries A/S

Cellulase: Cellulytic enzyme with an activity of 1000 CEVU/g, sold by NOVO Industries A/S under the trade name Carezym

Amylase: Amylolytic enzyme with an activity of 120 KNU/g, sold by NOVO Industries A/S under the trade name Termamyl 120T

Lipase: Lipolytic enzyme with an activity of 100 KLU/g, sold by NOVO Industries A/S under the trade name Lipolase

Endolase: Endoglucanase enzyme with an activity of 3000 CEVU/g, distributed by NOVO Industries A/S

PB4: Sodium perborate tetrahydrate of nominal formula NaBO2 ·3H2 O·H2 O2

PB1: Anhydrous sodium perborate bleach of nominal formula NaBO₂·H₂O₂

Percarbonate: Sodium percarbonate of nominal formula 2 Na2 CO3 ·3H2 O2

NOBS: Nonanoyloxybenzenesulfonate in the form of the sodium salt

TAED: Tetraacetylethylenediamine

Mn catalyst: MnIV₂(m-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂ as described in U.S. Pat. Nos. 5,246,621 and 5,244,594.

DTPA: Diethylenetriaminepentaacetic acid

DTPMP: Diethylenetriamine penta(methylenephosphonate), sold by Monsanto under the trade name Dequest 2060

Photoactivated bleach: sulfonated zinc phthalocyanine encapsulated in soluble bleach-dextrin polymer

Brightener 1: Disodium 4,4'-bis(2-sulfostyryl)biphenyl

Brightener 2: disodium 4,4'-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino)stilbene-2:2'-disulfonate

HEDP: 1,1-Hydroxyethanediphosphonic acid

EDDS: Ethylenediamine-N,N-disuccinic acid

QEA: Bis((C₂H₅O)(C₂H₅On)(CH₃)-N+-C₆H₁₂N⁺-(CH₃)bis(C₂H₅O)-(C₂H₄O)n), where n = 20 to 30

PEGXO: Polyethylene glycol with a molecular weight of X

PEOO: Polyethylene oxide with a molecular weight of 50000

TEPAE: Tetraethylene pentaamine ethoxylate

PVP: Polyvinylpyrolidone polymer

PVNO: Polyvinylpyridine N-oxide

PVPVI: Copolymer of polyvinylpyrolidone and vinylimidazole

SRP 1: Sulfobenzoyl and capped esters with oxyethyleneoxy and terephthaloyl backbone

SRP 2: Diethoxylated poly(1,2-propylene terephthalate) short block polymer

Silicone antifoam agent: polydimethylsiloxane foam regulator with siloxane-oxyalkylene copolymer as dispersant with a ratio of foam regulator to dispersant of 10:1 to 100:1

Wax: Paraffin wax

In the following examples, all levels are given as % by weight of the composition:

example 1

The following high density granular laundry detergent compositions A to F having particular utility under European machine washing conditions are examples of the present invention:

Example 2

The following granular laundry detergent compositions G to I having particular utility under European machine washing conditions are examples of the present invention:

Example 3

The following detergent formulations having particular utility under European machine washing conditions are examples of the present invention.

Example 4

The following granular detergent formulations are examples of the present invention. Formulation N is particularly suitable for use under Japanese machine wash conditions. Formulations O through S are particularly suitable for use under US machine wash conditions.

Example 5

The following granular detergent formulations are examples of the present invention. Formulations W and X are of particular utility under US machine laundering conditions. Y is of particular utility under Japanese machine laundering conditions

Example 6

The following granular detergent compositions having particular utility under European machine washing conditions are examples of the present invention.

Example 7

The following cleaning compositions are examples of the present invention:

Example 8

The following detergent formulations are examples of the present invention:

Example 9

The following laundry cleaning bar compositions are examples of the present invention.

Claims (16)

1. A granular cleaning composition comprising: (a) a mixture of cationic surfactants of formula I: R¹R²R³R⁴N⁺X⁻ (I) wherein R¹ is a hydroxyalkyl group having no more than 6 carbon atoms; each of R² and R³ is independently selected from C₁₋₄ alkyl or alkenyl; R⁴ is a C₅₋₁₁ alkyl or alkenyl, and for at least 10% by weight of the mixture, R⁴ is a C₅₋₉ alkyl or alkenyl; and X⁻ is a counterion; and (b) an anionic surfactant of formula II R&sup5;OSO&sub3;&supmin;M&spplus; (II) wherein R⁵ is an alkyl or alkenyl group having at least 14 carbon atoms, or as found in a secondary alkyl sulfate, and M⁺ is a counter ion. 2. A cleaning composition according to claim 1, wherein the cationic surfactant is present in an amount of 0.01 to 20% by weight of the composition. 3. A cleaning composition according to claim 2, wherein the cationic surfactant is present in an amount of 0.05 to 5% by weight of the composition. 4. Cleaning composition according to at least one preceding claim, wherein the anionic surfactant is present in an amount of at least 10% by weight, preferably at least 20% by weight of the cleaning composition. 5. A cleaning composition according to any preceding claim, wherein in the cationic compound of formula I, R¹ is -CH₂CH₂OH or -CH₂CH₂CH₂OH; R² and R³ are each methyl; R⁴ is C₆₋₁₁alkyl. 6. A cleaning composition according to any preceding claim, wherein in the cationic compound of formula I, R4 is a linear C6-11 alkyl group. 7. A cleaning composition according to any preceding claim, wherein the cationic surfactant comprises a compound of formula I, wherein R4 is a higher alkyl group having n carbon atoms, wherein n is 8 to 11, and a compound of formula I wherein R4 is a lower alkyl group having (n-2) carbon atoms. 8. A cleaning composition according to any preceding claim, wherein in the anionic surfactant R⁵ has at least 16 carbon atoms. 9. Cleaning composition according to at least one preceding claim, additionally comprising an anionic surfactant of formula III: R&sup6;SO&sub3;&supmin;M'&spplus; (III) wherein R6 is C10-20 alkylbenzene; and M'+ is selected from alkali metals, alkaline earth metals, alkanolammonium and ammonium. 10. A cleaning composition according to claim 9, wherein the anionic surfactant of formula III is present in the cleaning composition in a weight ratio to the anionic surfactant of formula II such that the weight ratio of II:III is in the range of 15:1 to 1:2. 11. A cleaning composition according to claim 9 or claim 10, wherein the anionic surfactant II is a primary or secondary, linear or branched C₁₆₋₁₆ alkyl sulfate, and wherein the anionic surfactant III is a C₁₁₋₁₃ alkylbenzenesulfonate. 12. A cleaning composition according to any preceding claim, additionally comprising a nonionic surfactant selected from the group consisting of alcohol ethoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglucosides and mixtures thereof. 13. Composition according to at least one of claims 8 to 11, comprising: (a) 0.25 to 3 wt.% of a cationic surfactant of formula I R¹R²R³R⁴N⁺X⁻ (I) wherein R¹ is a hydroxyalkyl group having no more than 6 carbon atoms; each of R² and R³ is independently selected from C₁₋₄alkyl or alkenyl; R⁴ is C₅₋₁₁alkyl or alkenyl, and X is a counterion; (b) 3 to 60 wt.% of a straight-chain or branched-chain, primary or secondary alkyl sulfate as surfactant (II); (c) 6 to 23 wt.% alkylbenzenesulfonate as surfactant III; and (d) 0.5 to 20 wt.% of a nonionic surfactant. 14. A composition according to any preceding claim, which is substantially free of bleach. 15. A cleaning composition according to claim 1 which is formed by combining a cationic surfactant of formula I: R¹R²R³R⁴N⁺X⁻ (I) wherein R¹ is a hydroxyalkyl group having not more than 6 carbon atoms; each of R² and R³ is independently selected from C₁₋₄alkyl or alkenyl; R⁴ is a C₅₋₁₁alkyl or alkenyl, and X is a counterion, with an anionic surfactant of formula II: R&sup5;OSO&sub3;&supmin;M&spplus; (II) wherein R⁵ is a linear or branched alkyl group having at least 14 carbon atoms, or as found in a secondary alkyl sulfate, and M⁺ is a counter ion, and one or more optional detergent components. 16. A method for washing laundry in a household washing machine, wherein a dispensing device containing an effective amount of a solid A cleaning composition according to any preceding claim, introduced into the washing machine before commencing washing, the dispensing device enabling progressive release of the cleaning composition into the wash liquor during washing.