DE69719568T2 - CLEANING COMPOSITIONS CONTAINING OXIDOREDUCTASE - Google Patents

Description

Field of the invention

The present invention relates to cleaning compositions, including laundry and dishwashing compositions, hard surface cleaners and oral/dental cleaning compositions, comprising a surfactant system, an organic acid, a hydrogen peroxide source and an oxidoreductase having an α/β-hydrolase fold and a catalytic triad consisting of the amino acid residues serine, histidine and aspartic acid.

Background of the invention

The performance of a cleaning product for use in a rinse/wash or cleaning process is assessed by a number of factors, including the ability to remove soils and the ability to prevent redeposition of the soils or the degradation products of the soils on the garments during the wash.

Coloured stains/soils are often difficult to remove effectively from a soiled object. Strongly coloured stains and soils, i.e. those originating from fruits and/or plants, are soils that present a particular challenge for removal. These stains and soils contain colour bodies based on carotenoid compounds such as α-, β- and γ-carotene as well as lycopene and xanthophylls, on porphyrins such as chlorophyll and on flavonoid pigments and colouring components. This latter group of natural flavonoid colouring components includes the strongly coloured anthocyanin dyes and pigments based on pelargonidin, cyanidin, delphidin and their methyl esters and the anthoxanthins. These compounds are the source of most of the orange, red, purple and blue pigments found in fruit and are present in large numbers in all berries, cherries, red and black currants, grapefruit, passion fruit, oranges, lemons, apples, pears, pomegranates, red cabbage, beetroot and also flowers. Derivatives of cyanidin are present in up to 80% of pigmented leaves, in up to 70% of fruits and in up to 50% of flowers. Specific examples of such stains would include stains from tea, coffee, spices such as curry and peppers, orange, tomato, banana, tea, mango, broccoli, carrot, beetroot, spinach and grass. Ink from ballpoint pens is also known to produce colour stains which are very difficult to remove.

In addition, the complex nature of common "human" soiling, which is typically found on pillowcases, T-shirts, collars and socks present a continuing, unique cleaning challenge for cleaning products. These soils are difficult to remove completely and often accumulate as residues on the fabric, causing greying and yellowing. Common human soiling also occurs on sanitary and kitchen surfaces such as bathtubs, toilet bowls and dishes.

The objects can be textiles, hard surfaces, dishes such as plastic dishes, glasses or porcelain, the teeth and the mouth.

Traditionally, high levels of bleaching agents, optionally together with bleach precursors and/or bleach enhancers, have been included in cleaning compositions. Bleaching agents are compounds which are precursors of hydrogen peroxide, which is formed during the washing process. Perborates and percarbonates are the most important examples of such hydrogen peroxide precursors.

In view of the foregoing, there is clearly a continuing need for the provision of cleaning compositions which have excellent cleaning action. Accordingly, it is an object of the present invention to provide a cleaning composition which provides effective and efficient cleaning of colored and/or common human stains and/or soils. A further object is to provide a cleaning composition which provides cleaning and bleaching of fabric-like articles while avoiding color fading.

The above objective has been achieved by formulating cleaning compositions comprising a surfactant system, an organic acid, a hydrogen peroxide source and an oxidoreductase having an α/β hydrolase fold and a catalytic triad consisting of the amino acid residues serine, histidine and aspartic acid, commonly referred to as "non-heme haloperoxidase".

In a preferred embodiment, the present invention relates to a detergent composition comprising a surfactant system, an organic acid, a source of hydrogen peroxide and a non-heme halogen peroxidase, which further provides for cleaning and bleaching of fabric-like articles. In a second embodiment, the present invention relates to dishwashing or household cleaning compositions comprising a surfactant system, an organic acid, a source of hydrogen peroxide and a non-heme halogen peroxidase; and in a third embodiment, the present invention relates to oral/dental care compositions comprising a surfactant system, an organic acid, a source of hydrogen peroxide and a non-heme halogen peroxidase.

It has surprisingly been found that an enzymatic bleaching system based on a non-heme halogen peroxidase in a detergent composition provides similar benefits to a bleach in an unexpectedly wide range of performance areas such as soil removal, whiteness maintenance and stain removal. It has also been found that the cleaning compositions of the invention provide sanitation of the treated surfaces. It has further been found that the performance of the cleaning compositions of the invention is enhanced by the addition of another enzymatic bleaching system, a conventional activated bleaching system, a metallocatalyst-based bleaching system and/or another detergent enzyme.

WO 95/27046 discloses antimicrobial compositions comprising a vanadium haloperoxidase, a source of a halide and hydrogen peroxide or a source thereof, wherein the vanadium haloperoxidase is a chloroperoxidase obtainable from Curvularia inaequalis. These enzymatic antimicrobial compositions generally comprise from 0.01 to 50% by weight of one or more surfactants.

WO 96/06909 describes enzymatic ozone-releasing mixtures which could be used as oxidizing agents for the production of chemical compounds and in bleaching, cleaning and disinfecting agents. The mixtures contain an oxidoreductase with an α/β-hydrolase fold and a catalytic triad consisting of the amino acids serine, histidine and aspartic acid; a hydrogen peroxide source; and an aqueous solution of an organic acid or its salt. The organic acids or salts are converted into organic peracids at a pH of 3.5 to 6.0 and a temperature of 15°C to 80°C.

However, the use of an enzymatic bleaching system comprising an organic acid, a hydrogen peroxide source and an oxidoreductase with an α/β-hydrolase fold and a catalytic triad consisting of the amino acid residues serine, histidine and aspartic acid in a surfactant-containing cleaning composition has never been known before.

Summary of the invention

The present invention relates to cleaning compositions, including laundry and dishwashing compositions, hard surface cleaners and oral/dental cleaning compositions, having a pH of 7-12, comprising a surfactant system, an organic acid as specified in claim 1, a hydrogen peroxide source and an oxidoreductase having an α/β-hydrolase fold and a catalytic triad consisting of the amino acid residues serine, histidine and aspartic acid. The cleaning compositions of the invention provide effective and efficient cleaning of colored and/or common human stains and/or soils and sanitation of the treated surfaces.

In a preferred embodiment, the present invention relates to laundry detergent compositions which provide cleaning and bleaching of fabric-like articles while avoiding color fading.

Detailed description of the invention Non-heme halogen peroxidase enzyme

An essential component of the cleaning compositions of the invention is an oxidoreductase with an α/β-hydrolase fold and a catalytic triad consisting of the amino acid residues serine, histidine and aspartic acid, which is commonly referred to as non-heme halogen peroxidase.

It has been found that the cleaning compositions of the invention provide effective and efficient cleaning of coloured and common human stains and/or soils and in particular cleaning and bleaching of fabric-like articles while avoiding colour fading when formulated as a laundry detergent composition.

In addition, the cleaning compositions according to the invention provide for sanitation of the treated surfaces.

Sanitation includes all positive effects obtained by inhibiting or reducing microbial activity on textiles and other surfaces, such as preventing the development of bad odors and bacterial/fungal growth. For example, it provides for preventing the development of bad odors on stored and worn textiles, on stored dishes, in particular plastic kitchen utensils, and in toilets. In particular, the composition according to the invention at least inhibits or reduces bacterial and/or fungal proliferation on most textiles until they are subjected to a washing process, thus preventing the formation of bad odors. In addition, bacterial and/or fungal growth on hard surfaces such as tiles and their silicone joints or sanitary installations is prevented.

The sanitation potential of the cleaning compositions according to the invention can be enhanced by the addition of chemical disinfectants such as triclosan and/or hexemidine. Parfums Cosmétiques Actualités No. 125, November 1995, 51-54, describes suitable chemical disinfectants.

The sanitation benefits of the cleaning compositions of the present invention can be assessed by the Minimum Inhibitory Concentration (MIC) as described in Tuber. Lung. Dis. 75(4), August 1994, 286-290; J. Clin. Microbiol. 32(5), May 1994, 1261-1267; and J. Clin. Microbiol. 30(10), October 1992, 2692-2697.

Without being bound by theory, it is believed that the peroxyacids generated in situ by the non-heme halogen peroxidase have excellent bleaching performance on a wide range of bleachable substrates, including the removal and bleaching of common human (dirt deposits), colored stains/soils. In fact, it is believed that the small amount of organic peracid, which is formed by the action of non-heme halogen peroxidase on the organic acid, causes the oxidation of natural and synthetic dyes and dirt components in solution and on surfaces. The colored plant and fruit stains also contain strongly colored dye bodies that are associated with cell wall components. All of these natural dyes are based on strongly conjugated polyaromatic compounds. The color of these materials fades after oxidation by the peracid as a result of the destruction of the color-giving conjugated system in the compound.

Without being bound by theory, it is believed that the removal of body soils in the cleaning compositions of the invention is achieved by the oxidation of the body soil components by the small amount of organic peracid produced by the non-heme halogen peroxidase. This oxidation results in the hydrophilic substitution of the body soil component and/or the fragmentation of the body soil component. These mechanisms result in better removal of the body soil components from the garments during laundering.

Haloperoxidases are a widespread family of enzymes that catalyze the formation of carbon-halogen bonds in the presence of hydrogen peroxide, halide ions and a suitable organic substrate. According to their molecular and catalytic properties, these enzymes can be divided into two subgroups: the heme-containing and non-heme-containing haloperoxidases. The heme-containing enzymes usually contain a protoporphyrin IX as a prosthetic group and exhibit catalase and peroxidase enzyme activities. The non-heme enzymes can be further divided into two classes: eukaryotic halogen peroxidases, which contain vanadium, and bacterial non-heme halogen peroxidases, which require neither metal ions nor any other cofactors ("The Non-Haem Chloroperoxidase From Pseudomonas fluorescens and its Relationship to Pyrrolnitrin Biosynthesis" by Kirner S. et al., Microbiology 142 (1996), 2129-2135).

Halogenating enzymes have been extensively studied: "Bacterial Haloperoxidases and Their Role in Secondary Metabolism" by von Pée K. H., Biotech. Adv., Vol. 8 (1990); pp. 185-205, in which non-heme halogen peroxidases from several bacteria are compared in Table 2, page 198; "Biosynthesis of Halogenated Metabolites by Bacteria" by von Pée K. H., Annu. Rev. Microbiol. 50 (1996), 375-399, in which vanadium-containing non-heme halogen peroxidases are described on page 389 and bacterial non-heme halogen peroxidases on pages 389-392.

For the purposes of the present invention, enzymes are suitable which contain a catalytic triad consisting of the amino acids aspartate, histidine and serine, which is associated with the halogenation activity of the enzyme. The first step of the halogenation, which is catalyzed by the bacterial non-heme halogen peroxidase, is the formation of an acetate ester on the serine residue of the catalytic triad.

This ester is not hydrolyzed by water, but by hydrogen peroxide, resulting in the formation of peracetic acid. As strong oxidizing agents, peracids are able to nonspecifically oxidize bromide, chloride and aromatic amino to nitro groups. The non-heme halogen peroxidases are substrate nonspecific.

Non-heme bromoperoxidase enzymes are preparable from Corallina marina algae (JP63 196 295 and JP61 242 577). Suitable non-heme haloperoxidases for the purposes of the present invention can be obtained as set out below:

1. Non-heme chloro- and bromo-peroxidases from Pseudomonas species and Streptomyces species and Serratia species, described in WO 96/06909 by Degussa, pp. 7-9:

1.1. Non-heme chloroperoxidase from Serratia marcescens as described in Microbiol. Lett., vol. 129 (1995), pp. 255-260.

1.2. Non-heme bromoperoxidase from Streptomyces aureofaciens ATCC 10762 in J. Gen. Microbiol. 137 (1992), pp. 2539-2546.

1.3. Non-heme chloroperoxidase from Pseudomonas fluorescens as described in Microbiology 142 (1996), 2129-2135, by Kirner S. et al.

2. Non-heme bromoperoxidase from Corallina marina algae (e.g. C. officinalis, C. pilulifera, C. squamata, Serraticardia maxima and Calliarthron yessoense) as described in JP63196295 and JP61242577, both from Amano Pharm KK.

Preferred non-heme haloperoxidases for use in the invention are the enzymes obtained as described in WO 96/06909. A more preferred enzyme is the non-heme chloroperoxidase obtained from Serratia marcescens.

The non-heme halogen peroxidase is preferably included in the cleaning compositions of the invention at a level of 0.0001 to 2%, more preferably 0.001 to 1.0%, most preferably 0.005 to 0.1% pure enzyme, based on the weight of the composition.

Preferred non-heme halogen peroxidases for specific applications are alkaline, i.e. enzymes having an enzyme activity of at least 10%, preferably at least 25%, more preferably at least 40%, of their maximum activity at a pH in the range of 7 to 12. More preferred non-heme halogen peroxidases are enzymes whose maximum activity is at a pH in the range of 7 to 12.

Enzymes homologous to the non-heme halogen peroxidase enzymes of the invention are also included. The term "homologous" is intended to refer to a polypeptide encoded by a DNA that hybridizes to the same probe as the DNA encoding the non-heme halogen peroxidase enzyme having that amino acid sequence under certain specific conditions (such as pre-soaking in 5x SSC and prehybridizing for 1 h at ~40°C in a solution of 20% formamide, 5x Denhardt's solution, 50 mM sodium phosphate, pH 6.8, and 50 µg denatured sonicated calf thymus DNA, followed by hybridization in the same solution supplemented with 100 µM ATP for 18 h at ~40ºC). The term is intended to include derivatives of the non-heme halogen peroxidase enzyme sequence obtained by the addition of one or more amino acid residues to the C- and/or N-terminus of the native sequence, the substitution of one or more amino acid residues at one or more sites in the native sequence, the deletion of one or more amino acid residues at one or both ends of the native amino acid sequence or at one or more sites within the native sequence, or the insertion of one or more amino acid residues into one or more sites in the native sequence.

The above mentioned enzymes can be of any suitable origin, such as from plants, animals, bacteria, fungi and yeasts. The origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic etc.). Purified or unpurified forms of these enzymes can be used. It is now common to modify wild type enzymes using protein/genetic engineering techniques to optimize their performance in the cleaning compositions of the invention. For example, the variants can be designed to increase the compatibility of the enzyme with commonly occurring ingredients of such compositions. Alternatively, the variant can be designed to adapt the optimum pH, bleaching or chelating stability, catalytic activity and the like of the enzyme variant so that it is suitable for the particular cleaning application.

In particular, amino acids that are sensitive to oxidation should be taken into account in the case of bleach stability and surface charges for surfactant compatibility. The isoelectric point of such enzymes can be modified by the substitution of some charged amino acids; e.g., increasing the isoelectric point can help to improve compatibility with anionic surfactants. The stability of the enzymes can be further increased by the formation of, e.g., additional salt bridges and forcing calcium binding sites to increase chelator stability.

Organic acid

A second essential element of the cleaning compositions of the invention is an organic acid. The organic acid is characterized by a pKa value at 20°C between 2 and 10, preferably between 3 and 9, and more preferably between 3.5 and 8.

Suitable acids are listed in the CRC Handbook for Chemistry and Physics, Lide DR, 71st edition, CRC Press, Section 8, pp. 35-36. Suitable organic acids are acetic, propionic, butyric, hexanoic, octanoic, decanoic, malic, oxalic, benzoic and citric acid and/or mixtures thereof and/or salts thereof. Also suitable are Lactic acid, fruit acids, benzoic acid, phthalic acid and/or mixtures thereof and/or salts thereof.

Preferred organic acids are monocarboxylic acids of the formula RnH(n+1)COOH, where n = 1-9, such as acetic acid, propionic acid, nonanoic acid and/or their corresponding sodium salts.

The organic acids are generally included in the cleaning compositions of the invention in an amount of 0.1 to 50%, preferably 0.5 to 40%, more preferably 1 to 20%, based on the total composition.

Hydrogen peroxide source

A third essential element of the cleaning compositions of the invention is a source of hydrogen peroxide. A suitable hydrogen peroxide source is a compound or system that can release hydrogen peroxide into the washing solution. Examples are percarbonate, perborate or enzymatic systems that generate hydrogen peroxide in situ, such as oxidases.

Sources of hydrogen peroxide suitable for use in the invention include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate or perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates, peroxyhydrates and urea hydrogen peroxide. Preferred bleaching agents are percarbonates and perborates.

It may also be desirable to utilize an enzymatic process for hydrogen peroxide formation. Thus, the process of the invention may additionally comprise the addition of an enzymatic system (i.e. an enzyme and a substrate therefor) capable of generating hydrogen peroxide during the washing process. One such category of hydrogen peroxide generating systems includes enzymes capable of converting molecular oxygen and an organic or inorganic substrate into hydrogen peroxide or the oxidized substrate, respectively. These enzymes generate only small amounts of hydrogen peroxide, but they can be used very advantageously in the process of the invention since the presence of an oxidase ensures efficient utilization of the hydrogen peroxide generated. Preferred hydrogen peroxide generating systems are those which act on inexpensive and readily available substrates, which may be suitably included in the cleaning compositions. For example, one can use an amine oxidase and an amine, an amino acid oxidase and an amino acid, a lactate oxidase and a lactate, a cholesterol oxidase and cholesterol, a uric acid oxidase and uric acid, or a xanthine oxidase with xanthine. Other suitable oxidases are urate oxidase, galactose oxidase, alcohol oxidase, and amyloglucosidase.

The preferred enzymatic systems are alcohol and aldehyde oxidases. The more preferred systems for use in granular detergents would include solid alcohols, e.g. glucose, whose oxidation by a glucose oxidase to Glucuronic acid is catalyzed to form hydrogen peroxide. The combination of glucose oxidase and glucose is preferred. The amount of glucose oxidase depends on its specific activity and the activity of the remaining catalase which may be present, but for example it can generally be stated that the detergent composition according to the invention contains 10 to 1,000, preferably 20 to 500, units of glucose oxidase per gram or milliliter of detergent composition, one unit of enzyme activity being defined as the amount required to convert 1 µmol of substrate per minute under standard conditions.

The more preferred systems for use in liquid detergents would include liquid alcohols which may also act as solvents, for example. One example is ethanol/ethanol oxidase. Such enzymatic systems are disclosed in EP patent application EP 537 381, filed October 9, 1991.

The proportion of hydrogen peroxide in the wash solution is crucial for the stability of the non-heme halogen peroxidase. Therefore, the controlled release of hydrogen peroxide into the wash solution could be used in the enzymatic non-heme halogen peroxidase bleaching system.

The hydrogen peroxide is generally present in the washing solution in a proportion of 0.0001-10 mmol, preferably 0.0001-2 mmol, more preferably 0.0001-0.3 mmol, which is preferably maintained by means of a controlled release system.

The hydrogen peroxide can be produced by a perborate, percarbonate or an enzymatic system for producing hydrogen peroxide in a proportion of 0.1-0.2 mmol.

A release agent is an agent that releases the entrapped hydrogen peroxide source into the wash environment in a controlled manner.

For granular and powdered cleaning products, the hydrogen peroxide source may be contained in a granulate. The granulate may suitably further contain various granulation aids, binders, fillers, plasticizers, lubricants, cores and the like. Examples include cellulose (e.g. cellulose in fibrous or microcrystalline form), dextrins (e.g. yellow dextrin), polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivatives (such as CMC, MC, HPC or HPMC), gelatin, starch, sugars, salts (e.g. sodium sulfate, sodium chloride, calcium sulfate or calcium carbonate), titanium dioxide, talc and clays (e.g. kaolin or bentonite). Other materials which are relevant for inclusion in the granules of the type in question are described, for example, in EP 0 304 331 B1 and are well known to those skilled in the art.

The release agent can be, for example, a coating. The coating protects the granules (co-granules) in the washing environment for a certain period of time. The coating is usually applied to the granules (co- Granules) in an amount in the range of 1 to 50 wt.% (calculated on the basis of the weight of the uncoated dry granules), preferably in the range of 5 to 40 wt.%. The amount of coating to be applied to the granules depends to a considerable extent on the type and composition of the coating desired and the type of protection the coating is intended to provide for the granules. For example, the thickness of the coating or a multi-layer coating applied to any of the above granules may determine the period of time over which the contents of the granules are released. A possible multi-layer coating may be a coating wherein, for example, a fast release coating is overcoated with a slow release coating.

Suitable release coatings are coatings which effect a release of the contents of the granules of the invention containing a source of peroxide under the conditions prevailing during use thereof. Consequently, when a preparation of the invention is introduced into a wash liquor containing a detergent (normally comprising, for example, one or more types of surfactant), the coating should, for example, be one which ensures the release of the contents of the granules by the release agent when introduced into the wash medium.

Preferred release coatings are coatings which are substantially insoluble in water. Release coatings which are suitable in wash media suitably comprise substances selected from the following: tallow; hydrogenated tallow; partially hydrogenated tallow; fatty acids and fatty alcohols of natural and synthetic origin; long chain fatty acid mono-, di- and triesters of glycerol (e.g. glycerol monostearate); ethoxylated fatty alcohols; latexes; hydrocarbons having a melting point in the range of 50-80°C; and waxes. Melting coatings are a preferred class of fast or slow release coatings which can be used without dilution with water. For further information on slow release coatings, reference may be made to Controlled Release Systems: Fabrication Technology, Vol. I, CRC Press, 1988.

Coatings may suitably further comprise substances such as clays (e.g. kaolin), titanium dioxide, pigments, salts (such as calcium carbonate) and the like. Other coating components relevant to the present invention are known to those skilled in the art.

In the liquid cleaning compositions of the present invention, the hydrogen peroxide source may be included as a dispersion of particles further containing a release agent. The hydrogen peroxide source may be in liquid or solid form. Suitable particles are made of a porous hydrophobic material (e.g., silica having an average pore diameter of 5 x 10-8 m (500 angstroms) or more) as described in EP 583,512 to Surutzidiz A. et al.

The release agent could be a coating which protects the particles in the wash cycle for a certain period of time. The coating is preferably a hydrophobic material, e.g. a hydrophobic liquid polymer. The polymer can be an organopolysiloxane oil, alternatively a high molecular weight hydrocarbon or a water-insoluble but water-permeable polymeric material, e.g. CMC, PVA or PVP. The polymer properties are chosen to achieve a suitable release profile of the source of its peroxide in the wash solution.

Surfactant system

The cleaning compositions of the invention comprise a surfactant system, wherein the surfactant can be selected from nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semipolar surfactants.

The surfactant is typically present at a level of 0.1 to 60% by weight. More preferred incorporation levels are 1 to 35% by weight, most preferably 1 to 30% by weight, of the cleaning compositions of the invention.

The surfactant is preferably formulated to be compatible with enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated to promote the stability of, or at least not degrade, any enzyme in those compositions.

Preferred surfactant systems for use according to the invention comprise as surfactant one or more of the nonionic and/or anionic surfactants described herein.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing 6 to 14 carbon atoms, preferably 8 to 14 carbon atoms, in either a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount corresponding to 2 to 25 moles, more preferably 3 to 15 moles, of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal™ CO-630, sold by GAF Corporation; and Triton™ X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g. alkylphenol ethoxylates).

The condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitable for use as nonionic surfactants in the nonionic surfactant systems according to the invention. The alkyl chain of the aliphatic alcohol can be either straight or branched, primary or secondary and generally contains 8 to 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, with 2 to 10 moles of ethylene oxide per mole of alcohol. In the condensation products there are 2 to 7 moles of ethylene oxide and most preferably 2 to 5 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of a C₁₁-C₁₅ linear alcohol with 9 moles of ethylene oxide) and TergitolTM 24- L-6 NMW (the condensation product of a C₁₂-C₁₄ primary alcohol with 6 moles of ethylene oxide having a narrow molecular weight distribution), both sold by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of a linear C₁₄-C₁₅ alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of a linear C₁₂-C₁₃ alcohol with 3 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of a linear C₁₄-C₁₅ alcohol with 7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of a linear C₁₄-C₁₅ alcohol with 5 moles of ethylene oxide), sold by Shell Chemical Company; KyroTM EOB (the condensation product of a C13-C15 alcohol with 9 moles of ethylene oxide) sold by The Procter & Gamble Company; and Genapol LA O3O or O5O (the condensation product of a C12-C14 alcohol with 3 or 5 moles of ethylene oxide) sold by Hoechst. The preferred HLB range in these products is 8-11 and most preferably 8-10.

Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkyl polysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, which have a hydrophobic group containing 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, and a hydrophilic polysaccharide group, e.g., a polyglycoside containing 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7, saccharide units. Any reducing saccharide having 5 or 6 carbon atoms can be used; e.g., For example, glucose, galactose and galactosyl groups can be substituted for the glucosyl groups (optionally the hydrophobic group is attached in the 2-, 3-, 4-, etc. positions, thus obtaining a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be present, for example, between the 1-position of the additional saccharide units and the 2-, 3-, 4- and/or 6-positions in the preceding saccharide units.

The 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 from 10 to 18, preferably 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is 0 to 10, preferably 0; and x is 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose or a source of glucose to form the glucoside. (bound in the 1-position). The additional glycosyl units can then be bound between their 1-position and the preceding glycosyl units in the 2-, 3-, 4- and/or 6-position, preferably predominantly in the 2-position.

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as additional nonionic surfactant systems of the invention. The hydrophobic portion of these compounds preferably has a molecular weight of from 1,500 to 1,800 and exhibits water insolubility. The addition of polyoxyethylene groups to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is maintained until the polyoxyethylene content is 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available PlurafacTM LF404 and PluronicTM surfactants sold by BASF.

Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic group of these products consists of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of 2,500 to 3,000. This hydrophobic group is condensed with ethylene oxide to the extent that the condensation product contains 40 to 80 weight percent polyoxyethylene and has a molecular weight of 5,000 to 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic™ compounds sold by BASF.

Preferred for use as nonionic surfactant in the surfactant systems of the invention are polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide, alkyl polysaccharides and mixtures thereof. Most preferred are C8-C14 alkylphenol ethoxylates having 3 to 15 ethoxy groups and C8-C18 alcohol ethoxylates (preferably on average C10) having 2 to 10 ethoxy groups and mixtures thereof.

Particularly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

wherein R¹ is H or R¹ is a C₁₋₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R² is C₅₋₃₁ hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyl groups directly attached to the chain, or an alkoxylated derivative thereof. Preferably R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl or C₁₅₋₁₇ alkyl or alkenyl chain such as coconut alkyl, or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose or lactose in a reductive amination reaction.

Suitable anionic surfactants which can be used are linear alkylbenzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e. fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society" 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances, e.g. derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, particularly for washing applications, includes alkyl ester sulfonate surfactants of the structural formula:

wherein R3 is C8-C20 hydrocarbyl, preferably alkyl or a combination thereof, R4 is C1-C6 hydrocarbyl, preferably alkyl or a combination thereof, and M is a cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, as well as substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R3 is C10-C16 alkyl and R4 is methyl, ethyl or isopropyl. Particularly preferred are the methyl ester sulfonates, wherein R3 is C10-C16 alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactants, which are water soluble salts or acids of the formula ROSO₃M, where R is preferably a C₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀-C₂₀ alkyl moiety, more preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation, e.g. B. an alkali metal cation (e.g. sodium, potassium or lithium) or ammonium or substituted ammonium (e.g. methyl, dimethyl and trimethyl ammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Typically, alkyl chains of C₁₂₋₁₆ are preferred for low wash temperatures (e.g. below 50°C); and C₁₆₋₁₈ alkyl chains are preferred for higher wash temperatures (e.g. above 50°C).

Other anionic surfactants useful for cleaning purposes may also be included in the cleaning compositions of the invention. These may be salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, primary or secondary C₈-C₂₂ alkanesulfonates, C₈-C₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by the sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g. B. as described in British Patent Specification No. 1,082,179, C₈-C₂₄-alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide), alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (particularly saturated and unsaturated C₁₂-C₁₈-monoesters) and diesters of sulfosuccinates (particularly saturated and unsaturated C₆-C₁₂-diesters), sulfates of alkyl polysaccharides such as the sulfates of alkyl polyglucoside (the nonionic nonsulfated compounds described below), branched primary alkyl sulfates and alkyl polyethoxycarboxylates such as those of the formula RO(CH₂CH₂O)k-CH₂COO⁻M⁺, wherein R is C₈-C₂₂ alkyl, k is an integer from 0 to 10 and M is a cation which forms a soluble salt. Resin acids and hydrogenated resin acids are also suitable, such as rosin or hydrogenated rosin, as well as resin acids and hydrogenated resin acids found in or derived from tall oil.

Further examples are described in "Surface Active Agents and Detergents" (Vols. I and II, by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin et al., at column 23, line 58 through column 29, line 23 (incorporated herein by reference).

If included therein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 20%, by weight of such anionic surfactants.

Particularly preferred anionic surfactants include alkoxylated alkyl sulfate surfactants which are water soluble salts or acids of the formula RO(A)mSO3M, wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl moiety, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably a C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy moiety, m is greater than 0, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which is, for example, a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Ethoxylated alkyl sulfates as well as propoxylated alkyl sulfates are included here. Specific examples of substituted ammonium cations include methyl, dimethyl and trimethylammonium cations as well as quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and those derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like. Exemplary surfactants are C₁₂-C₁₈-alkyl polyethoxylate (1,0) sulfate (C₁₂- C₁₈E(1,0)M), C₁₂-C₁₈-alkyl polyethoxylate (2,25) sulfate (C₁₂-C₁₈E(2,25)M), C₁₂-C₁₈-alkyl polyethoxylate (3,0) sulfate (C₁₂-C₁₈E(3,0)M) and C₁₂-C₁₈ alkyl polyethoxylate (4,0) sulfate (C₁₂-C₁₈E(4,0)M), wherein M is conveniently selected from sodium and potassium.

The cleaning compositions of the invention may also contain cationic, ampholytic, zwitterionic and semipolar surfactants as well as other nonionic and/or anionic surfactants than those already described herein.

Cationic detersive surfactants suitable for use in the cleaning compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halides and those surfactants having the formula:

[R²(OR³)y][R⁴(OR³)y]₂R⁵N⁺X⁻

wherein R2 is an alkyl or alkylbenzyl group having 8 to 18 carbon atoms in the alkyl chain; each R3 is selected from the group consisting of -CH2CH2-, -CH2CH- (CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by linking the two R4 groups, -CH2CHOH- CHOHCOR6CHOHCH2OH, wherein R6 is is any hexose or hexose polymer having a molecular weight of less than 1,000, and hydrogen when y is not 0; R⁵ has the same meaning as R⁴ or is an alkyl chain wherein the total number of carbon atoms of R² plus R⁵ is not more than 18; each y is 0 to 10 and the sum of the y values is 0 to 15; and X is any compatible anion.

A quaternary ammonium surfactant suitable according to the invention has the formula (I): Formula (I)

wherein R₁ is a short chain alkyl (C6-C10) or an alkylamidoalkyl of formula (II): Formula (II)

wherein y is 2-4, preferably 3;

wherein R₂ is H or C₁-C₃ alkyl;

where x is 0-4, preferably 0-2, most preferably 0;

wherein R₃, R₄ and R₅ are either the same or different and are either a short chain alkyl (C1-C3) or an alkoxylated alkyl of formula (III); and

where X⊃min; is a counter ion, preferably a halide, e.g. chloride or methyl sulfate. Formula (III)

wherein R₆ is C₁-C₄ and z is 1 or 2.

Preferred quaternary ammonium surfactants are those defined in formula (I), wherein:

R₁, C₈, C₁₀ or mixtures thereof; x = 0;

R₃, R₄ = CH₃; and R₅ = CH₂CH₂OH.

Particularly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the composition of the invention, according to the formula:

R&sub1;R&sub2;R&sub3;R&sub4;N&spplus;X&supmin; (i)

wherein R₁ is C₈-C₁₆ alkyl, each R₂, R₃ and R₄ are independently C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl and -(C₂H₄O)xH, where x has a value of 2 to 5, and X is an anion ; where no more than one of R₂, R₃ or R₄ should be benzyl.

The preferred alkyl chain length for R1 is C12-C15, especially when the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or is synthetically derived via olefin buildup or OXO alcohol synthesis. Preferred groups for R2, R3 and R4 are methyl and hydroxyethyl groups, and the anion X can be selected from halide, methosulfate, acetate and phosphate ions.

Examples of suitable quaternary ammonium compounds of formula (i) for use herein are:

Coconut trimethylammonium chloride or bromide;

coconut methyl dihydroxyethyl ammonium chloride or bromide;

Decyltriethylammonium chloride;

Decyldimethylhydroxyethylammonium chloride or bromide;

C12-15 dimethylhydroxyethyl ammonium chloride or bromide;

Coconut dimethylhydroxyethylammonium chloride or bromide;

myristyl trimethyl ammonium methyl sulfate;

Lauryldimethylbenzyl ammonium chloride or bromide;

Lauryldimethyl(ethenoxy)₄-ammonium chloride or bromide;

Choline esters (compounds of formula (i) wherein R₁ is:

and R₂, R₃ and R₄ are methyl); and

Dialkylimidazolines (compounds of formula (i)).

Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, and in European Patent Application EP- 000,224.

Typical cationic fabric softener components include the water-insoluble quaternary ammonium fabric softener actives or their corresponding amine precursors, the most commonly used being long-chain dialkylammonium chlorides or methyl sulfates.

Preferred cationic softeners among these include the following:

1) Ditallowdimethylammonium chloride (DTDMAC);

2) dihydrogenated tallowdimethyl ammonium chloride;

3) dihydrogenated tallow dimethyl ammonium methyl sulfate;

4) Distearyldimethylammonium chloride;

5) Dioleyldimethylammonium chloride;

6) Dipalmitylhydroxyethylmethylammonium chloride;

7) Stearylbenzyldimethylammonium chloride;

8) Tallowtrimethylammonium chloride;

9) hydrogenated tallow trimethyl ammonium chloride;

10) C12-14 alkylhydroxyethyldimethylammonium chloride;

11) C12-18 alkyldihydroxyethylmethylammonium chloride;

12) Di(stearoyloxyethyl)dimethylammonium chloride (DSOEDMAC);

13) Di(tallowoxyethyl)dimethylammonium chloride;

14) Ditallowimidazolinium methyl sulfate;

15) 1-(2-tallowylamidoethyl)-2-tallowylimidazolinium methyl sulfate.

Biodegradable quaternary ammonium compounds have been presented as alternatives to the traditionally used long-chain dialkylammonium chlorides and methyl sulfates. Such quaternary ammonium compounds contain long-chain alk(en)yl groups interrupted by functional groups such as carboxy groups. These materials and fabric softening compositions containing them are disclosed in numerous publications, e.g. EP-A-0,040,562 and EP-A-0,239,910.

The quaternary ammonium compounds and amine precursors herein have the following formula (I) or (II):

wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR⁴-C(O)- and -C(O)-NR⁴-;

R¹ is (CH₂)n-Q-T² or T³;

R² is (CH₂)m-Q-T⁴ or T⁵ or R³;

R³ is C₁-C₄alkyl or C₁-C₄hydroxyalkyl or H;

R⁴ is H or C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl;

T¹, T², T³, T⁴ and T⁵ are independently C₁₁-C₂₂ alkyl or alkenyl;

n and m are integers from 1 to 4; and

X⊃min; is a plasticizer compatible anion.

Non-limiting examples of plasticizer compatible anions include chloride or methyl sulfate.

The alkyl or alkenyl chain T¹, T², T³, T⁴, T⁵ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain can be straight or branched.

Tallow is a convenient and inexpensive source of the long chain alkyl and alkenyl material. The compounds wherein T¹, T², T³, T⁴, T⁵ represent a mixture of long chain materials typical of tallow are particularly preferred.

Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softener compositions herein include:

1) N,N-Di(tallowoyloxyethyl)-N,N-dimethylammonium chloride;

2) N,N-Di(tallowyloxyethyl)-N-methyl-N-(2-hydroxyethyl)ammonium methyl sulfate;

3) N,N-Di-(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammonium chloride;

4) N,N-Di-(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium chloride;

5) N-(2-tallowyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammonium chloride;

6) N,N,N-Tri(tallowyloxyethyl)-N-methylammonium chloride;

7) N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethylammonium chloride; and

8) 1,2-Ditallowyloxy-3-trimethylammoniopropane chloride;

and mixtures of any of the above materials.

If included, the cleaning compositions of the invention typically comprise from 0.2 to 25% by weight, preferably from 1 to 8% by weight, of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the cleaning compositions of the invention. These surfactants can be generally described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic moiety can be straight or branched chain. One of the aliphatic substituents contains at least 8 carbon atoms, typically 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate or sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975, at column 19, lines 18-35, for examples of ampholytic surfactants.

If included, the cleaning compositions of the invention typically comprise from 0.2 to 15% by weight, preferably from 1 to 10% by weight, of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in cleaning compositions. These surfactants can be generally 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. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975, at column 19, line 18 through column 22, line 48, for examples of zwitterionic surfactants.

If included, the cleaning compositions of the invention typically comprise from 0.2 to 15% by weight, preferably from 1 to 10% by weight, of such zwitterionic surfactants.

Semipolar nonionic surfactants are a special category of nonionic surfactants which includes water-soluble amine oxides containing one alkyl group having 10 to 18 carbon atoms and two groups selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl group having 10 to 18 carbon atoms and two groups selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl group having 10 to 18 carbon atoms and one group selected from the group consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxide surfactants with the formula:

wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing 8 to 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; x is 0 to 3; and each R5 is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide groups. The R5 groups can be linked together to form a ring structure, for example via an oxygen or nitrogen atom.

These amine oxide surfactants include, in particular, C₁₀-C₁₈ alkyldimethylamine oxides and C₈-C₁₂ alkoxyethyldihydroxyethylamine oxides.

If included, the cleaning compositions of the invention typically comprise from 0.2 to 15% by weight, preferably from 1 to 10% by weight, of such zwitterionic surfactants.

The cleaning composition of the invention may further comprise a co-surfactant selected from the group of primary or tertiary amines. Suitable primary amines for use herein include amines according to the formula R₁NH₂, wherein R₁ is a C₆-C₁₂, preferably C₆-C₁₀ alkyl chain or R₄X(CH₂)n, wherein X is -O-, -C(O)NH- or -NH-, R₄ is a C₆-C₁₂ alkyl chain, and n is between 1 to 5 and preferably 3. R₁ alkyl chains may be straight or branched and may be interrupted by up to 12, preferably less than 5, ethylene oxide groups. Preferred amines according to the above formula are n-alkylamines. Suitable amines for use herein may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amidopropylamine.

Suitable tertiary amines for use herein include tertiary amines of the formula R₁R₂R₃N, wherein R₁ and R₂ are C₁-C₈ alkyl chains or

are;

R₃ is either a C₆-C₁₂ or preferably a C₆-C₁₀ alkyl chain or R₃ has the meaning R₄X(CH₂)n, where X has the meaning -O-, -C(o)NH- or -NH-, R₄ is a C₄-C₁₂ alkyl chain and n is between 1 to 5 and preferably 2-3. R₅ is H or C₁-C₂ alkyl and x is between 1 to 6.

R₃ and R₄ can be linear or branched; R₃ alkyl chains can be interrupted by up to 12, preferably less than 5, ethylene oxide groups.

Preferred tertiary amines correspond to the formula R₁R₂R₃N, wherein R₁ is a C₆-C₁₂-alkyl chain, R₂ and R₃ are C₁-C₃-alkyl or

wherein R₅ is H or CH₃ and x = 1-2.

Also preferred are the amidoamines of the formula:

wherein R₁ is C₆-C₁₂ alkyl; n is 2-4, preferably n is 3; and R₂ and R₃ are C₁-C₄ .

Most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C₈-C₁₀-oxypropylamine, N-coco-1,3-diaminopropane, coconut alkyldimethylamine, lauryldimethylamine, laurylbis(hydroxyethyl)amine, Cocobis(hydroxyethyl)amine, laurylamine propoxylated with 2 moles, octylamine propoxylated with 2 moles, laurylamidopropyldimethylamine, C8-C10 amidopropyldimethylamine and C10 amidopropyldimethylamine.

The most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine and 1-dodecylamine. Particularly preferred are n-dodecyldimethylamine and bishydroxyethyl coconut alkylamine and 7-fold ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.

Detergent components

The cleaning compositions of the invention may also contain additional detergent components. The precise nature of these additional components and the incorporation levels thereof will depend on the physical form of the composition and the type of cleaning process for which it is to be used.

In a preferred embodiment, the present invention relates to a detergent and/or fabric care composition comprising a surfactant system and a non-heme halogen peroxidase (Examples 1-18). In a second embodiment, the present invention relates to dishwashing or household cleaning compositions, including sanitation formulations (Examples 18-28); and in a third embodiment, the present invention relates to oral/dental care compositions (Examples 29-30).

The cleaning compositions of the invention may be liquids, pastes, gels, bars, tablets, sprays, foams, powders or granules. Granular compositions may also be in "compact" form; the liquid compositions may also be in "concentrated" form.

The compositions of the invention can be formulated, for example, as manual and machine dishwashing compositions, manual and machine laundry detergent compositions, including laundry additive compositions and compositions suitable for use in soaking and/or pretreating stained fabrics, rinse-added fabric softening compositions and compositions for general household use in hard surface cleaning processes. Non-heme halogen peroxidase-containing compositions can also be formulated as oral/dental care compositions.

When formulated as compositions for use in manual dishwashing processes, the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from organic polymeric compounds, suds boosters, Group II metal ions, solvents, hydrotropes and additional enzymes.

When formulated as compositions suitable for use in a machine laundry process, the inventive Compositions preferably contain both a surfactant and a builder compound and additionally one or more detergent components, preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime soap dispersants, soil suspending and antiredeposition agents and corrosion inhibitors. Detergent compositions may also contain softeners as additional detergent components.

Compositions containing a surfactant system and a non-heme halogen peroxidase can provide fabric cleaning, stain removal, whiteness maintenance, softening, color refreshment and dye transfer inhibition when formulated as laundry detergent compositions.

The compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or enhance the performance of conventional detergent compositions.

Optionally, the density of the laundry detergent compositions herein ranges from 400 to 1,200 g/litre, preferably 600 to 950 g/litre, of the composition, measured at 20ºC.

The "compact" form of the compositions herein can best be illustrated by the density and, compositionally, by the amount of inorganic filler salt. Inorganic filler salts are conventional components of detergent compositions in powder form. In conventional detergent compositions, the filler salts are present in substantial amounts; typically 17-35% by weight of the total composition.

In the compact compositions, the filler salt is present in amounts not exceeding 15% by weight of the total composition, preferably 10% by weight, most preferably 5% by weight of the composition.

The inorganic filler salts as referred to in the present compositions are selected from the alkali and alkaline earth metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate.

Liquid detergent compositions according to the invention can also be in "concentrated" form. In such a case, the liquid detergent compositions according to the invention contain a smaller amount of water compared to conventional liquid detergents.

Typically, the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20%, by weight of the cleaning composition.

Conventional detergent enzymes

The cleaning compositions may further comprise, in addition to the non-heme halogen peroxidase enzyme, one or more enzymes which provide cleaning performance and/or fabric care benefits. It has been found that the combination of the non-heme halogen peroxidase with a detergent enzyme provides improved cleaning of coloured and/or common human stains and/or soils and, when formulated as a detergent composition, improved cleaning and bleaching of fabric-like articles.

The enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, 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 is a cleaning composition with a cocktail of conventionally usable enzymes, such as protease, amylase, lipase, cutinase and/or cellulase, in conjunction with one or more enzymes which degrade the plant cell wall.

The cellulases usable in the invention include both bacterial and fungal cellulases. Preferably they have a pH optimum between 5 and 12 and an activity of over 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in US Patent 4,435,307, Barbesgoard et al., J-61078384, and WO 96/02653, which disclose fungal cellulases produced by Humicola insolens, Trichoderma, Thielavia and Sporotrichum, respectively. EP-739 982 describes cellulases isolated from new Bacillus species. Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2,095,275; DE-OS-2,247,832; and WO 95/26398.

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, having a molecular weight of 50 kDa, an isoelectric point of 5.5 and containing 415 amino acids; and a 43 kDa 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. WO 91/17243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum, which are described in WO 94/21801, Genencor, published September 29, 1994. Particularly suitable cellulases are the cellulases with color care benefits. Examples of such cellulases are cellulases described in European Patent Application No. 91202879.2, filed on 6 November 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are particularly useful. See also WO 91/17244 and WO 91/21801. Other suitable cellulases with fabric care and/or cleaning properties are described in WO 96/34092, WO 96/17994 and WO 95/24471.

The cellulases are normally included in the cleaning composition in amounts of 0.0001 to 2% active enzyme based on the weight of the cleaning composition.

Other preferred enzymes which may be included in the cleaning compositions of the invention include lipases. Suitable lipase enzymes for use in cleaning compositions include those produced by microorganisms of the Pseudomonas group, e.g. Pseudomonas stutzeri 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 the lipase produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", hereinafter referred to as Amano-P. Other suitable commercial lipases include Amano-CES; lipases from Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., USA, and Disoynth Co., Netherlands; and lipases from Pseudomonas gladioli. Particularly suitable lipases are lipases such as M1-Lipase® and Lipomax® (Gist-Brocades) as well as Lipolase® and Lipolase Ultra® (Novo), which have been found to be very effective when used in combination with the compositions of the invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by 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 surface activation. The addition of cutinases to detergent compositions has been described, for example, in WO-A 88/09367 (Genencor); WO 90/09446 (Plant Genetic System); and WO 94/14963 and WO 94/14964 (Unilever).

The lipases and/or cutinases are normally included in the detergent composition in proportions of 0.0001 to 2% active enzyme based on the weight of the detergent composition.

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 strain of Bacillus which has maximum activity over the pH range of 8-12; developed and sold as ESPERASE® by Novo Industries A/S. Denmark, hereinafter "Novo". The manufacture 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-modified Maxacal) from Gist-Brocades. Proteolytic enzymes also include modified bacterial Serine proteases, e.g. those described in European Patent Application No. 87 303761.8, filed on April 28, 1987 (particularly pages 17, 24 and 98), which relates to a modified bacterial serine protease enzyme, referred to herein as "Protease A". Also suitable is the protease referred to herein as "Protease C", which is a variant of an alkaline serine protease from Bacillus in which arginine in position 27 has been replaced by lysine, valine in position 104 by tyrosine, asparagine in position 123 by serine and threonine in position 274 by alanine. Protease C is described in EP 90915958.4, corresponding to WO 91/06637, published on May 16, 1991. Genetically modified variants, in particular of protease C, are also included here.

A preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant having a non-naturally occurring amino acid sequence which is derived from a precursor carbonyl hydrolase by substituting another amino acid with a plurality of amino acid residues at a position in said carbonyl hydrolase corresponding to position +76, preferably also in combination with one or more amino acid residues corresponding to positions 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 WO 95/10591 and in the patent application of Ghosh C. et al., "Bleaching Compositions Comprising Protease Enzymes", with US application number 08/322,677, filed October 13, 1994.

Also suitable according to the invention are proteases which are described in the patent applications EP 251 446 and WO 91/06637, as well as protease BLAP®, which is described in WO 91/02792, and its variants which are described in WO 95/23221.

See also a high pH active protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. Optionally, a protease having reduced adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents useful herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 to Unilever.

The proteolytic enzymes are included in the detergent compositions of the invention in an amount of 0.0001 to 2%, preferably 0.001 to 0.2%, more preferably 0.005 to 0.1%, active enzyme, based on the weight of the composition.

Amylases (α and/or β) may be included to remove carbohydrate stains. WO 94/02597, Novo Nordisk A/S, published February 3, 1994, describes cleaning compositions which include mutated amylases. See also WO 95/10603, 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 described in US 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 amylases with improved stability described in WO94/18314, published August 18, 1994, and WO 96/05295, Genencor, published February 22, 1996, and amylase variants with additional modification in the immediate parent form available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277,216; WO 95/26397; and WO 96/23873 (all from Novo Nordisk).

Examples of commercial α-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A/S, Denmark. WO 95/26397 describes other suitable amylases: α-amylases characterized by a specific activity that is at least 25% higher than the specific activity of Termamyl® in a temperature range of 25ºC to 55ºC and a pH in the range 8 to 10, measured by the Phadebas® α-amylase activity test. Suitable are variants of the above enzymes described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties in terms of activity level and the combination of heat stability and a higher activity level are described in WO 95/35382.

The amylolytic enzymes are included in the detergent compositions of the invention at a level of 0.0001 to 2%, preferably 0.00018 to 0.06%, more preferably 0.00024 to 0.048% pure enzyme, based on the weight of the composition.

The enzymes mentioned above can be of any suitable origin, such as from plants, animals, bacteria, fungi and yeasts. The origin can also be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes can be used. Also included by definition are mutants of native enzymes. Mutants can be obtained, for example, by protein and/or genetic engineering techniques, chemical and/or physical modifications of native enzymes. It is also common practice to express the enzyme using host organisms into which the genetic material responsible for the production of the enzyme has been cloned.

The enzymes are normally present in the cleaning composition in proportions of 0.0001 to 2% active enzyme, based on the weight of the cleaning composition, The enzymes can be added as separate individual components (prills, granules, stabilized liquids, etc. containing an enzyme) or as mixtures of two or more enzymes (e.g. co-granules).

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

A number of enzyme materials and means for incorporating them into synthetic detergent compositions are also disclosed in WO 93/072263 A and WO 93/07260 A to Genencor International; WO 89/08694 A to Novo; and US 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in US 4,101,457, Place et al., July 18, 1978; and in US 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are disclosed 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 illustrated 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 species, AC13, which yields proteases, xylanases and cellulases, is described in WO 94/01532 A to Novo.

Bleach

Preferred additional optional detergent ingredients that can be included in the cleaning compositions of the invention include conventional, activated, other enzymatic and/or metallocatalyst bleaching systems. It has been found that the combination of the non-heme halogen peroxidase with another bleaching system provides improved cleaning of colored and/or common human stains and/or soils and, when formulated as a detergent composition, improved cleaning and bleaching of fabric-like articles.

The bleach component for use herein can be any of the bleaching agents useful for cleaning compositions, including oxygen bleaching agents as well as other bleaching agents known in the art. The bleaching agent useful in the present invention can be an activated or non-activated bleaching agent.

The bleaching agents include, for example, hydrogen peroxide, PB1, PB4 and percarbonate with a particle size of 400-800 microns. These bleach components may include one or more oxygen bleaching agents and, depending on the bleaching agent chosen, one or more bleach activators. If present, the oxygen bleaching compounds are typically present in proportions of 1 to 25%.

The hydrogen peroxide releasing agents can be used in combination with bleach activators, e.g. tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5,5-trimethylhexanoyloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG) or phenolsulfonate esters of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO 94/28106), which are perhydrolyzed to form a peracid as an active bleaching species, resulting in an improved bleaching effect. Also suitable activators are acylated citrate esters as disclosed in copending European patent application EP 624 154 and unsymmetrical acyclic imide bleach activators as disclosed in copending patent application WO 98/04664 of Procter & Gamble, of the following formula:

wherein R1 is a linear or branched chain, saturated or unsaturated C7 -C13 alkyl group, R2 is a linear or branched chain, saturated or unsaturated C1 -C8 alkyl group, and R3 is a linear or branched chain, saturated or unsaturated C1 -C4 alkyl group.

One category of useful oxygen bleaching agents includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934. Particularly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid, as described in U.S. Patent 4,634,551.

Another category of bleaching agents that can be used comprises the halogen bleaching agents. Examples of hypohalite bleaching agents include, for example, trichloroisocyanuric acid and the sodium and potassium dichloroisocyanurates, as well as N-chloro and N-bromoalkanesulfonamides. Such materials are normally added at 0.5-10% by weight of the final product, preferably 1-5% by weight.

Useful bleaching agents, including peroxyacids and bleaching systems, comprising bleach activators and peroxygen bleach compounds, for use in the cleaning compositions of the invention are described in the inventors' copending applications WO 95/10592, WO 97/00937, WO 95/27772, WO 95/27773, WO 95/27774 and WO 95/27775.

The hydrogen peroxide can also be provided by the addition of an enzymatic system (ie an enzyme and a substrate therefor) capable of producing hydrogen peroxide at the beginning or during the washing and/or rinsing cycle Such enzymatic systems are disclosed in EP patent application EP 537 381, filed on October 9, 1991.

Peroxidase enzymes are used in combination with hydrogen peroxide, oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc., and a bleach enhancer. They are used for "bleaching in solution", i.e. to prevent the transfer of dyes or pigments removed from substrates during washing processes to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and a haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing cleaning compositions are disclosed, for example, in International PCT Application WO 89/099813, WO 89/09813 and in European Patent Application EP 540 784, filed November 6, 1991. Also suitable is the laccase enzyme.

Enhancers are generally included at a level of 0.1 to 5% by weight of the total composition. Preferred enhancers are substituted phenthiazine and phenoxasine 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) as well as substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

The peroxidases are normally included in the cleaning composition in amounts of 0.0001 to 2% active enzyme by weight of the cleaning composition.

Metal-containing catalysts for use in bleaching compositions include cobalt-containing catalysts such as pentaamine acetate cobalt (III) salts and manganese-containing catalysts such as those described in EPA 549 271; EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398, EPA 458 397; US 5,194,416 and US 5,114,611. A bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a complexing agent is described in patent application EP 718 398.

A preferred metal-containing catalyst for the purposes of the present invention is a transition metal complex of a macropolycyclic rigid ligand. The term "macropolycyclic rigid ligand" is sometimes abbreviated to "MRL" in the discussion below. The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably about 0.05 ppm to about 500 ppm (where "ppb" means parts per billion by weight and "ppm" means parts per million by weight).

Suitable transition metals, e.g. Mn, are illustrated below. "Macropolycyclic" means that an MRL is both a macrocycle and polycyclic "Polycyclic" means at least bicyclic. The term "rigid" as used herein includes "having a superstructure" and "cross-bridged". "Rigid" has been defined as the enforced opposite of flexibility; see Busch DH, Chemical Reviews 93 (1993), 847-860, incorporated by reference. More specifically, "rigid" as used herein means that the MRL must be determinably more rigid than a macrocycle ("parent macrocycle") that is otherwise identical (having the same ring size and type and number of atoms in the main ring) but lacks superstructure (particularly linking groups or preferably cross-bridging groups) found in MRLs. In determining the relative rigidity of macrocycles with and without superstructures, the skilled person will use the free form (not the metal-bound form) of the macrocycles. It is well known that rigidity is useful in comparing macrocycles. Suitable tools for determining, measuring or comparing rigidity include computational methods (see, for example, Zimmer, Chemical Reviews 95(38) (1995), 2629-2648, or Hancock et al., Inorganica Chimica Acta 164 (1989), 73-84). Determining whether one macrocycle is more rigid than another can often be done by simply constructing a molecular model, thus it is generally not necessary to know the configuration energies in absolute terms or to calculate them precisely. Excellent relative determinations of the rigidity of one macrocycle compared to another can be made using inexpensive personal computer-based computational tools such as ALCHEMY III, commercially available from Tripos Associates. Much more expensive software is also available from Tripos which allows not only comparative but absolute determinations; alternatively SHAPES can be used (see Zimmer, mentioned above). An observation of importance in the context of the present invention is that an optimum for the present purposes exists when the starting macrocycle is significantly flexible compared to the cross-bridged form. Thus, unexpectedly, it is preferred to use starting macrocycles containing at least four donor atoms, such as cyclam derivatives, and to cross-bridge them, rather than starting from a more rigid starting macrocycle. Another observation is that cross-bridged macrocycles are significantly preferred over macrocycles bridged in other ways.

The MRLs preferred herein are a particular type of ultrarigid ligand that is cross-bridged. A "cross-bridge" is illustrated non-limitingly in 1.11 below. In 1.11, the cross-bridge is a -CH2CH2- group. It bridges N1 and N8 in the illustrative structure. In comparison, an "equilateral" bridge, for example if one had been introduced across N1 and N12 in 1.11, would not be sufficient to constitute a "cross-bridge" and would accordingly not be preferred.

Suitable metals in the rigid ligand complexes include Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III) and Ru(IV). Preferred transition metals in the present transition metal bleach catalyst include manganese, iron and chromium. Preferred oxidation states include the (II) and (III) oxidation states. Manganese(II) in the form of the "low spin" configuration and/or "high spin" configuration complexes is included. It should be noted that complexes such as the "low spin" Mn(II) complexes are rather rare in all of coordination chemistry. The designation (II) or (III) indicates a coordinated transition metal with the required oxidation state. The coordinated metal atom is not a free ion or one that has only water as a ligand.

In general, as used herein, a "ligand" is any group capable of directing covalent bonding to a metal ion. Ligands may be charged or neutral and may be very diverse, including simple monovalent donors, e.g. chloride, or simple amines, which form a single coordinate bond and a single attachment site to a metal, oxygen or ethylene, which may form a three-membered ring with a metal and thus have two possible attachment sites to larger groups such as ethylenediamine or aza-macrocycles, which form the maximum number of single bonds with one or more metals possible by the available sites on the metal and the number of ion pairs or other binding sites of the free ligand. Many ligands may form bonds other than simple donor bonds and may have multiple attachment sites.

Ligands useful herein can be divided into several groups: the MRL, preferably a cross-bridged macropolycycle (preferably one MRL is present in a useful transition metal complex, however more, for example two, may be present, but not in preferred single-ring transition metal complexes); other optional ligands which are generally different from the MRL (generally 0 to 4, preferably 1 to 3, such ligands are present); and ligands which are temporarily associated with the metal as part of the catalytic cycle, the latter typically associated with water, hydroxide, oxygen and peroxides. Ligands of the third group are not essential to the definition of the metal bleach catalyst, which is a stable, isolable chemical compound which can be fully characterized. Ligands that bind metals via donor atoms each have at least a single unpaired electron pair that is available for donation to a metal that has a donor capacity or potential interlocking at least equal to the number of donor atoms. In general, the donor capacity can be fully or only partially exerted.

In general, the MRLs herein can be viewed as the result of imposing additional structural rigidity on specifically selected "starting macrocycles".

More generally, the MRLs herein (and the corresponding transition metal catalysts) suitably include:

(a) at least one macrocycle main ring comprising four or more heteroatoms;

and

(b) a covalently linked non-metal superstructure which can increase the rigidity of the macrocycle, preferably selected from

(i) a bridging superstructure, e.g. a linking group;

(ii) a cross-bridging superstructure, e.g. a cross-bridging linking group; and

(iii) combinations thereof.

The term "superstructure" is used herein as defined in the literature by Busch et al.; see for example the articles by Busch in "Chemical Reviews".

Preferred superstructures herein not only increase the rigidity of the parent macrocycle, but also promote folding of the macrocycle so that it coordinates to a metal in a cleft. Suitable superstructures can be extremely simple; for example, a linking group such as any of those illustrated in 1.9 and 1.10 below can be used.

wherein n is an integer, for example 2 to 8, preferably less than 6, typically 2 to 4; or

wherein m and n are integers from 1 to 8, more preferably 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkylammonium, halogen, nitro, sulfonate or the like. The aromatic ring in 1.10 may be replaced by a saturated ring, wherein the atom in Z which joins into the ring may contain N, O, S or C.

Without being bound by theory, it is believed that the preorganization built into the MRLs, which results in additional kinetic and/or thermodynamic stability of their metal complexes, arises either from topological hindrances or increased rigidity (loss of flexibility) compared to the free parent macrocycle, which has no superstructure. The MRLs as defined herein and their preferred cross-bridged subfamily, which is "ultra-rigid", combine two sources of fixed preorganization. In the preferred MRLs MRL's are the linking groups and the parent macrocycle rings combined to form ligands which exhibit a significant degree of "folding", typically greater than in many known superstructure ligands in which a superstructure is attached to a largely planar, often unsaturated macrocycle. See, for example: Busch DH, Chemical Reviews 93 (1993), 847-880. Furthermore, the MRL's preferred herein possess a number of special properties, including: (1) they are characterized by very high proton affinities, as in so-called "proton sponges"; (2) they tend to react slowly with multivalent transition metals, which, when combined with point (1) above, makes the synthesis of their complexes with certain hydrolyzable metal ions in hydroxylic solvents difficult; (3) when coordinated to transition metal atoms, as indicated herein, the MRLs result in complexes that exhibit exceptional kinetic stability, such that the metal ions dissociate only extremely slowly under conditions that would destroy complexes with ordinary ligands; and (4) these complexes possess exceptional thermodynamic stability; however, the unusual kinetics of MRL dissociation from the transition metal may defeat conventional equilibrium measurements that could quantify this property.

In one aspect of the present invention, the MRL's include those comprising:

(i) an organic macrocyclic ring containing four or more donor atoms (preferably at least 3, more preferably at least 4, of these donor atoms are N), separated from each other by covalent bonds of at least one, preferably two or three non-donor atoms, wherein two to five (preferably three to four, more preferably four) of these donor atoms are coordinated to the same transition metal in the complex; and

(ii) a linking group, preferably a cross-bridging chain, which covalently links at least two (preferably non-adjacent) donor atoms of the organic macrocycle ring, wherein the covalently linked (preferably non-adjacent) donor atoms are bridgehead donor atoms which are coordinated to the same transition metal in the complex, and wherein the linking group (preferably a cross-bridging chain) comprises 2 to 10 atoms (preferably the cross-bridging chain is selected from 2, 3 or 4 non-donor atoms and 4-6 non-donor atoms with a further donor atom).

Suitable MRLs are further illustrated, but not limited to, the following compound:

This compound is an MRL of the invention which is a particularly preferred cross-bridged methyl-substituted (all nitrogen atoms are tertiary) derivative of cyclam. Formally, this ligand is referred to as 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993", Panico R., Powell W. H. and Richer J.-C. (eds.), Blackwell Scientific Publications, Boston, 1993; see especially Section R-2.4.2.1. According to conventional terminology, N1 and N8 are "bridgehead atoms" as defined herein, more specifically "bridgehead donor atoms" since they have unpaired electron pairs capable of donation to a metal. N1 is connected to two non-bridgehead donor atoms, N5 and N12, by the distinct saturated carbon chains 2,3,4 and 14,13 and to the bridgehead donor atom N8 by a "linking group" a,b, which is herein a saturated carbon chain of two carbon atoms. N8 is connected to two non-bridgehead donor atoms, N5 and N12, by the distinct chains 6,7 and 9,10,11. The chain a,b is a "linking group" as defined herein and corresponds to a special, preferred type called a "cross-bridging" group. The "macrocyclic ring" of the above ligand or the "main ring" (IUPAC) includes all four donor atoms and the chains 2,3,4; 6,7; 9,10,11 and 13,14, but not a, b. This ligand is conventionally bicyclic. The short bridge or "linking group" a, b is a "cross-bridge" as defined herein, where a, b bisects the macrocyclic ring:

The MRL's herein are, of course, not limited to synthesis from any preformed macrocycle plus a preformed "stiffening" or "conformation-modifying" element; rather, a wide variety of synthetic means, e.g., template synthesis, are useful. See, for example, Busch et al., reviewed in "Heterocyclic Compounds: Aza-Crown Macrocycles," Bradshaw J. S. et al.

Transition metal bleach catalysts useful in the compositions of the present invention can include generally known compounds if they conform to the definition herein and, more preferably, any of a large number of novel compounds specifically developed for the present washing or cleaning applications and are illustrated by any of the following, without limitation:

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II);

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) hexafluorophosphate;

Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate;

Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane manganese(II) hexafluorophosphate;

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) tetrafluoroborate;

Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II) tetrafluoroborate;

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(III) hexafluorophosphate;

Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane iron(II);

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane iron(II);

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane copper(II);

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanecopper(II);

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane cobalt(II);

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane cobalt(II);

Dichloro-5,12-dimethyl-4-phenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II);

Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II);

Dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II);

Dichloro-2,4,5,9,11,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-2,2,4,5,9,11,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-3,5,10,12-tetramethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-3-butyl-,5,10,12-trimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II);

Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane iron(II);

Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane iron(II);

Aquo-chloro-2-(2-hydroxyphenyl)-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Aquo-chloro-10-(2-hydroxybenzyl)-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II);

Chloro-2-(2-hydroxybenzyl)-5-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II);

Chloro-10-(2-hydroxybenzyl)-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II);

Chloro-5-methyl-12-(2-picolyl)-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II) chloride;

Chloro-4-methyl-10-(2-picolyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane manganese(II) chloride;

Dichloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III);

Aquo-chloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Aquo-chloro-5-(3-sulfonopropyl)-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Dichloro-5-(trimethylammoniopropyl)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]-hexadecane manganese(III) chloride;

Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo[8.5.2]heptadecanemanganese(II);

Dichloro-14,20-dimethyl-1,10,14,20-tetraazabicyclo[8.6.6]docosa-3(8),4,6-trienemanganese(II);

Dichloro-4,11-dimethyl-1,4,7,11-tetraazabicyclo[6.5.2]pentadecanemanganese(II);

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[7.6.2]heptadecanemanganese(II);

Dichloro-5,13-dimethyl-1,5,9,13-tetraazabicyclo[7.7.2]heptadecanemanganese(II);

Dichloro-3,10-bis(butylcarboxy)-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Diaquo-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II);

Chloro-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.13,7.111,15]pentacosa-3,5,7(24),11,13,15(25)-hexaenemanganese(II) -hexafluorophosphate;

Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.13,7.111,15]pentacosa-3,5,7(24),11,13,15(25)-hexaenemanganese(II) -trifluoromethanesulfonate;

Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.13,7.111,15]pentacosa-3,5,7(24),11,13,15(25)-hexaeniron(II) -trifluoromethanesulfonate;

Chlorine-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecane manganese(II) hexafluorophosphate;

Chlorine-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecane manganese(II) hexafluorophosphate;

Chlorine-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecane manganese(II) chloride;

Chlorine-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecane manganese(II) chloride.

Those skilled in the art may further benefit if certain terms are additionally defined and illustrated. As used herein, "macrocyclic rings" are covalently linked rings formed from four or more donor atoms (i.e., heteroatoms such as nitrogen or oxygen) together with carbon chains connecting them; and any macrocyclic ring as defined herein must contain a total of at least 10, preferably at least 12, atoms in the macrocyclic ring. An MRL may contain more than one ring of any type per ligand, but at least one macrocyclic ring must be identifiable. Additionally, in the preferred embodiments, no two heteroatoms are directly linked to each other. Preferred transition metal bleach catalysts are those wherein the MRL comprises an organic macrocyclic ring (main ring) containing at least 10-20 atoms, preferably 12-18 atoms, more preferably 12 to 20 atoms, most preferably 12 to 16 atoms.

"Donor atoms" herein are heteroatoms such as nitrogen, oxygen, phosphorus or sulfur which, when incorporated into a ligand, still have at least one unpaired electron pair available to form a donor-acceptor bond with a metal. Preferred transition metal bleach catalysts are those wherein the donor atoms in the organic macrocycle ring of the cross-bridged MRL are selected from the group consisting of N, O, S and P, preferably N and O; and most preferably all are N. Also preferred are cross-bridged MRLs which comprise 4 or 5 donor atoms all coordinated to the same transition metal. The most preferred transition metal bleach catalysts are those wherein the cross-bridged MRL comprises four nitrogen donor atoms all coordinated to the same transition metal and those wherein the cross-bridged MRL comprises five nitrogen atoms all coordinated to the same transition metal.

"Non-donor atoms" of the MRL herein are most commonly carbon atoms, although a variety of atom types may be included, particularly in optional exocyclic substituents (such as "side groups" as illustrated below) of the macrocycles, which are neither donor atoms required to form the metal catalysts nor carbon atoms. Thus, the term "non-donor atoms" may refer in the broadest sense to any atom not required to form donor bonds with the metal of the catalyst. Examples of such atoms may include heteroatoms such as sulfur as incorporated into a non-coordinable sulfonate group, phosphorus as incorporated into a phosphonium salt group, phosphorus as incorporated into a P(V) oxide, a non-transition metal, or the like. In certain preferred embodiments, all non-donor atoms are carbon atoms.

Transition metal complexes of MRLs can be prepared in a conventional manner. Two such preparations are illustrated below: Synthesis of [Mn(Bcyclam)Cl₂]

(a) Method I

"Bcyclam" (5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane) is prepared by a synthetic procedure described by Weisman G. R. et al., J. Amer. Chem. Soc. 112 (1990), 8604. Bcyclam (1.00 g, 3.93 mol) is dissolved in dry CH3CN (35 mL, distilled from CaH2). The solution is then evacuated at 15 mm until the CH3CN begins to boil. The flask is then brought to atmospheric pressure with Ar. This degassing procedure is repeated four times. Mn(pyridine)2Cl2 (1.12 g, 3.93 mmol), synthesized according to a procedure in the literature by Witteveen H. T, et al., J. Inorg. Nucl. Chem. 36 (1974), 1535, is added under Ar. The cloudy reaction solution begins to darken slowly. After stirring overnight at room temperature, the reaction solution becomes dark brown with suspended fine particles. The reaction solution is filtered with a 0.2 u filter. The filtrate is light brown in color. This filtrate is evaporated to dryness using a rotary evaporator. After drying overnight at 0.05 mm at room temperature, 1.35 g of an off-white solid product is obtained; yield 90%. Elemental analysis: %Mn = 14.45; %C = 44.22; %H = 7.95; theoretical for [Mn(Bcyclam)Cl2], MnC14H30N4Cl2, MW = 380.26. Found: %Mn = 14.98; %C = 44.48; %H = 7.86. Ion atomization mass spectroscopy shows a major peak at 354 mu corresponding to [Mn(Bcyclam)(formate)]+ .

(b) Method II

Freshly distilled bcyclam (25.00 g, 0.0984 mol), prepared by the same procedure as above, is dissolved in dry CH3CN (900 mL, distilled from CaH2). The solution is then evacuated at 15 mm until the CH3CN begins to boil. The flask is then brought to atmospheric pressure with Ar. This degassing procedure is repeated four times. MnCl2 (11.25 g, 0.0894 mmol) is added under Ar. The cloudy reaction solution immediately turns dark. After stirring for 4 h under reflux, the Reaction solution dark brown with suspended fine particles. The reaction solution is filtered through a 0.2 u filter under dry conditions. The filtrate is light brown in color. This filtrate is evaporated to dryness using a rotary evaporator. The resulting light brown solid is dried at 0.05 mm at room temperature overnight. The solid is suspended in toluene (100 mL) and heated to reflux. The toluene is decanted and the procedure is repeated with another 100 mL of toluene. The residual toluene is removed using a rotary evaporator. After drying overnight at 0.05 mm at room temperature, 31.75 g of a light blue solid product is obtained; yield 93.5%. Elemental analysis: %Mn = 14.45; %C = 44.22; %H = 7.95; %N = 14.73; %Cl = 18.65; theoretical for [Mn(Bcyclam)Cl2], MnC14H30NaCl2, MW = 380.26. Found: %Mn = 14.69; %C = 44.69; %H = 7.99; %N = 14.78; %Cl = 18.90 (Karl Fischer water = 0.68%). Ion atomization mass spectroscopy shows a major peak at 354 mu corresponding to [Mn(Bcyclam)(formate)]+.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One type of non-oxygen bleaching agent of particular interest includes light-activated bleaching agents, e.g., the sulfonated zinc and/or aluminum phthalocyanines. These materials can deposit on the substrate during the washing process. Upon exposure to light in the presence of oxygen, such as by hanging the garments to dry in daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. A preferred zinc phthalocyanine and light-activated bleaching process are described in U.S. Patent 4,033,718. Typically, the detergent compositions contain from 0.025 to 1.25% by weight of a sulfonated zinc phthalocyanine.

Color care and textile care benefits

Technologies that provide a color care benefit may also be included. Examples of these technologies are metallocatalysts for color retention. Such metallocatalysts are described in co-pending European patent application EP 596 184. Dye fixatives, a polyolefin dispersion for anti-wrinkle benefits and improved water absorption, a fragrance and an amino-functional polymer for color care treatment, and a fragrance substantivity are further examples of color care/fabric care technologies and are described in co-pending European patent application EP 841 390, filed November 7, 1996.

Fabric softening agents may also be included in the cleaning compositions of the invention. These agents may be of the inorganic or organic type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and USP 5,019,292. Organic fabric softening agents include the water-insoluble tertiary amines as disclosed in GB-A-1 514276 and EP-B-0 011 340, and their combination with C 12 -C 14 quaternary monoammonium salts as disclosed in EP-B-0 026 527 and EP-B-0 026 528, and di-long chain amides as disclosed in EP-B-0 242 919. Other useful organic components of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.

Levels of smectite clay are normally in the range of 2 to 20 wt%, more preferably 5 to 15 wt%, with the material being added as a dry-blended component to the remainder of the formulation. Organic fabric softening agents, such as the water-insoluble tertiary amine or di-long chain amide materials, are included in levels of 0.5 to 5 wt%, normally 1 to 3 wt%, while the high molecular weight polyethylene oxide materials and the water-soluble cationic materials are added in levels of 0.1 to 2 wt%, normally 0.15 to 1.5 wt%. These materials are normally added to the spray dried part of the composition, although in some cases it may be more convenient to add them as a dry-blended particle or to spray them as a molten liquid onto the other solid components of the composition.

Builder system

The compositions of the invention may further comprise a builder system. Any conventional builder system is suitable for use herein, including aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic acid and fatty acids, materials such as ethylenediaminetetraacetate, diethylenetriaminepentamethylene acetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Phosphate builders may also be used herein.

Suitable builders may be an inorganic ion exchange material, usually an inorganic hydrated aluminosilicate material, more specifically a hydrated synthetic zeolite, e.g. hydrated zeolite A, X, B, HS or MAP.

Another suitable inorganic builder material is a layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na₂Si₂O₅).

Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. 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 described in German Offenlegungsschrift 2,446,686 and 2,446,687 and in US Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing 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 Dutch Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing 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 containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent No. 1,439,000, while polycarboxylates having phosphonic substituents are described in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran cis,cis,cis-tetracarboxylates, 2,5-tetrahydrofuran cis-dicarboxylates, 2,2,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

The preferred polycarboxylates of the above are hydroxycarboxylates containing up to three carboxy groups per molecule, more preferably citrates.

Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or a layered silicate (SKS-6) and a water-soluble carboxylate complexing agent such as citric acid.

Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A and a water-soluble carboxylate complexing agent such as citric acid. Preferred builder systems for use in the liquid detergent compositions of the invention are soaps and polycarboxylates.

Other builder materials which may form part of the builder system for use in granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates and silicates, and organic materials such as the organic phosphonates, aminopolyalkylene phosphonates and aminopolycarboxylates.

Other suitable water-soluble organic salts are the homo- or copolymeric acids and their salts, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2,000-5,000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000 to 70,000, in particular about 40,000.

Detergent builder salts are normally included in amounts of from 5 to 80% by weight of the composition, preferably 10 to 70% and most usually 30 to 60% .

Complexing agents

The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, all as defined below. Without wishing to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from wash solutions by the formation of soluble chelates.

Aminocarboxylates useful as optional complexing agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates and ethanoldiglycines, alkali metal, ammonium and substituted ammonium salts thereof, and mixtures thereof.

Aminophosphonates are also suitable for use as complexing agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions and include ethylenediaminetetrakis(methylenephosphonates) such as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in the acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine disuccinate ("EDDS"), particularly the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987 to Hartman and Perkins.

The compositions herein may also contain water-soluble methylglycinediacetic acid (MGDA) salts (or the acid form) as complexing agents or co-builders which are useful, for example, together with insoluble builders such as zeolites, layered silicates and the like.

If used, these chelating agents generally comprise from 0.1 to 15 wt% of the detergent compositions herein. More preferably, if used, the chelating agents comprise from 0.1 to 3.0 wt% of such compositions.

Foam suppressor

Another optional ingredient is a suds suppressor, exemplified by silicones and silica-silicone blends. Silicones may be generally represented by alkylated polysiloxane materials, while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and various hydrophobic silica types. These materials may be included as particles wherein the suds suppressor is advantageously releasably encased in a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier. Alternatively, the suds suppressor may be dissolved or dispersed in a liquid carrier and applied by spraying onto one or more of the other components.

A preferred silicone foam control agent is disclosed in Bartollota et al., U.S. Patent 3,933,672. Other particularly useful foam suppressors are the self-emulsifying silicone foam suppressors described in German Patent Application DTOS-2 646 126, published April 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. A particularly preferred foam control agent is the foam suppression system comprising a mixture of silicone oils and 2-alkylalkanols. A suitable 2-alkylalkanol is 2-butyloctanol, commercially available under the trade name Isofol 12.

Such a foam suppression system is described in copending European Patent Application EP 593 841, filed November 10, 1992.

Particularly preferred silicone foam control agents are described in copending European Patent Application EP 595 699. The compositions may comprise a silicone/silica mixture in combination with non-porous silica powder such as Aerosil®.

The foam suppressors described above are normally used in amounts of 0.001 to 2% by weight of the composition, preferably 0.01 to 1% by weight.

Other components

Other components used in cleaning compositions may be used, such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, anti-tarnish agents, colorants and/or encapsulated or non-encapsulated fragrances.

Particularly suitable encapsulation materials are water-soluble capsules, which consist of a matrix of polysaccharide and polyhydroxy compounds, as described in GB 1,464,616.

Other suitable water-soluble encapsulating materials include dextrins derived from non-gelatinized starch acid esters of substituted dicarboxylic acids as described in US 3,455,838. These acid ester dextrins are preferably made from such starches as waxy corn starch, waxy sorghum starch, sago, tapioca and potato starch. Suitable examples of the encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists of a modified corn starch and glucose. The starch is modified by the addition of monofunctional substituted groups such as octenyl succinic anhydride.

Antiredeposition and soil suspending agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers already mentioned as builders, and copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used in amounts of from 0.5 to 10%, more preferably from 0.75 to 8%, most preferably from 1 to 6%, by weight of the composition.

Preferred optical brighteners have an anionic character. Examples of these are disodium 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2,2'-disulfonate, disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene-2,2'-disulfonate, disodium 4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2,2'-disulfonate, Mononatrium-4',4"-bis-(2,4-dianilino-s-triazin-6-ylamino)-stilben-2-sulfonat, Dinatrium-4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilben- 2,2'-disulfonat, Dinatrium-4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilben-2,2'-disulfonat, Dinatrium-4,4'-bis-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilben-2,2'-disulfonat, Natrium-2-(stilbyl-4"-(naphtho-1',2',4,5)-1,2,3-triazol-2"-sulfonat and 4,4'-bis-(2-sulfostyryl)biphenyl. Particularly preferred brighteners are the specific authentic brighteners of the co-pending European patent application EP 753 567.

Other useful polymeric materials are the polyethylene glycols, particularly those having a molecular weight of 1,000 to 10,000, more preferably 2,000 to 8,000 and most preferably about 4,000. These are used in proportions of 0.20 to 5 wt.%, more preferably 0.25 to 2.5 wt.%. These polymers and the already mentioned homo- or copolymeric polycarboxylate salts are useful for improving brightness retention, textile ash removal and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal contaminants.

Soil release agents useful in the compositions of the invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples Such polymers are disclosed in commonly assigned US Patent Nos. 4116885 and 4711730 and published European Patent Application No. 0 272 033. A particularly preferred polymer according to EP-A-0 272 033 corresponds to the formula:

(CH3(PEG)43)0.75(POH)0.25[(T-PO)2.8(T-PEG)0.4]T(PO-H)0.25((PEG)43CH3)0.75 wherein PEG represents -(OC2H4)O-, PO(OC3H6O) and T represents (pcOC6H4CO).

Also very useful are modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol, where the end groups consist primarily of sulfobenzoate and secondarily of monoesters of ethylene glycol and/or propanediol. The goal is to obtain a polymer which is capped at both ends with sulfobenzoate groups, where "primary" in the present context means that most of the copolymers are end-capped with sulfobenzoate groups. However, some copolymers are not fully capped and therefore their end groups may have a monoester of ethylene glycol and/or propane-1,2-diol and therefore "secondarily" consist of such species.

The polyesters selected herein contain 46 wt.% dimethyl terephthalic acid, 16 wt.% propane-1,2-diol, about 10 wt.% ethylene glycol, 13 wt.% dimethyl sulfobenzoic acid and 15 wt.% sulfoisophthalic acid and have a molecular weight of 3,000. The polyesters and their manufacturing processes are described in detail in EPA 311 342.

It is well known in the art that free chlorine in tap water rapidly deactivates the enzymes included in detergent compositions. Therefore, using a chlorine scavenger such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine in a level above 0.1% by weight of the total composition in the formulas provides improved stability of the detergent enzymes during washing. Compositions comprising chlorine scavengers are described in European Patent Application EP 553 607, filed January 31, 1992.

Alkoxylated polycarboxylates, such as those made from polyacrylates, are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4f, incorporated herein by reference. Chemically, these materials comprise polyacrylates which have one ethoxy side chain for every 7-8 acrylate units. The side chains correspond to the formula -(CH2CH2O)m(CH2)nCH3, where m is 2-3 and n is 6-12. The side chains are attached to the polyacrylate "backbone" via ester linkages to provide a "comb-like" polymer structure. The molecular weight can vary, but is typically in the range of 2,000 to 50,000. Such alkoxylated polycarboxylates can comprise 0.05 to 10 weight percent of the compositions herein.

Dispersants

The cleaning composition according to the invention may also contain dispersants. Suitable water-soluble organic salts are the homo- or copolymeric acids or salts thereof in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2,000-5,000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 1,000 to 100,000.

In particular, a copolymer of acrylate and methyl acrylate, e.g. 480N, with a molecular weight of 4,000 in a proportion of 0.5-20% by weight of the composition can be added to the cleaning compositions according to the invention.

The compositions of the invention may contain a lime soap peptizing compound having a lime soap dispersing power (LSDP), as defined below, of not more than 8, preferably not more than 7, most preferably not more than 6. The lime soap peptizing compound is preferably present in a proportion of 0 to 20% by weight.

A numerical measure of the effectiveness of a lime soap peptizer is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersion test as described in an article by Borghetty H. C. and Bergman C. A., J. Am. Oil. Chem. Soc., vol. 27 (1950), pp. 88-90. This lime soap dispersion test method is widely used by those skilled in the art and is referenced, for example, in the following review articles: Linfield W. N., Surfactant Science Series, vol. 7, p. 3; Linfield W. N., Tenside Surf. Det., vol. 27 (1990), pp. 159-163; and Nagarajan M. K., Masler W. F., Cosmetics and Toiletries, Volume 104 (1989), pages 71-73. The LSDP is the weight percent ratio of dispersant to sodium oleate required to disperse the lime soap deposits formed by 0.025 g sodium oleate in 30 ml water of 333 ppm CaCO3 (Ca:Mg = 3:2) equivalent hardness.

Surfactants with sufficient lime soap peptizing capacity include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.

Exemplary surfactants having an LSDP of no more than 8 for use in the present invention include C16-C18 dimethylamine oxide, C12-C18 alkyl ethoxysulfates having an average degree of ethoxylation of 1-5, particularly a C12-C15 alkyl ethoxysulfate surfactant having a degree of ethoxylation as high as 3 (LSDP = 4), and the ethoxylated C14-C15 alcohols having an average degree of ethoxylation of either 12 (LSDP = 6) or 30, sold under the trade names Lutensol A012 and Lutensol A030, respectively, by BASF GmbH.

Polymeric lime soap peptizers suitable for use herein are described in the article by Nagarajan M. K. and Masler W. F. found in Cosmetics and Toiletries, Volume 104 (1989), pages 71-73.

Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzenesulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzenesulfonate, 4-[N-decanoyl-6-aminohexanoyl]benzenesulfonate and mixtures thereof, as well as nonanoyloxybenzenesulfonate together with hydrophilic/hydrophobic bleach formulations can also be used as lime soap peptizer compounds.

Dye transfer inhibition

The cleaning compositions of the present invention may also include compounds for inhibiting dye transfer of solubilized and suspended dyes that occur during laundry processes in connection with colored fabrics from one fabric to another.

Polymeric dye transfer inhibitors

The cleaning compositions of the present invention may also comprise from 0.001 to 10% by weight, preferably from 0.01 to 2% by weight, more preferably from 0.05 to 1% by weight, of polymeric dye transfer inhibitors. The polymeric dye transfer inhibitors are normally included in the cleaning compositions to inhibit the transfer of dyes from colored fabrics to fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed from colored fabrics before the dyes have an opportunity to be absorbed onto other items in the wash.

Particularly suitable polymeric dye transfer inhibitors are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.

The addition of such polymers also increases the performance of the enzymes according to the invention.

a) Polyamine N-oxide polymers

The usable polyamine N-oxide polymers contain units with the following structural formula:

wherein P is a polymerizable moiety to which the RNO group may be attached, or wherein the RNO group forms part of the polymerizable moiety, or a combination of both.

-O-, -S-, -N-; x is 0 or 1;

R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof to which the nitrogen atom of the N-O group may be attached or wherein the nitrogen atom of the N-O group is part of that group.

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

wherein R1, R2 and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and/or y and/or z are 0 or 1, and wherein the nitrogen atom of the N-O group can be bonded, or wherein the nitrogen atom 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 bound 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 includes the group of polyamine N-oxides, wherein the nitrogen atom 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 pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen atom of the N-O group is bonded to the R group.

Other suitable polyamine N-oxides are the polyamine oxides in which the N-O group is bonded to the polymerizable unit.

A preferred class of these polyamine N-oxides are the polyamine N-oxides of the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and wherein the nitrogen atom of the N-O functional group is part of the R group.

Examples of these classes are polyamine oxides, where R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.

Another preferred class of polyamine N-oxides are the polyamine oxides of the general formula (I) wherein R represents aromatic, heterocyclic or alicyclic groups and wherein the nitrogen atom of the functional N-O group is bonded to the R groups.

Examples of these classes are polyamine oxides, where the R groups can be aromatic, e.g. phenyl.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The amine N-oxide polymers of the invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Preferably, the ratio of amine to the amine N-oxide is 2:3 to 1:1,000,000, more preferably 1:4 to 1:1,000,000, most preferably 1:7 to 1:1,000,000. The polymers of the invention actually comprise random or block copolymers, wherein one type of monomer is an amine N-oxide and the other type of monomer is either an amine N-oxide or none. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably a pKa < 7 and more preferably a pKa < 6

The polyamine oxides can be obtained in virtually any degree of polymerization. The degree of polymerization is not critical, provided that the material has the desired water solubility and dye suspending power.

Typically, the average molecular weight is in the range of 500 to 1,000,000, preferably 1,000 to 50,000, more preferably 2,000 to 30,000, most preferably 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole-N-vinylpyrrolidone polymers used in the invention have an average molecular weight range of 5,000-1,000,000, preferably 5,000-200,000.

Particularly preferred polymers for use in the detergent compositions of the invention comprise a polymer selected from N-vinylimidazole-N-vinylpyrrolidone copolymers, the polymer having an average molecular weight range of 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.

The average molecular weight range was determined by light scattering as described in Barth H. G. and Mays J. W., Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization.

Particularly preferred N-vinylimidazole-N-vinylpyrrolidone copolymers have an average molecular weight range of 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.

The N-vinylimidazole-N-vinylpyrrolidone copolymers characterized by this average molecular weight range provide excellent dye transfer inhibition properties while not adversely affecting the cleaning performance of the detergent compositions formulated therewith.

The N-vinylimidazole-N-vinylpyrrolidone copolymer of the invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1 to 0.2, more preferably 0.8 to 0.3, most preferably 0.6 to 0.4.

c) Polyvinylpyrrolidone

The detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product designations PVP K-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000), and PVP K-90 (average molecular weight 360,000). Other suitable polyvinylpyrrolidones commercially available from BASF Corporation include Sokalan HP 165 and Sokalan HP 12. Polyvinylpyrrolidones are well known to those skilled in the cleaning art (see, for example, EP-A-262,897 and EP-A-256,696).

d) Polyvinyloxazolidone

The detergent compositions of the present invention may also use polyvinyloxazolidone as a polymeric dye transfer inhibitor. The polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000.

e) Polyvinylimidazol

The detergent compositions of the present invention may also use polyvinylimidazole as a polymeric dye transfer inhibitor. The polyvinylimidazoles have an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000.

f) Cross-linked polymers

Crosslinked polymers are polymers whose backbone is interlocked to some degree. These compounds can be chemical or physical in nature, optionally with active groups in the backbone or at branches. Crosslinked polymers have been described in the Journal of Polymer Science, Volume 22, pages 1035-1039.

In one embodiment, the cross-linked polymers are prepared in such a way that they form a three-dimensional rigid structure that can trap dyes in the pores formed by the three-dimensional structure. In another embodiment, the cross-linked polymers trap the dyes by swelling.

Such cross-linked polymers are described in the co-pending patent application EP 719 856.

Washing process

The compositions of the invention can be used in essentially any washing/rinsing or cleaning process, including soaking processes, pretreatment processes and processes with rinsing steps for which a separate rinse aid composition can be added.

The process described herein comprises contacting the fabrics with a washing solution in the conventional manner and illustrated below.

The method according to the invention is suitably carried out in the course of the cleaning process. The cleaning process is preferably carried out at 5°C to 95°C, in particular between 10°C and 60°C. The pH of the treatment solution is 7 to 12.

A preferred machine dishwashing process comprises treating the soiled items with an aqueous liquid having dissolved or dispersed therein an effective amount of the machine dishwashing detergent or rinse aid composition. A conventional effective amount of the machine dishwashing detergent composition means 8-60 g of the product dissolved or dispersed in a wash volume of 3-10 liters.

According to a manual dishwashing method, the soiled dishes are contacted with an effective amount of the dishwashing composition, typically 0.5-20 g (per 25 dishes treated). Preferred manual dishwashing methods include applying a concentrated solution to the surfaces of the dishes or soaking in a large volume of a dilute solution of the detergent composition.

The following examples are intended to illustrate the compositions of the invention, but do not necessarily limit or otherwise define the scope of the invention.

In the cleaning compositions, the enzyme levels are expressed as pure enzyme by weight of the total composition and, unless otherwise stated, the detergent ingredients are by weight of the total composition. The abbreviated names of the components herein have the following meanings:

LAS: Linear sodium C11-13 alkyl benzene sulfonate.

TAS: sodium tallow alkyl sulfate.

CxyAS: sodium C1x-C1y alkyl sulfate.

CxySAS: secondary (2,3) sodium C1x-C1y-alkyl sulfate.

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

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

QAS: R₂·N⁺(CH₃)₂(C₂H₄OH) where R₂ = C₁₂-C₁₄.

QAS 1: R₂·N⁺(CH₃)₂(C₂H₄OH) where R₂ = C₈-C₁₁.

APA: C8-10 amidopropyldimethylamine.

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

Non-ionic: ethoxylated/propoxylated C₁₃-C₁₅ mixed fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5.

Neodol 45-13: C₁₄-C₁₅ linear primary alcohol ethoxylate, marketed by Shell Chemical Co.

STS: sodium toluenesulfonate.

CFAA: C12 -C14 alkyl-N-methylglucamide.

TFAA: C16 -C18 alkyl-N-methylglucamide.

TPKFA: Total distilled fraction of C₁₂-C₁₄ fatty acids.

DEQA: Di-(tallowoxyethyl)dimethylammonium chloride.

DEQA (2): Di-(soft tallowyloxyethyl)hydroxyethylmethylammonium methylsulfate.

DTDMAMS: Ditallowdimethylammonium methyl sulfate.

SDASA: 1:2 ratio of stearyldimethylamine to triple pressed stearic acid.

Silicate: Amorphous sodium silicate (SiO2 :Na2 O ratio = 1.6-3.2).

Metasilicate: Sodium metasilicate (SiO2 :Na2O ratio = 1.0).

Zeolite A: Hydrated sodium aluminosilicate of the formula Na₁₂(AlO₂SiO₂)₁₂·27H₂O having a predominant particle size in the range of 0.1 to 10 microns (expressed by weight on an aqueous basis).

NaSKS-6: Crystalline layered silicate of the formula δ-Na₂SiO₂O₅.

Citrate: Trisodium citrate dihydrate with an activity of 86.4%, with a particle size distribution between 425 and 850 micrometers.

Citric acid: Anhydrous citric acid.

Borate: sodium borate.

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

Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400 and 1,200 micrometers.

Sulfate: Anhydrous sodium sulfate.

Mg sulfate: anhydrous magnesium sulfate.

STPP: sodium tripolyphosphate.

TSPP: Tetrasodium pyrophosphate.

MA/AA: Random copolymer of acrylate/maleate (1:4), average molecular weight about 70,000-80,000.

MA/AA 1: Random copolymer of acrylate/maleate (6:4), average molecular weight about 10,000.

AA: Sodium polyacrylate polymer with an average molecular weight of 4,500.

PA30: Polyacrylic acid with an average molecular weight between approximately 4,500-8,000.

480N: Random copolymer of acrylate/methacrylate (7:3), average molecular weight about 3,500.

Polygel/Carbopol: High molecular weight cross-linked polyacrylates.

PB1: Anhydrous sodium perborate monohydrate of nominal formula NaBO₂·H₂O₂.

Hydrogen peroxide: Hydrogen peroxide, 30% solution, Sigma H1009.

Haloperoxidase: Non-heme chlorohaloperoxides obtained from Serratia marcescens as described in WO 96/06909 by Degussa.

Protease: Proteolytic enzyme sold under the trade names Savinase, Alcalase and Durazym by Novo Nordisk A/S. Maxacal and Maxapem, sold by Gist-Brocades, and proteases described in patents WO 91/06637 and/or WO 95/10591 and/or EP 251 446.

Amylase: Amylolytic enzyme sold under the trade name Purafact Ox Am®, described in WO 94/18314, WO 96/05295, sold by Genencor; Termamyl®, Fungamyl® and Duramyl®, all available from Novo Nordisk A/S. and those described in WO 95/26397.

Lipase: Lipolytic enzyme, sold under the trade names Lipolase and Lipolase Ultra by Novo Nordisk A/S. and Lipomax by Gist-Brocades.

Cellulase: Cellulytic enzyme sold under the trade name Carezyme, Celluzyme and/or Endolase by Novo Nordisk A/S.

CMC: sodium carboxymethylcellulose.

PVP: Polyvinyl polymer with an average molecular weight of 60,000.

PVNO: Polyvinylpyridine N-oxide with an average molecular weight of 50,000.

PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole with an average molecular weight of 20,000.

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.

Silicone antifoam agent: Polydimethylsiloxane foam control agent with a siloxane-oxyalkylene copolymer as dispersant with a ratio of foam control agent to dispersant of 10:1 to 100:1.

Foam suppressor: 12% silicone/silica, 18% stearyl alcohol, 70% starch in granular form.

Opacifier: Water-based monostyrene-latex mixture, sold by BASF Aktiengesellschaft under the trade name Lytron 621.

SRP 1: Anionic end-capped polyesters.

SRP 2: Short diethoxylated poly(1,2-propylene terephthalate) block polymer.

QEA: bis(C₂H₅O)(C₂H₄On)(CH₃)-N⁺-C₆H₁₂-N⁺-(CH₃)bis((C₂H₅)(C₂H₄O)n), where n = 20 to 30.

PEI: Polyethylenimine with an average molecular weight of 1,800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen

SCS: sodium cumene sulfonate.

HMWPEO: High molecular weight polyethylene oxide.

PEGx: Polyethylene glycol with a molecular weight of x.

PEO: Polyethylene oxide with an average molecular weight of 5,000.

TEPAE: Tetraethylene pentaamine ethoxylate.

BTA: benzotriazole.

Silica dental abrasives: Precipitated silica, referred to as Zeodent 119, offered by J. M. Huber.

Carboxyvinyl polymer: Carbopol, offered by B. F. Goodrich Chemical Company.

Carrageenan: Iota carrageenan, offered by Hercules Chemical Company.

pH: Measured as a 1% solution in distilled water at 20ºC.

example 1

The following high density laundry detergent compositions were prepared according to the invention:

Example 2

The following granular laundry detergent compositions, which are particularly useful under the washing conditions of European washing machines, were prepared according to the invention:

Example 3

The following detergent compositions, which are particularly useful under the washing conditions of European washing machines, were prepared according to the invention:

Example 4

The following granular detergent compositions were manufactured according to the invention:

Example 5

The following detergent compositions, which are particularly useful in washing colored garments, were prepared according to the invention:

Example 6

The following detergent compositions were prepared according to the invention:

Example 7

The following granular detergent compositions were prepared according to the invention:

Example 8

The following detergent compositions were prepared according to the invention:

Example 9

The following detergent compositions were prepared according to the invention:

Example 10

The following liquid detergent formulations were prepared according to the invention (the proportions are given in parts by weight; the enzymes are expressed as pure enzyme):

Example 11

The following liquid detergent formulations were prepared according to the invention (the proportions are given in parts by weight; the enzymes are expressed as pure enzyme):

Example 12

The following liquid detergent formulations were prepared according to the invention (the proportions are given in parts by weight; the enzymes are expressed as pure enzyme):

Example 13

The following liquid detergent formulations were prepared according to the invention (the proportions are given in parts by weight; the enzymes are expressed as pure enzyme):

Example 14

The following granular fabric detergent compositions providing "softening by washing" were prepared according to the invention:

Example 17

The following laundry detergent compositions in bar form were prepared according to the invention (the proportions are given in parts by weight; the enzymes are expressed as pure enzyme):

Example 19

The following compact high density (0.96 kg/l) dishwashing detergent compositions were prepared according to the invention:

Example 20

The following granular dishwashing detergent compositions with a bulk density of 1.02 kg/l were prepared according to the invention:

Example 21

The following detergent compositions in tablet form were prepared by compressing a granular dishwashing detergent composition at a pressure of 13 KN/cm2 using a conventional 12-head rotary press according to the invention:

Example 22

The following liquid dishwashing detergent compositions with a density of 1.40 kg/l were prepared according to the invention:

Example 23

The following liquid rinse aid composition was prepared according to the invention:

II

Non-ionic -

Non-ionic mixture 64.0

Halogen peroxidase 0.05

Acetic acid 2.0

Citric acid -

Hydrogen peroxide 0.5

Citric acid -

HEDP-

PEG5.0

SCS-

ethanol 8.0

pH of the liquid 7.5

Example 24

The following liquid dishwashing detergent compositions were prepared according to the invention:

Example 25

The following liquid hard surface cleaning compositions were prepared according to the invention:

* Na-4-ethylenediaminediacetic acid

** Diethylene glycol monohexyl ether

*** All formulas are adjusted to pH 7-12.

Example 26

The following spray composition for cleaning hard surfaces and removing mold in the home was prepared according to the invention:

Halogen peroxidase 0.05

Acetic acid 1.0

Hydrogen peroxide 0.2

Amylase 0.01

Proteases 0.01

Na-Octylsulfate 2.0

Na-dodecyl sulfate 4.0

Na hydroxide 0.8

Silicate 0.04

Butylcarbitol* 4.0

Fragrance 0.35

Water/accompanying substances to 100%

* Diethylene glycol monobutyl ether

Example 27

The following toilet cleaning compositions in block form were prepared according to the invention:

Example 28

The following toilet cleaning composition was prepared according to the invention:

Example 29

The following single-layer effervescent denture cleaning tablets were prepared according to the invention:

Example 30

The following dentifrice compositions were prepared according to the invention:

Claims (23)

1. A cleaning composition having a pH of 7-12 comprising: a) a surfactant system, b) an oxidoreductase with an α/β-hydrolase fold and a catalytic triad consisting of the amino acid residues serine, histidine and aspartic acid, c) a source of hydrogen peroxide, and d) an organic acid selected from the group consisting of monocarboxylic acids of the formula CnH(2n+1)COOH, where n = 1-9; malic acid, citric acid; lactic acid; fruit acids; benzoic acid; phthalic acid; their corresponding salts and mixtures thereof. 2. Cleaning composition according to claim 1, wherein the oxidoreductase is present in a proportion of 0.0001% to 2%, preferably 0.001% to 1%, more preferably 0.005% to 0.1%, pure enzyme, based on the weight of the total composition. 3. Cleaning composition according to claims 1 to 2, wherein the oxidoreductase is obtainable from the strain Serratia marcescens. 4. Cleaning composition according to claims 1 to 3, wherein the organic acid is present in a proportion of 0.1% to 50%, preferably 0.5% to 40%, more preferably 1% to 20%, based on the weight of the total composition. 5. Cleaning composition according to claim 1, wherein the organic acid is selected from acetic acid, propionic acid, nonanoic acid, and/or their corresponding sodium salts and/or mixtures thereof. 6. Cleaning composition according to at least one of the preceding claims, wherein the hydrogen peroxide source in the washing solution generates hydrogen peroxide in a proportion of 0.0001-10 mmoles, preferably 0.0001-2 mmoles, more preferably 0.0001-0.3 mmoles. 7. A cleaning composition according to claim 6, wherein the level of hydrogen peroxide is maintained by means of a controlled release system. 8. Cleaning composition according to at least one of the preceding claims, wherein the hydrogen peroxide source is selected from perborate and/or percarbonate. 9. Cleaning composition according to claims 1 to 7, wherein the hydrogen peroxide source is an enzymatic hydrogen peroxide generating system, preferably a glucose/glucose oxidase or lactate/lactate oxidase system. 10. Cleaning composition according to at least one of the preceding claims, further comprising a detergent enzyme, preferably selected from cellulase, lipase, protease, amylase and/or mixtures thereof. 11. A cleaning composition according to any one of the preceding claims, further comprising another bleaching system. 12. A cleaning composition according to claim 11, wherein the bleaching agent is selected from perborate and/or percarbonate and the activator is selected from tetraacetylethylenediamine, nonanoyloxybenzenesulfonate and/or 3,5-trimethylhexanoloxybenzenesulfonate. 13. The cleaning composition of claim 11, wherein the bleaching system is another enzymatic bleaching system. 14. The cleaning composition of claim 11, wherein the bleaching system is a metallocatalyst-based bleaching system. 15. The cleaning composition of claim 14, wherein the metallocatalyst is a transition metal complex of a macropolycyclic rigid ligand. 16. Cleaning composition according to claims 14-15, wherein the metallocatalyst is manganese. 17. A cleaning composition according to any one of the preceding claims, wherein the oxidoreductase is alkaline. 18. Cleaning composition according to at least one of the preceding claims, which is in the form of an additive. 19. Use of a composition according to any one of the preceding claims for textile cleaning and/or textile stain removal and/or textile whiteness maintenance and/or textile softening and/or textile colour appearance and/or textile dye transfer inhibition. 20. Use of a cleaning composition according to claims 1 to 18 for cleaning hard surfaces such as floors, walls, bathroom tiles. 21. Use of a cleaning composition according to claims 1 to 18 for hand and machine dishwashing. 22. Use of a cleaning composition according to claims 1 to 18 for oral and/or dental applications. 23. Use of a composition according to claims 1 to 18 for sterilizing the treated surfaces.