CN1268167A - Detergent compositions comprising a phospholipase - Google Patents

Abstract

The present invention relates to detergent compositions comprising a phospholipase, including laundry and hard-surface detergent compositions, which can effectively clean grease/oil, non-ferrous and/or day-to-day physical stains and/or dirt.

Description

Detergent composition comprising phospholipase

field of invention

The present invention relates to detergent compositions, including laundry and hard surface cleaner compositions, comprising phospholipases.

Background of the invention

The performance of a detergent product is judged by a number of factors, including the ability to remove soils, and the ability to inhibit redeposition of soils, or breakdown products of soils on items being washed. Food soils, in particular, are often difficult to remove effectively from soiled items.

Cleaning of greasy/oily soils and stains is known to be challenging, and is often accomplished by adding lipolytic enzymes to detergent compositions. In fact, the use of lipolytic enzymes to enhance the removal of triglyceride-containing soils and stains from fabrics is known in the art.

Highly pigmented or "dry-on" soils, eg from fruit and/or vegetables, are also particularly difficult soils to remove. These colored stains contain groups of pigments and dyes based on carotenoid compounds such as α-, β- and γ-carotene and lycopene and lutein (zeaxanthin or capsanthin), based on porphyrins such as chlorophyll and flavonoids Highly pigmented chromophores. This latter group of flavonoid-based natural dye components includes highly pigmented anthocyanin dyes and pigments based on geranium pigments, anthocyanins, delphinidins and their methyl esters and antoxanthins. These compounds are the source of most of the orange, red, purple and blue colors present in fruit and are present in abundance in all berries, cherries, red and black currants, grapefruit, passion fruit, orange, lemon, Apples, pears, pomegranates, red cabbage, red beets, and flowers. Carotenoid dirt occurs in carrots and tomatoes and any processed products containing these ingredients, as well as certain tropical fruits and saffron. Ballpoint pen ink is also known to be a particularly difficult colored stain to remove.

Traditionally, high levels of bleaching agents, optionally and bleach precursors, have been added to detergent compositions. Bleach is a precursor compound to hydrogen peroxide formed during the washing process. Perborate and percarbonate are the most important examples of such hydrogen peroxide precursors.

In addition, the complex nature of everyday "body" soils commonly found on pillowcases, T-shirts, collars and socks makes cleaning products challenging to clean thoroughly in succession. These soils are difficult to remove completely and often the residue builds up on the fabric causing dullness and yellowing.

From the foregoing it can be seen that there is a continuing need to formulate detergent compositions having excellent cleaning performance. It is therefore an object of the present invention to provide a detergent composition which is effective in cleaning greasy/oily, colored and/or everyday body stains and/or soils. It is a further object of the present invention to provide a detergent composition which cleans and whitens fabric objects.

The above objects are achieved by formulating detergent compositions comprising phospholipases. In a preferred embodiment, the present invention relates to laundry and/or fabric care compositions comprising phospholipases, which provide cleaning and whitening benefits to fabric objects. In a second embodiment, the present invention is directed to a hard surface cleaner composition comprising a phospholipase.

It is a further object of the present invention to provide a detergent composition which provides improved cleaning of greasy/oily, colored and/or everyday body stains and/or soils. A subsequent object is to provide detergent compositions which provide improved cleaning and whitening of fabric objects.

The above objects are achieved by formulating detergent compositions which also comprise one or more detergent components selected from anionic surfactants, dispersants and/or another detergent enzyme, in particular Lipase, amylase, protease, enzymes that increase the water solubility of stains/soils containing saturated fatty acids.

Phospholipases are described in the prior art: J07177884 describes the preparation of phospholipase-containing enzymes for detergents and leather processing. GB2247025 discloses enzymatic dishwashing or rinsing compositions comprising phospholipase. When combined with a proteolytic enzyme, the composition is said to be effective in removing egg yolk soils and thus reducing spotting on glassware.

However, the use of phospholipases in laundry and hard surface cleaner compositions to effectively remove greasy/oily, highly pigmented and everyday body soils and stains has never been recognized before.

Summary of the invention

The present invention relates to detergent compositions, including laundry and hard surface cleaner compositions, comprising phospholipases for effective removal of greasy/oily, highly pigmented and/or everyday body soils and/or stains.

Detailed description of the invention

An essential component of the compositions of the present invention is a phospholipase. It has surprisingly been found that the compositions of the present invention are effective in cleaning greasy/oily, colored and/or everyday body stains and/or soils. A further object is to provide a laundry and/or fabric care composition which cleans and whitens fabric items.

Without wishing to be bound by theory, it is indeed believed that phospholipases are capable of cleaving lecithin or phosphorylated lipids to produce water-soluble lysophospholipids which are more easily removed during washing. In addition, it is believed that foods and/or plant materials contain very low amounts of phospholipids that bind chromophores and enhance their color. Enzymatic hydrolysis of phospholipids releases the chromophores, thus reducing the intensity of the color.

Suitable phospholipases of the invention are:

EC3.1.1.32 Phospholipase A1

EC3.1.1.4 Phospholipase A2

EC3.1.1.5 Lysophospholipase

EC3.1.4.3 Phospholipase C

EC3.1.4.4 Phospholipase D

Preferred phospholipases for detergent compositions of the invention are EC 3.1.1.4 phospholipase A2 and EC 3.1.1.5 lysophospholipase. Commercially available phospholipases are Lecitase ^(R) from Novo Nordisk A/S and phospholipase A2 from Sigma.

Generally, the content of phospholipase in the composition of the present invention is 0.0001%-2%, preferably 0.001%-1%, more preferably 0.05%-0.5% pure enzyme by weight of the total composition.

Preferred phospholipases for particular applications are of the alkaline type, ie enzymes having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of the maximum activity at pH 7-12. More preferred phospholipases are enzymes that have their maximal activity at pH 7-12.

The aforementioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. The source may also be mesophilic or extremophilic (psychrophilic, cold-eating, thermophilic, barophilic, basophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes can be used. It is currently common practice to modify wild-type enzymes by protein/genetic engineering techniques in order to optimize their performance in the detergent compositions of the present invention. For example, the variant can be designed such that the enzyme has increased compatibility with components normally included in such compositions. Additionally, the variant can be designed such that the optimal pH, bleach or chelator stability, catalytic activity, etc. of the enzyme variant is tailored to a particular cleaning application.

In particular, attention should be focused on oxidation-sensitive amino acids for bleach stability and surface charge for surfactant compatibility. The isoelectric point of this enzyme can be improved by substituting certain charged amino acids, for example, increasing the isoelectric point can help improve the compatibility with anionic surfactants. Enzyme stability can also be enhanced by creating, for example, additional salt bridges and strengthening calcium binding sites to increase chelator stability.

detergent components

The detergent compositions of the present invention may also contain additional detergent ingredients. The exact nature of these additional components and their incorporation levels will depend upon the physical form of the composition and the type of cleaning operation for which it is used.

The detergent compositions according to the invention preferably further comprise one or more detergent components selected from anionic surfactants, dispersants and/or another detergent enzyme, especially lipase, amylase, protease, Saturated Fatty Acid Stain/Soil Water Soluble Enzyme.

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

In a preferred embodiment, the invention relates to laundry and/or fabric care compositions comprising a phospholipase (Examples 1-17). In a second embodiment, the present invention is directed to hard surface cleaner compositions (Examples 18-19).

The compositions of the present invention may, for example, be formulated as hand wash or machine laundry detergent compositions comprising laundry additive compositions and compositions suitable for soaking/pretreating soiled fabrics, rinse added fabric softener compositions, and for use in Compositions for typical household hard surface cleaning operations.

Such compositions containing phospholipases, when formulated as laundry detergent compositions, provide cleaning, stain removal, whiteness maintenance, softness, color appearance and dye transfer inhibition to fabrics.

When formulated as compositions suitable for use in washing machine washing methods, the compositions of the present invention preferably contain both components, a surfactant and a builder compound, and additionally one or more detergent components, the detergent composition The subparts are preferably selected from organic polymers, bleaching agents, additional enzymes, suds suppressors, dispersants, lime soap dispersants, soil suspending and antiredeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents as additional detergent ingredients.

The compositions of the present invention are also useful as detergent additive products. Such additive products are used to supplement or boost the performance of conventional detergent compositions.

If desired, the laundry detergent compositions according to the invention have a density measured at 20°C of from 400 to 1200 g/l, preferably from 600 to 950 g/l of composition.

The "compact" form of the compositions of the present invention is best reflected by density and, in terms of composition, by the amount of inorganic filler salt. Inorganic filler salts are conventional components of powdered detergent compositions. In conventional detergent compositions filler salts are present in significant amounts, typically 17-35% by weight of the total composition. In compact compositions, the content of filler salts does not exceed 15%, preferably does not exceed 10%, most preferably does not exceed 5% by weight of the composition. Inorganic filler salts, for example in the compositions of the present invention are meant to be selected from alkali metal and alkaline earth metal sulfates and chlorides. A preferred filler salt is sodium sulfate.

The liquid detergent compositions according to the invention may also be in "concentrated form", in which case the liquid detergent compositions according to the invention will contain lower amounts of water than conventional liquid detergents. Typically concentrated liquid detergents will preferably have a water content of less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.

anionic surfactant

It has surprisingly been found that detergent compositions according to the invention which also comprise an anionic surfactant provide improved cleaning of greasy/oily, colored and/or everyday body stains and/or soils. In addition, these compositions when formulated as laundry detergent/fabric care compositions provide improved cleaning and whitening of fabric items.

Suitable anionic surfactants for use are linear alkylbenzene sulfonate, alkyl ester sulfonate surfactants, including those described in "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329 for sulfonated linear _C8 - _C20 carboxylic acid (ie fatty acid) esters with gaseous _SO3 . Suitable materials include natural fatty materials such as those derived from tallow, palm oil and the like.

Preferred alkyl ester sulfonate surfactants, particularly for laundry applications, include those having the formula: Wherein R ³ is a C ₈ -C ₂₀ hydrocarbon group, preferably an alkyl group, or a combination thereof, R ⁴ is a C ₁ -C ₆ hydrocarbon group, preferably an alkyl group, or a combination thereof, and M is a cation that forms a water-soluble compound with an alkyl ester sulfonate sexual salt. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates in which R ³ is C ₁₀ -C ₁₆ alkyl.

Other suitable anionic surfactants include alkyl sulfate surfactants, which are water-soluble salts or acids of formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbon group, preferably an alkyl group or has a C ₁₀ -C ₂₀ Hydroxyalkyl of the alkyl moiety, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation such as an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl , dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof ammonium cation, etc.). _C12 - _C16 alkyl chains are generally preferred for lower wash temperatures (e.g., below about 50°C), and _C16 - _{C18 alkyl} chains are preferred for higher wash temperatures (e.g., above about 50°C). chain.

Other anionic surfactants useful for detersive purposes can also be included in the detergent compositions of the present invention. These may include salts of soaps (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di-, and triethanolamine salts), C ₈ -C ₂₂ primary or secondary alkane sulfonates, C ₈ -C ₂₄ olefin sulfonic acids Salts, sulfonated polycarboxylic acids prepared by sulfonating pyrolysis products of alkaline earth metal citrates, such as described in British Patent Specification No. 1,082,179; C ₈ -C ₂₄ alkyl polyglycol ether sulfuric acid Salts (containing up to 10 moles of oxyethylene); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkylphenoxyethylene ether sulfates, paraffin sulfonates, alkyl phosphates Salts, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinic acid monoesters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and sulfosuccinic acid diesters (especially saturated and unsaturated C ₆ -C ₁₂ diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as alkyl polyglucosides Sulfates (nonionic, non-sulfated compounds described below) _, branched primary alkyl sulfates _, and alkyl polyethoxy carboxylates such as those having the formula RO( _CH2CH2O ) _kCH2 A salt of COO ^- M ⁺ , wherein R is a C ₈ -C ₂₂ alkyl group, k is an integer from 1 to 10, and M is a cation that forms a soluble salt. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.

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

When present, the laundry detergent compositions herein will typically contain from about 1% to about 40%, preferably from about 3% to about 20%, by weight of such anionic surfactants.

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants which are water soluble salts or acids of formula RO(A) _m SO ₃ M where R is an unsubstituted C ₁₀ -C ₂₄ alkane or hydroxyalkyl having a C ₁₀ -C ₂₄ alkyl moiety, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is ethoxy or propyl Oxygen units, m value greater than 0, generally between about 0.5 to about 6, more preferably between about 0.5 to about 3, M is H or a cation, which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cations. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated by the present invention. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and those formed from alkylamines such as ethylamine, diethylamine, Cations derived from amines, triethylamine and their mixtures, etc. Exemplary surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₈ E(1.0)M), C ₁₂ -C ₁₈ alkyl polyethoxylate ( 2.25) Sulfate (C ₁₂ -C ₁₈ E(2.25)M), C ₁₂ -C ₁₈ Alkyl Polyethoxylate (3.0) Sulfate (C ₁₂ -C ₁₈ E(3.0)M) and C ₁₂ - C ₁₈ alkyl polyethoxylate (4.0) sulfate (C ₁₂ -C ₁₈ E(4.0)M), where M is suitably selected from sodium and potassium.

Dispersant

It has surprisingly been found that detergent compositions according to the invention which also comprise a dispersant provide improved cleaning of greasy/oily, colored and/or everyday body stains and/or soils. In addition, these compositions when formulated as laundry detergent/fabric care compositions provide improved cleaning and whitening of fabric items.

Suitable dispersants are water-soluble organic salts which are homo- or copolymeric acids or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl groups separated from each other by not more than 2 carbon atoms.

Polymers of this type are disclosed in GB-A-1596756. Examples of such salts are polyacrylates of MW 2000-5000, and their copolymers with maleic anhydride, such copolymers having a molecular weight of 1000-100000.

In particular copolymers of acrylate and methacrylate, eg 480N with a molecular weight of 4000, may be incorporated into the detergent compositions of the present invention at levels from 0.5% to 20% by weight of the composition.

Also suitable are lime soap peptizer compounds which preferably have a lime soap dispersing power (LSDP) of not more than 8, preferably not more than 7, most preferably not more than 6, as defined below. Lime soap peptizers are preferably present at levels of 0% to 20% by weight.

A numerical measure of the effectiveness of lime soap peptizers is given by lime soap dispersant power (LSDP), which was reported using HC Borghetty and CA Bergman in J.Am.Oil.Chem.Soc. .) Experimental determination of calcium soap dispersants described in the article in Vol. 27, pp. 88-90 (1950). This calcium soap dispersion test method is widely used by those skilled in the art, see for example, the following review articles; WN Linfield, Surfactant Science Series, Vol. 7, p. 3; WN Linfield, Surfactant Detergents (Tenside Surf. Det.), Vol. 27, pp. 159-163 (1990); and MK Nagarajan, WF Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73 (1989) . LSDP is the weight % ratio of the dispersant and sodium oleate needed for dispersing calcium soap deposits, said calcium soap deposits are made of 333ppm CaCO in 30ml ₃ (Ca: Mg=3: 2) 0.025g in water of equivalent hardness Formed from sodium oleate.

Surfactants with good lime soap peptizing capabilities include certain amine oxides, betaines, sultaines, alkyl ethoxy sulfates and ethoxylated alcohols.

Examples of surfactants useful in the present invention having an LSDP of not more than 8 include C ₁₆ -C ₁₈ dimethyl amine oxide, C ₁₂ -C ₁₈ alkyl ethoxy sulfates having an average degree of ethoxylation of 1-5 , especially C ₁₂ -C ₁₅ alkyl ethoxysulfate surfactants having a degree of ethoxylation of 3 (LSDP=4), and having an average degree of ethoxylation of 12 (LSDP=6) or 30 C ₁₄ -C ₁₅ ethoxylated alcohols sold by BASF GmbH under the trade names Lutensol A012 and Lutensol A030, respectively.

Polymeric calcium soap peptizers suitable for use in the present invention are described in the article by M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73 (1989).

Hydrophobic bleaches such as 4-[N-octanoyl-6-aminocaproyl]benzenesulfonate, 4-[N-nonanoyl-6-aminocaproyl]benzenesulfonate, 4-[N-decanoyl- 6-aminocaproyl]benzenesulfonate and mixtures thereof; and nonanoyloxybenzenesulfonate in combination with hydrophilic/hydrophobic bleach formulations are also useful as calcium soap peptizer compounds.

Regular Detergent Enzyme

Surprisingly it has been found that further detergent enzymes, especially lipases, amylases, proteases, water-soluble enzymes which enhance the water solubility of stains/soils containing saturated fatty acids, provide cleaning performance, fabric care and/or sanitizing action. Enzymatic detergent compositions of the invention provide improved cleaning of greasy/oily, colored and/or everyday body stains and/or soils. In addition, these compositions when formulated as laundry detergent/fabric care compositions provide improved cleaning and whitening of fabric items.

Said enzymes include those selected from the group consisting of cellulase, hemicellulase, peroxidase, protease, gluco-amylase, amylase, xylanase, lipase, esterase, cutinase , pectinase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase (malanase), β- Dextranase, arabinosidase, hyaluronase, chondroitinase, laccase, or mixtures thereof.

Suitable lipases for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1372034. Suitable lipases include those produced by the microorganism Pseudomonas fluorescens IAM 1057 that exhibit a positive immunological cross-reaction with antibodies to the lipase. This lipase is commercially 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, a lipase obtained from Chromobacter viscosum, such as Chromobacter viscosum variant lipolyticum NRRLB 3673 obtained from Toyo Jozo Corporation, Tagata, Japan; from USBiochemical Corporation, Chromobacterium viscous lipase obtained from USA and Disoynth in the Netherlands and lipase obtained from Pseudomonas gladioli. Particularly suitable lipases are lipases such as M1 Lipase ^R and lipomax ^R (Gist-Brocades) and Lipolase ^R and Lipolase Ultra ^R (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 by Novo Nordisk in EP258068, WO92/05249 and WO95/22615 and by Unilever in WO94/03578, WO95/35381 and WO96/00292.

Also suitable enzymes are cutinases [EC 3.1.1.50], which are considered a special class of lipases, ie lipases that do not require interfacial activation. The incorporation of cutinases in detergent compositions has been described eg in WO-A-88/09367 (Genencor); WO90/09446 (Plant Genetic System) and WO94/14963 and WO94/14964 (Unilever).

Lipase and/or cutinase are generally incorporated in detergent compositions in an amount of 0.0001% to 2% active enzyme by weight of the detergent composition.

Suitable proteases are subtilisins, which are obtained from special strains of Bacillus subtilis and Bacillus licheniformis (subtilisins BPN and BPN'). A suitable protease is obtained from the Bacillus strain, which has maximum activity in the pH range of 8-12, developed by Novo Industries A/S, Denmark and sold as ESPERASE ^(R) , hereinafter "Novo". The preparation of this and similar enzymes is described in British Patent Specification GB1243784 to Novo. Other suitable proteases include ALCALASE® ^{, DURAZYM®} and ^SAVINASE® from Novo, and ^MAXATASE® , ^MAXACAL® , PROPERASE® ^{and MAXAPEM®} (Maxacal for Protein Engineering) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases such as those described in European Patent Application Serial No. 87303761.8 filed April 28, 1987 (particularly pages 17, 24 and 98), which are referred to herein as "Protease B", and those described in European Patent Application 199404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme, referred to herein as "Protease A". Suitable are the proteases referred to herein as "Protease C", which are variants of alkaline serine proteases obtained from Bacillus in which lysine is substituted for arginine at position 27 and tyrosine is substituted for valine at position 104 acid, serine for asparagine at position 123, and alanine for threonine at position 274. Protease C is described in EP90915958:4 which corresponds to WO91/06637 published May 16,1991. Genetically modified variants, especially variants of Protease C are also included in the present invention.

A preferred protease known as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a carbonyl hydrolase precursor according to the Bacillus amyloliquefaciens subtilisin , at the position corresponding to +76 in the carbonyl hydrolase, it is also preferred to bind correspondingly to the group selected from +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 at one or more amino acid residue positions of +274, substituting different amino acids for multiple amino acid residues at said positions, as in WO95/10591 and C. Ghosh et al. filed on October 13, 1994 described in U.S. Patent Application Serial No. 08/322,677 entitled "Bleaching Compositions Containing Proteases." Also suitable are the carbonyl hydrolase variants of the proteases described in WO 95/10591, the amino acid sequence of which is obtained by substituting amino acid residues corresponding to position +210 in the enzyme precursor in combination with a substitution at one of the following positions or multiple residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered positions correspond to the naturally occurring Subtilisin or other carbonyl hydrolases or equivalent amino acid residues of subtilisins such as B. lentus subtilisin (copending patent application US Serial No. 60/048550 filed June 4, 1997).

Also suitable for the present invention are the proteases described in patent applications EP251446 and WO91/06637, the protease BLAP ^(R) described in WO91/02792 and their variants described in WO95/23221.

See also the high pH protease from Bacillus NCIMB 40338 described in WO 9318140A to Novo. Enzyme detergents containing a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529A to Novo. When desired, proteases with reduced adsorption and increased hydrolysis can be obtained as described in WO 9507791 to Procter & Gamble. Trypsin-like recombinant proteases suitable for the detergents of the present invention are described in WO 9425583 to Novo. Other suitable proteases are described in EP516200 to Unilever.

The amount of proteolytic enzyme incorporated in the detergent composition of the present invention is 0.0001%-2%, preferably 0.001%-0.2%, more preferably 0.005%-0.1% pure enzyme by weight of the composition.

Amylases (alpha and/or beta) may be included for removal of carbohydrate based stains. WO 94/02597, Novo Nordisk A/S, published February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also WO95/10603, NovoNordisk A/S, published April 20, 1995. Other known amylases for use in cleaning compositions include alpha- and beta-amylases. α-Amylases are known in the art and include those disclosed in US5003257; EP252666; WO91/00353; FR2676456; EP285123; Other suitable amylases are the stability-enhanced amylases described in WO 94/18314, published 18.08.1994 and WO 96/05295, Genencor, published 22.02.1996; and in 04.95. Amylase variants commercially available from NovoNordisk A/S with additional modifications to the immediate parent disclosed in published WO 95/10603. Also suitable are the amylases described in EP277216, WO95/26397 and WO96/23873 (all filed by NovoNordisk).

Examples of commercial a-amylase products are Purafect Ox ^Am® available from Genencor and ^Termamyl® , ^Ban® , ^Fungamyl® and ^Duramyl® available from Novo Nordisk A/S Denmark. WO95/26397 describes other suitable amylases: α-amylases characterized by specific activities at temperatures from 25°C to 55°C and pH values in the range 8-10 as determined by the ^Phadebas® α-amylase activity assay At least 25% greater than the specific activity of ^Termamyl® . Suitable are variants of the above enzymes described in WO96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to activity levels and thermostability combined with higher activity levels are described in WO95/35382.

Also suitable are isoamylases (EC 3.2.1.68). These debranching enzymes hydrolyze 1,6-alpha-D-glucosidic branches in glycogen, amylopectin and their beta-limiting dextrins.

The amount of amylolytic enzyme incorporated in the detergent composition of the present invention is 0.0001%-2%, preferably 0.00018%-0.06%, more preferably 0.00024%-0.048% pure enzyme by weight of the composition.

Enzymes and their possible cofactors for enhancing the water solubility of stains/soils containing saturated fatty acids are described in co-pending patent application PCT/US97/10972, filed June 23,1997.

Suitable acid-thiol ligases for the purposes of the present invention are described under EC 6.2.1 and require an esterification compound and an energy source. Preferred acid-thiol ligases are EC6.2.1.3 long-chain fatty acid CoA ligase, also known as Acyl-CoA synthetase; EC6.2.1.10 acid-CoA ligase, also known as Acyl-CoA synthetase; EC6.2.1.20 Long chain fatty acid-ACP ligase, also known as Acyl-ACP synthetase.

The esterified compound is a strong nucleophile, and the energy source is a molecule with hydrolysis free energy greater than or equal to 11 kcal/mole. Examples of esterified compounds are coenzyme A (CoA), acyl carrier protein (ACP), glutathione (tripeptide of cysteine, glutamic acid and glycine) or polyamines such as N-(aminoethyl) ethyl Amines ( _NH2 - _CH2CH2 -NH _{- CH2CH3} ), and they are commercially available from Boehringer _Mannheim or Sigma. They will generally be present in the detergent compositions herein at a level of from 0.01% to 10%, preferably from 0.1% to 5%, by weight of the total composition. Examples of such energy sources are adenosine-5'-triphosphate (ATP), phosphoenolpyruvate, phosphocreatine, acetyl phosphate and are commercially available from Boehringer Mannheim, Sigma or Aldrian. They will generally be present in the detergent compositions herein at a level of from 0.01% to 10%, preferably from 0.1% to 5%, by weight of the total composition.

Suitable desaturases for the purposes of the present invention are EC 1.14.99.5 stearoyl-CoA desaturases and EC 1.14.99.6 Acyl-ACP desaturases and require an electron donating system.

The electron donating system is a reducing agent that provides electrons to convert Fe ³⁺ into Fe ²⁺ , corresponding to a redox potential higher than 0.771V. Examples of electron donating systems are ferredoxin, the reduced form of nicotinamide adenine dinucleotide phosphate (NADPH), and ferredoxin:NADPH(+) oxidoreductase, where NADPH can potentially be used as an efficient reducing system Instead, the reducing system consists of ferredoxin, grana (spinach chloroplast) lamellae, ascorbic acid, dichloroindophenol and light/dithiothreitol and reduced glutathione/dithionite or ascorbic acid Salt composition, for example described in Arcxh Biochem. Biophys (Biochem.Biophys), 162, p. 158 (1974) and J.Biol.Chem.243, p. 4626 (1968) and available from Boehringer Mannheim or Sigma . They will generally be present in the detergent compositions of the present invention at a level of from 0.001% to 10%, preferably from 0.01% to 5%, by weight of the total composition.

Suitable glutathione S-transferases for the purposes of the present invention are described under EC 2.5.1.18. G6636 and G8642 are commercially available glutathione S-transferases sold by Sigma.

Cellulases useful in the present invention include bacterial and fungal cellulases. Preferably they have an optimum pH range of 5-12 and an activity above 50 CEVU (Cellulose Viscosity Units). Suitable cellulases are disclosed in U.S. Patent No. 4,435,307 to Barbesgoard et al., J61078384 and WO96/02653, which disclose fungal cellulases produced by Humicola insolens, Trichoderma, Rhizopus and Sporotrichum, respectively. . EP739982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275; DE-OS-2247832 and WO95/26398.

Examples of such cellulases are cellulases produced by Humicola insolens (Humicola griseus var. thermoidea) strains, in particular Humicola genus strain DSM1800.

Other suitable cellulases are cellulases derived from Humicola insolens, having a molecular weight of approximately 50 KDa, an isoelectric point of 5.5, and containing 415 amino acids, and a ~43 kD insolase derived from Humicola insolens, DSM1800, having cellulase activity. Glucanase; the preferred endoglucanase component has the amino acid sequence disclosed in PCT patent application WO 91/17243. Also suitable cellulases are the EGIII cellulases obtained from Trichodermal longibrachiatum described in WO 94/21801, Genencor, published September 29,1994. Particularly suitable cellulases are cellulases with a color care effect. Examples of such cellulases are those described in European Patent Application No. 91202879.2, filed November 6,1991. Carezyme and Celluzyme (Novo Nordisk A/S) are particularly suitable. See also WO91/17244 and WO91/21801. Other suitable cellulases having fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471.

The cellulase is generally incorporated in the detergent composition in an amount of 0.0001%-2% active enzyme by weight of the detergent composition.

Peroxidase is used in combination with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for "solution bleaching", ie to inhibit the migration of dyes or pigments that have been released from a substrate during the wash to other substrates in the wash solution. Peroxidases are known in the art herein and include, for example, horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- and bromo-peroxidases. Detergent compositions containing peroxidase are disclosed, for example, in PCT International Applications WO 89/099813, WO 89/09813 and in European Patent Application No. 91202882.6 filed on November 6, 1991 and filed on February 20, 1996 EP96870013.8. Builders generally comprise from 0.1% to 5% by weight of the total composition. Preferred synergists are substituted phenothiazines and phenoxazines, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or sodium perborate are preferred sources of hydrogen peroxide.

The peroxidase is generally incorporated in the detergent composition in an amount of 0.0001%-2% active enzyme by weight of the detergent composition.

The aforementioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. The source may also be mesophilic or extremophilic (psychrophilic, cold-eating, thermophilic, barophilic, basophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes can be used. Also included by definition are mutants of the native enzyme. Mutants can be obtained, for example, by protein and/or genetic engineering, chemical and/or physical modification of native enzymes. It is common practice to express the enzyme by a host organism in which the genetic material responsible for the production of the enzyme is cloned.

The enzymes are typically incorporated into detergent compositions at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. The enzyme can be added as a separate single component (pellets, granules, stabilized liquid, etc. containing one enzyme) or as a mixture of two or more enzymes (eg composite granules).

Other suitable detergent ingredients that may be added are enzyme oxidation scavengers, which are described in co-pending European patent application 92870018.6, filed January 31,1992. An example of such an enzyme oxidation scavenger is ethoxylated tetraethylenepolyamine.

Various enzyme materials and methods for their incorporation into synthetic detergent compositions are also disclosed in WO 9307263A and WO 9307260A of Genencor International, WO 8908694A of Novo, and U.S. Patent of McCarty et al. issued January 5, 1971 US3553139. Some enzymes are also disclosed in US Pat. No. 4,101,457, Place et al., issued July 18, 1978, and US Pat. Enzyme materials useful in liquid detergent formulations and methods of their incorporation into such formulations are disclosed in US Patent 4,261,868, Hora et al., issued April 14,1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US Patent 3,600,319, Gedge et al., issued August 17, 1971, EP 199,405, and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described eg in US Pat. No. 3,519,570. A useful Bacillus AC13 producing proteases, xylanases and cellulases is described in WO 9401532A to Novo.

Additional Surfactant System

The detergent compositions of the invention may also comprise a surfactant system, wherein the surfactant may be selected from nonionic and/or cationic and/or amphoteric and/or zwitterionic and/or semipolar surfactants.

Surfactants will generally be present at levels of from 0.1% to 60% by weight, more preferably incorporated at levels of from 1% to 35% by weight of the detergent compositions herein, most preferably from 1% to 30%.

Surfactants are preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzymes in these compositions.

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

Polyoxyethylene, polyoxypropylene and polyoxybutylene condensates of alkylphenols are suitable for use as nonionic surfactants in the surfactant system of the present invention, preferably polyoxyethylene condensates. These compounds include the condensation products of alkylphenols with alkylene oxides having an alkyl group having from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in a linear or branched configuration. In a preferred embodiment, oxyethylene is present in an amount equal to about 2 to about 25 moles, more preferably about 3 to about 15 moles of oxyethylene 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, which are all Sold by Rohm & Haas. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The condensation products of primary and secondary fatty alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant in the nonionic surfactant system of the present invention. The alkyl chains of the fatty alcohols can be straight or branched, primary or secondary, and generally contain from about 8 to about 22 carbon atoms. Preferred are condensation products of alcohols with from about 2 to about 10 moles of ethylene oxide, per mole of alcohol, wherein the alkyl group of the alcohol contains from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms . From about 2 to about 7 moles of oxyethylene, most preferably from 2 to 5 moles of oxyethylene, are present in the condensation product per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ^™ 15-S-9 (a condensation product of C ₁₁ -C ₁₅ linear alcohols with 9 moles of ethylene oxide), Tergitol ^™ 24- L-6NMW (condensation product of C ₁₂ -C ₁₄ primary alcohols with 6 moles of ethylene oxide and has a narrow molecular weight distribution), both sold by Union Carbide Corporation; also Neodol ^TM 45-9 sold by Shell Chemical Company (condensation product of C ₁₄ -C ₁₅ linear alcohols with 9 moles of ethylene oxide), Neodol ^TM 23-3 (condensation product of C ₁₂ -C ₁₃ linear alcohols with 3.0 moles of ethylene oxide), Neodol ^TM 45 -7 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol and 7 moles of ethylene oxide), Neodol ^TM 45-5 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol and 5 moles of ethylene oxide); by Kyro ^™ EOB (condensation product of C ₁₃ -C ₁₅ alcohols with 9 moles of ethylene oxide) sold by Procter & Gamble Company; and Genapol LA030 or LA 050 (C ₁₂ -C ₁₄ alcohols with 3 or 5 moles of epoxy condensation products of ethane). The preferred HLB range for these products is 8-11, most preferably 8-10.

Also suitable for use as the nonionic surfactant in the surfactant system of the present invention are the alkyl polysaccharides disclosed in U.S. Patent No. 4,565,647 issued to Llenado on January 21, 1986, which have from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, a hydrophobic group and a polysaccharide such as a polyglycoside hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably about 1.3 to about 2.7 sugar units. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example glucose, galactose and galactosyl moieties can be used to replace the glucosyl moiety (hydrophobic groups are optionally attached at 2-, 3-, 4-, etc. positions, Thereby obtaining glucose or galactose as opposed to glucoside or galactoside). An intersaccharide linkage may be, for example, between the 2-, 3-, 4- and/or 6-position of the preceding saccharide unit and a position of the additional saccharide unit.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains from about 10 to about 18 carbon atoms, preferably about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; x is about 1.3 to about 10, preferably about 1.3 to about 3, most Preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is first prepared and then reacted with glucose or a source of glucose to form the glucoside (attachment at the 1-position). The 1-position of the additional glycosyl unit may then be linked to the 2-, 3-, 4- and/or 6-position, preferably primarily the 2-position, of the preceding glycosyl unit.

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 the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Addition of a polyoxyethylene moiety to the hydrophobic moiety tends to increase the water solubility of the overall molecule, and the liquid character of the product is maintained to the point where the polyoxyethylene content is about 50% by weight of the total condensation product, which is equivalent to Up to about 40 moles of ethylene oxide condense. Examples of compounds of this type include certain commercially available Plurafac ^™ LF404 and Pluronic ^™ surfactants, which are sold by BASF.

Also suitable for use as the nonionic surfactant in 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 portion of these products consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of from about 2500 to about 3000. The hydrophobic moiety is condensed with ethylene oxide to such an extent that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of nonionic surfactants of this type include some of the commercially available Tetronic ^™ compounds, sold by BASF.

Preferred for use as the nonionic surfactant in the surfactant system of the present invention are polyoxyethylene condensates of alkylphenols, condensation products of primary and secondary fatty alcohols with about 1 to about 25 moles of ethylene oxide, alkanes polysaccharides and their mixtures. Most preferred are C ₈ -C ₁₄ alkylphenol ethoxylates with 3 to 15 ethoxy groups and C ₈ -C ₁₈ alcohol ethoxylates with 2 to 10 ethoxy groups (preferably C ₁₀ average ), and mixtures thereof.

Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula: Wherein R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C _5-31 hydrocarbyl, Z is a Polyhydroxyl hydrocarbyls of linear hydrocarbyl chains, or alkoxylated derivatives thereof. Preferably ^R is methyl, ^R is a straight chain C _11-15 alkyl or C _16-18 alkyl or alkenyl chain such as coconut oil alkyl or a mixture thereof, and Z is determined by the reduction in a reductive amination reaction Sugars such as glucose, fructose, maltose, lactose are obtained.

The detergent compositions of the present invention may also contain cationic, amphoteric, zwitterionic and semi-polar surfactants, as well as nonionic and/or anionic surfactants not already described herein.

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

[R ² (OR ³ ) _y ][R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X wherein R ² is an alkyl or alkyl benzyl having about 8 to about 18 carbon atoms in its alkyl chain Each R ³ is selected from the group consisting of -CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )-, -CH ₂ CH(CH ₂ OH)-, -CH ₂ CH ₂ CH ₂ - and mixtures thereof; each R ⁴ is selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl ring structure formed by linking two R ⁴ groups, -CH ₂ CHOH-CHOHCOR ⁶ CHOHCH ₂ OH, wherein R ⁶ is any hexose or hexose polymer group having a molecular weight less than about 1000, and hydrogen (when y is other than 0); ^R5 is the same group as ^R4 , or the carbon atom where ^R2 is added to ^R5 the total number of alkyl chains is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; x is any compatible anion.

Quaternary ammonium surfactants suitable for use in the present invention have the formula (I):

Wherein _R is an alkyl group (C6-C10) of short chain length, or an alkylamidoalkyl group of formula (II):

y is 2-4, preferably 3.

Wherein R ₂ is H or C1-C3 alkyl,

wherein x is 0-4, preferably 0-2, most preferably 0,

Wherein R ₃ , R ₄ and R ₅ are the same or different, and can be short-chain alkyl (C1-C3), or alkoxylated alkyl of formula III,

where X ^- is a counterion, preferably a halide, such as chloride or methylsulfate,

R ₆ is C ₁ -C ₄ , and z is 1 or 2.

Preferred quaternary ammonium surfactants are those defined by formula I: wherein

R ₁ is C ₈ , C ₁₀ or a mixture thereof, x=0,

R ₃ , R ₄ =CH ₃ , and R ₅ =CH ₂ CH ₂ OH.

Highly preferred cationic surfactants suitable for use in the compositions of the present invention are water-soluble quaternary ammonium compounds having the formula:

R ₁ R ₂ R ₃ R ₄ N ⁺ X ^- (i)

wherein R ₁ is C ₈ -C ₁₆ alkyl, each R ₂ , R ₃ and R ₄ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl and -(C ₂ H ₄ O) _x H, where x has a value from 2 to 5 and X is an anion. Not more than one of R ₂ , R ₃ , R ₄ should be benzyl.

Preferred alkyl chain lengths for R ₁ are C ₁₂ -C ₁₅ . In particular, the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or obtained by olefin synthesis or oxo alcohol synthesis. Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl, and the anion X may be selected from halide, methylsulfate, acetate and phosphate ions.

Examples of suitable quaternary ammonium compounds of formula (i) for use in the present invention are:

Cocotrimonium Chloride or Ammonium Bromide;

Coconut oil methyl dihydroxyethyl ammonium chloride or ammonium bromide;

Decyltriethylammonium chloride;

Decyldimethylhydroxyethylammonium chloride or ammonium bromide;

C ₁₂ -C ₁₅ dimethyl hydroxyethyl ammonium chloride or ammonium bromide;

Coco Dimethyl Hydroxyethyl Ammonium Chloride or Ammonium Bromide;

Myristyltrimethylammonium methylsulfate;

Lauryldimethylbenzyl ammonium chloride or ammonium bromide;

Lauryldimethyl(oxyethylene) ammonium _chloride or ammonium bromide;

Choline esters (compounds of formula (i), wherein R ₁ is CH ₂ -CH ₂ -OC(O)-C _12-14 alkyl, and R ₂ , R ₃ , R ₄ are methyl);

Dialkylimidazolines [compounds of formula (i)].

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

Typical cationic fabric softening ingredients include water insoluble quaternary ammonium fabric softening actives or their corresponding amine precursors, most commonly dilong chain alkylammonium chlorides or methylsulfates.

Wherein preferred cationic softener includes following:

1) ditallow dimethyl ammonium chloride (DTDMAC);

2) dihydrogenated tallow dimethyl ammonium chloride;

3) Methyl sulfated dihydrogenated tallow dimethyl ammonium;

4) distearyl dimethyl ammonium chloride;

5) dioleyl dimethyl ammonium chloride;

6) dipalmityl hydroxyethyl methyl ammonium chloride;

7) stearyl benzyl dimethyl ammonium chloride;

8) tallow trimethylammonium chloride;

9) tallow trimethyl ammonium hydrochloride;

10) C _12-14 alkyl hydroxyethyl dimethyl ammonium chloride;

11) C _12-18 alkyl dihydroxyethyl methyl ammonium chloride;

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

13) Di(tallowoxyethyl)dimethylammonium chloride;

14) Ditallow imidazolinium methyl sulfate;

15) 1-(2-tallowamidoethyl)-2-tallowyl imidazolinium methylsulfate.

Biodegradable quaternary ammonium compounds have emerged as alternatives to the traditionally used di-long chain alkylammonium chlorides and methylsulfates. Such quaternary ammonium compounds contain long chain alk(en)yl groups interrupted by functional groups such as carboxyl groups. Said materials and fabric softening compositions containing them are disclosed in a number of publications, for example EP-A-0040562 and EP-A-0239910.

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

Wherein Q is selected from -OC(O)-, -C(O)-O-, -OC(O)-O-, -NR ⁴ -C(O)-, -C(O)-NR ⁴ -;

R ¹ is (CH ₂ ) _n -QT ² or T ³ ;

R ² is (CH ₂ ) _m -QT ⁴ or T ⁵ or R ³ ;

R ³ is C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl or H;

R ⁴ is H or C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl;

T ¹ , T ² , T ³ , T ⁴ , T ⁵ are independently C ₁₁ -C ₂₂ alkyl or alkenyl;

n and m are integers from 1 to 4; and

X ^- is a softener compatible anion.

Non-limiting examples of softener compatible anions include chloride or methylsulfate.

The alkyl or alkenyl chains T ¹ , T ² , T ³ , T ⁴ , T ⁵ 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 long chain alkyl and alkenyl species. Compounds in which T ¹ , T ² , T ³ , T ⁴ , T ⁵ represent typical tallow mixed long chains are particularly preferred.

Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions of the present invention include:

1) N, N-di(tallowoxyethyl)-N, N-dimethylammonium chloride;

2) N, N-di(tallowoxyethyl) N-methyl, N-(2-hydroxyethyl) ammonium methylsulfate;

3) N,N-bis(2-tallowoxy-2-oxoethyl)-N,N-dimethylammonium chloride;

4) N,N-bis(2-tallowoxy-ethylcarbonyloxyethyl)-N,N-dimethylammonium chloride;

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

6) N,N,N-tris(tallowoxy-ethyl)-N-methylammonium chloride;

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

8) 1,2-Ditallowoxy-3-trimethylammonium propane chloride; and mixtures of any of the foregoing.

When included, the detergent compositions herein will typically contain from 0.2% to about 25%, preferably from about 1% to about 8%, by weight of such cationic surfactants.

Amphoteric surfactants are also suitable for use in the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic group may be straight or branched. One aliphatic substituent contains at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one aliphatic substituent contains a water-soluble anionic group, eg, carboxy, sulfonate, sulfate. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, lines 18-35, for examples of amphoteric surfactants.

When included, the detergent compositions herein will typically contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of such amphoteric surfactants.

Zwitterionic surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium salts, quaternary phosphonium or tertiary sulfonium compounds. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.

When included, the detergent compositions herein will typically contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of such zwitterionic surfactants.

Semi-polar nonionic surfactants are a specific class of nonionic surfactants that include water-soluble amine oxides that contain an alkyl moiety of about 10 to about 18 carbon atoms and two alkyl moieties selected from the group consisting of about 1 to Alkyl and hydroxyalkyl moieties of about 3 carbon atoms; water-soluble phosphine oxides comprising an alkyl moiety of about 10 to about 18 carbon atoms and 2 and hydroxyalkyl moieties; and water-soluble sulfoxides comprising an alkyl moiety of about 10 to about 18 carbon atoms and a moiety selected from alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms part.

其中R³是含有约8至约22个碳原子的烷基、羟烷基或烷基苯基、或它们的混合物；R⁴是含有约2至约3个碳原子的亚烷基或羟亚烷基或它们的混合物；x为0至约3；每个R⁵是含有约1至约3个碳原子的烷基或羟烷基或含有约1至约3个氧乙烯基团的聚氧乙烯基团。R⁵基团可彼此连接，例如通过氧或氮原子连接形成环状结构。Semi-polar nonionic detergent surfactants include amine oxide surfactants having the formula:

wherein ^R3 is alkyl, hydroxyalkyl or alkylphenyl, or mixtures thereof containing from about 8 to about 22 carbon atoms; ^R4 is alkylene or hydroxyalkylene containing from about 2 to about 3 carbon atoms Alkyl or mixtures thereof; x is from 0 to about 3; each ^R is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyoxyl group containing from about 1 to about 3 oxyethylene groups Vinyl group. The ^R5 groups may be linked to each other, for example via an oxygen or nitrogen atom to form a ring structure.

These amine oxide surfactants include in particular C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides.

When included, the detergent compositions herein will typically contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of such semi-polar nonionic surfactants.

The detergent compositions of the present invention may also comprise cosurfactants selected from primary or tertiary amines. Suitable primary amines for use in the present invention include amines of the formula R ₁ NH ₂ , wherein R ₁ is a C ₆ -C ₁₂ , preferably C ₆ -C ₁₀ alkyl chain, or R ₄ X(CH ₂ ) _n , where X is -O-, -C(O)NH- or -NH-, R ₄ is a C ₆ -C ₁₂ alkyl chain, n is 1-5, preferably 3. The _R alkyl chain may be straight or branched and may be spaced by up to 12, preferably less than 5, oxyethylene moieties.

Preferred amines according to the above formula are n-alkylamines. Suitable amines for use in the present invention 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.

R₃是C₆-C₁₂，优选C₆-C₁₀烷基链，或R₃是R₄X(CH₂)_n，其中X是-O-，-C(O)NH-或-NH-，R₄是C₄-C₁₂，n是1-5，优选2-3，R₅是H或C₁-C₂烷基，x是1-6。R₃和R₄可以是直链或支链；R₃烷基链可间隔最多至12个，优选少于5个氧乙烯部分。Suitable tertiary amines for use in the present invention include tertiary amines of the formula R ₁ R ₂ R ₃ N, wherein R ₁ and R ₂ are C ₁ -C ₈ alkyl chains or

R ₃ is C ₆ -C ₁₂ , preferably C ₆ -C ₁₀ alkyl chain, or R ₃ is R ₄ X(CH ₂ ) _n , where X is -O-, -C(O)NH- or -NH- , R ₄ is C ₄ -C ₁₂ , n is 1-5, preferably 2-3, R ₅ is H or C ₁ -C ₂ alkyl, x is 1-6. _R3 and _R4 may be linear or branched; the _R3 alkyl chain may be separated by up to 12, preferably less than 5, oxyethylene moieties.

Preferred tertiary amines are R ₁ R ₂ R ₃ N, where R ₁ is a C ₆ -C ₁₂ alkyl chain, R ₂ and R ₃ are C ₁ -C ₃ alkyl or Wherein R ₅ is H or CH ₃ , x=1-2.

其中R₁是C₆-C₁₂烷基；n是2-4，优选n是3；R₂和R₃是C₁-C₄。Also preferred are amidoamines of the formula:

Wherein R ₁ is C ₆ -C ₁₂ alkyl; n is 2-4, preferably n is 3; R ₂ and R ₃ are C ₁ -C ₄ .

The most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C8-C10 oxypropylamine, N-coconut oil 1-3 diaminopropane, coconut Oleyl Dimethylamine, Lauryl Dimethylamine, Lauryl Di(Hydroxyethyl)amine, Coco Di(Hydroxyethyl)amine, 2 Moles Propoxylated Laurylamine, 2 Moles Propoxy Octylamine, lauryl amidopropyl dimethylamine, C8-C10 amidopropyl dimethylamine and C10 amidopropyl dimethylamine.

The most preferred amines for use in the compositions of the present invention are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly suitable are n-dodecyldimethylamine and dihydroxyethylcocoalkylamine and 7 mole ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.

Color care and fabric care

Techniques to provide a color-care effect may also be included. Examples of these technologies are metal catalysts for color retention. Such metal catalysts are described in co-pending European Patent Application No. 92870181.2. Further examples of color care/fabric care technologies are dye fixatives, polyolefin dispersions for wrinkle resistance and improved water absorption, fragrance and amino functional polymers for color care treatments and fragrance substantivity, described in 1996 In pending patent application No. 96870140.9 filed on November 7, 2009.

Fabric softening agents can also be incorporated into the detergent compositions herein. These softeners can be of inorganic or organic type. Examples of inorganic softeners are the smectites disclosed in GB-A-1400898 and USP 5,019,292. Organic fabric softeners include water insoluble tertiary amines as disclosed in GB-A 1 514 276 and EP-B 0 011 340 and the former tertiary amines combined with mono Mixtures of C12-C14 quaternary ammonium salts, and double long chain amides as disclosed in EP-B-0242919. Other suitable organic components for fabric softening systems include the high molecular weight polyoxyethylene materials disclosed in EP-A-0 299 575 and 0 313 146.

The content of smectite clay is usually 2% to 20%, more preferably 5% to 15% by weight, this material is added as a dry blend component to the remaining ingredients of the formulation. The blending amount of organic fabric softener such as water-insoluble tertiary amine or double long-chain amide material is 0.5% to 5% by weight, usually 1% to 3% by weight, while the addition of high molecular weight polyoxyethylene material and water-soluble cationic material The amount is 0.1% to 2%, usually 0.15% to 1.5% by weight. These materials are usually added to the spray-dried portion of the composition, although in some cases it may be more convenient to add them as dry-mixed granules or to spray them as a molten liquid onto the other solid components of the composition.

bleach

Other optional detergent ingredients which may be included in the detergent compositions of the present invention include bleaches such as hydrogen peroxide, PB1, PB4 and percarbonates having a particle size of 400-800 microns. These bleach components may include one or more oxygen bleaches, and depending on the bleach selected, one or more bleach activators. When present, oxygen bleaching compounds are generally present at levels of from about 1% to about 25%.

The bleaching agent component used herein can be any bleaching agent suitable for use in detergent compositions, including oxygen bleaching agents and others known in the art. Bleaching agents suitable for use in the present invention may be activated or non-activated bleaching agents.

One class of oxygen bleaches which can be used includes percarboxylic acid bleaches and their salts. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, magnesium 4-nonylamino-4-oxoperoxybutyrate and diperoxydodecane di Magnesium acid. These bleaching agents are disclosed in US Patent 4,483,781, US Patent Application 740,446, European Patent Application 0133354 and US Patent 4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in US Patent No. 4,634,551.

Another class of bleaches that can be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, trichloroisocyanuric acid, sodium and potassium dichloroisocyanurates and N-chloro and N-bromoalkanesulfonamides. Such substances are generally added in an amount of 0.5-10% by weight of the finished product, preferably 1-5% by weight.

Hydrogen peroxide-releasing agents can be combined with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxy Phenylbenzenesulfonate (ISONOBS, described in EP 120,591), pentaacetylglucose (PAG) or phenolsulfonate of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO94/28106) Used in combination, these bleach activators perhydrolyze to form peracids as the active bleaching species, resulting in improved bleaching performance. Also suitable activators are acylated citrates such as those disclosed in co-pending European Patent Application No. 91870207.7.

Suitable bleaching agents for use in the detergent compositions of the present invention include peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds, which are described in our co-pending application USSN 08/136,626, PCT/US95/ 07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775.

Hydrogen peroxide can also be provided by adding an enzymatic system (ie enzyme and corresponding substrate) capable of generating hydrogen peroxide at the beginning or during the wash and/or rinse process. This enzymatic system is disclosed in EP patent application 91202655.6 filed on October 9,1991.

Metal-containing catalysts for use in bleach compositions include cobalt-containing catalysts such as cobalt(III) pentaamine acetate and manganese-containing catalysts such as those described in EPA549271, EPA549272; EPA458397; US5246621; EPA458398; US5194416 and US5114611 Those ones. Bleaching compositions containing peroxygen compounds, manganese-containing bleach catalysts and chelating agents are described in patent application 94870206.3.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be used in the present invention. One class of non-oxygen bleaches of particular interest includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines. These materials can deposit on the substrate during the washing process. When irradiated with light in the presence of oxygen, such as when clothes are hung out to dry in the sun, the sulfonated zinc phthalocyanine is activated, thereby bleaching the substrate. A preferred zinc phthalocyanine and photoactivated bleaching process is described in US Patent No. 4,033,718. Typically, detergent compositions will contain from about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine.

Builder system

The compositions of the present invention may also comprise a builder system. Any conventional builder system is suitable for use herein, including aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic acids and fatty acids, such as ethylenediaminetetraacetate, di Materials for ethylenetriaminepentamethylene acetate, metal ion sequestrants such as amino polyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid . Phosphate builders are also useful herein.

Suitable builders may be inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, more particularly hydrated synthetic zeolites such as hydrated zeolites A, X, B, HS or MAP.

Another suitable inorganic builder material is layered silicate, eg SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate composed of sodium silicate (Na ₂ Si ₂ O ₅ ).

Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and their ether derivatives as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, malonic acid, and fumaric acid , and the ether carboxylates described in German Patents 2,446,686 and 2,446,687 and US Patent No. 3,935,257, and the thionyl carboxylates described in Belgian Patent 840,623. Polycarboxylates containing three carboxy groups include, inter alia, the water-soluble citrates, aconitates and citraconates, and succinate derivatives such as carboxymethoxysuccinate as described in British Patent 1,379,241 , lactoxysuccinates as described in Dutch Patent Application 7205873, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylates as described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates disclosed in British Patent No. 1,261,829 Carboxylate and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Patent No. 3,936,448, and the sulfonated pyrolytic Citrates, and polycarboxylates containing phosphine substituents are disclosed in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylate, cyclopentadienide pentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran tetracarboxylate, 1,2,3,4,5,6-hexane hexa Carboxylate salts and carboxymethyl derivatives of polyalcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include derivatives of mellitic acid, pyromellitic acid and phthalic acid disclosed in British Patent No. 1,425,343.

Among the above compounds, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

Preferred builder systems for use in the compositions of the present invention include water-insoluble aluminosilicate builders such as zeolite A or layered silicates (SKS-6) with water-soluble carboxylate chelating agents such as lemon A mixture of acids.

A preferred builder system comprises a mixture of a water insoluble aluminosilicate builder such as zeolite A with a water soluble carboxylate chelating agent such as citric acid. Preferred builder systems for use in the liquid detergent compositions of the present invention are soaps and polycarboxylates.

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

Other suitable water-soluble organic salts are homo- or co-polymeric acids or their salts, wherein the polycarboxylic acid contains at least two carboxyl groups 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 with MW 2000-5000, and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000 to 70,000, especially about 40,000.

Typical levels of detergency builder salts are from 5% to 80%, preferably from 10% to 70%, most usually from 30% to 60%, by weight of the composition.

Chelating agent

The detergent compositions of the present invention may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all chelating agents being as defined hereinafter. Without being bound by theory, it is believed that the advantages of these materials lie in part in their extraordinary ability to remove iron and manganese from wash solutions by forming soluble chelates.

Amino carboxylates used as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, Triethylenetetraamine hexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

When at least low levels of total phosphorus are permitted in the detergent compositions herein, amino phosphonates are also suitable for use as chelating agents in the compositions herein, including: ethylenediamine tetrakis (methylene phosphonates) , for DEQUEST. These amino phosphonates preferably do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

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

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), especially as described in US Pat. S, S] isomers.

The compositions of the present invention may also contain water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a chelating agent, or as an adjunct to, for example, insoluble builders such as zeolites, layered silicates, etc. Builder.

If utilized, chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. If utilized, chelating agents are more preferably present in an amount of from about 0.1% to 3.0% by weight of the composition.

Foam suppressor

Another optional ingredient is a suds suppressor, exemplified by silicones and silica-polysiloxane mixtures. Polysiloxane is generally represented by alkylated polysiloxane substances, while silica is generally used in the form of fine powder, examples are silica airgel and xerogel and various types of hydrophobic di silicon oxide. These materials may be incorporated in the form of granules wherein the suds suppressor is advantageously releasably incorporated into a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier. Alternatively, the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying onto one or more of the other ingredients.

Preferred silicone suds control agents are disclosed in US Patent 3,933,672 to Bartollota et al. Other particularly useful suds suppressors are the self-emulsifying silicone suds 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-diol copolymer. Especially preferred suds control agents are suds suppressor systems comprising a mixture of silicone oils and 2-alkyl alkanols. A suitable 2-alkyl alkanol is 2-butyloctanol, which is commercially available under the tradename Isofol 12 R.

Such suds suppressor systems are described in co-pending European Patent Application No. 92870174.7, filed November 10,1992.

Particularly preferred silicone suds control agents are described in co-pending European Patent Application No. 92201649.8. The composition may comprise a polysiloxane/silica mixture in combination with a fumed non-porous silica such as Aerosil ^R.

The above-mentioned anti-foaming agent is generally used in an amount of 0.001% to 2%, preferably 0.01% to 1%, by weight of the composition.

other

Other components used in detergent compositions, such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, colorants, and/or encapsulated or non-encapsulated of spices.

A particularly suitable encapsulating material is a water-soluble capsule consisting of a matrix of polysaccharides and polyols, such as described in GB 1,464,616.

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

Antiredeposition and soil suspension agents suitable for use herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts. Polymers of this type include the aforementioned polyacrylates as builders and copolymers of maleic anhydride and acrylic acid, and copolymers of maleic anhydride and ethylene, methyl vinyl ether or methacrylic acid, maleic anhydride The anhydride comprises at least 20 mole percent of the copolymer. These materials are generally 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 are anionic in nature, examples of which are 4,4'-bis(2-ethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'- Disodium disulfonate, 4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene-2: 2'-disodium disulfonate, 4,4 '-Bis(2,4-dianilino-s-triazin-6-ylamino)stilbene-2: 2'-disulfonate disodium, 4',4"-bis(2,4-dianilino -s-triazin-6-ylamino)stilbene-2'-sulfonic acid monosodium, 4,4'-bis(2-anilino-4-(N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino)stilbene-2: disodium 2'-disulfonate, 4,4'-bis(4-phenyl-2,1,3-triazol-2-yl)stilbene -2: 2'-disodium disulfonate, 4,4'-bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino) Stilbene-2: disodium 2'-disulfonate, 2-(stilbene-4"-(naphtho-1',2':4,5)-1,2,3-triazole-2"-sulfo sodium biphenyl and 4,4'-bis(2-sulfostyryl)biphenyl. Highly preferred brighteners are those specified in co-pending European Patent Application No. 95201943.8.

Other useful polymeric materials are polyethylene glycols, especially those having a molecular weight of 1,000-10,000, more preferably 2,000-8,000, most preferably about 4,000. These substances are used in amounts of 0.20% to 5%, more preferably 0.25% to 2.5% by weight. These polymers and the aforementioned homo- or co-polymeric polycarboxylates are useful for improving whiteness maintenance, fabric dust deposition and cleaning performance on earthy, proteinaceous and oxidizable soils in the presence of transition metal impurities. All aspects are valuable.

Soil release agents useful in the compositions of the present invention are generally copolymers or terpolymers of terephthalic acid and ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in commonly assigned US Patents 4,116,885 and 4,711,730 and European Published Patent Application No, 0 272 033. According to EP-A-0272033, a particularly preferred polymer has the formula: (CH ₃ (PEG) ₄₃ ) _0.75 (POH) _0.25 [T-PO) _2.8 (T-PEG) _0.4 ]T(POH) _0.25 (( PEG) ₄₃ CH ₃ ) _0.75

where PEG is -(OC ₂ H ₄ )O-, PO is (OC ₃ H ₆ O), and T is (pcOC ₆ H ₄ CO).

Also very useful are modified polyesters such as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol, the end groups of which are mainly composed of sulfo benzoate and, secondarily, monoesters of ethylene glycol and/or propylene glycol. The aim is to obtain a polymer terminated at both ends by sulfobenzoate groups. "Predominantly" in this context means that the majority of said copolymers are terminated with sulfobenzoate groups. However, some copolymers are not completely capped, so their end groups may consist of monoesters of ethylene glycol and/or 1,2-propanediol, which are "minor" constituents of this class.

The polyester selected herein contains about 46% by weight dimethyl terephthalate, about 16% by weight 1,2-propanediol, about 10% by weight ethylene glycol, about 13% by weight dimethyl sulfobenzoate and about 15% weight sulfoisophthalic acid, which has a molecular weight of about 3000. The polyesters and their preparation are described in detail in EPA311342.

It is known in the art that free chlorine in tap water can rapidly inactivate enzymes included in detergent compositions. Therefore, the use of chlorine scavengers such as perborate, ammonium sulphate, sodium sulphite or polyethyleneimine at greater than 0.1% by weight of the total composition in the formulation will provide improved detergent enzyme stabilization throughout the wash cycle. sex. Compositions comprising chlorine scavengers are described in European Patent Application 92870018.6 filed 31 January 1992.

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are also suitable herein to provide additional grease removal performance. Such materials are described in WO91/08281 and PCT90/01815, pages 4 et seq., incorporated herein by reference. Chemically, these materials include polyacrylates having one ethoxy side chain per 7-8 acrylate units. The side chain has the formula: -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , where m is 2-3 and n is 6-12. The side chains are attached to the polyacrylate "backbone" by ester linkages, resulting in a "comb" structure type of polymer, the molecular weight of which can vary, but is generally in the range of about 2,000-50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the compositions herein.

dye transfer inhibition

The detergent compositions of the present invention may also include compounds for inhibiting the transfer of dissolved and suspended dyes from one fabric to another encountered during laundering operations involving colored fabrics.

polymeric dye transfer inhibitor

The detergent compositions herein also comprise from 0.001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1%, by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are generally incorporated into cleaning compositions in order to inhibit the transfer of dyes from colored fabrics to fabrics which are simultaneously laundered. These polymers have the ability to complex or adsorb fugitive dyes washed from dyed fabrics before they have a chance to contact other items in the wash.

Particularly suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinyl imidazoles or their mixtures.

The addition of such polymers also enhances the performance of the enzymes of the invention.

a) Polyamine N-oxide polymers

Suitable polyamine N-oxide polymers contain units of the formula:

wherein P is a polymerizable unit to which the RNO group may be attached or wherein the RNO group forms part of the polymerizable unit or a mixture of the two. A is for NC, CO, 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 can be attached or wherein the nitrogen atom of the N-O group is part of the group.

其中R₁、R₂和R₃是脂族基团、芳族、杂环或脂环基团或它们的组合，x或/和y或/和z是0或1，其中N-O基团的氮原子可连接在其上或其中N-O基团的氮原子是这些基团的一部分。The NO group can be represented by the following general structure:

Wherein R ₁ , R ₂ and R ₃ are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z are 0 or 1, wherein the nitrogen of the NO group The nitrogen atom to which the atom may be attached or where the NO group is part of these groups.

The N-O group is part of the polymerizable unit (P) or can be attached to the polymeric backbone or a mixture of both.

Suitable polyamine N-oxides in which the N-O group forms part of the polymerisable unit include polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides includes polyamine N-oxides in which 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 pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of said polyamine N-oxides includes polyamine N-oxides in which the nitrogen atom of the N-O group is attached to the R group.

Other suitable polyamine N-oxides are polyamine N-oxides in which the N—O group is attached to the polymerisable unit.

A preferred class of these polyamine N-oxides are polyamine N-oxides having the general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen atom of the N-O functional group is said part of the R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and their derivatives.

Another preferred class of polyamine N-oxides are polyamine oxides of general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen atom of the N-O functional group is attached to said R on the group.

Examples of these types are polyamine oxides wherein the R group is an aromatic group such as phenyl.

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

The amine N-oxide polymers of the present invention typically have a ratio of amine to amine N-oxide of from 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or by suitable degree of N-oxidation. Preferably the ratio of amine to amine N-oxide is from 2:3 to 1:1000000, more preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present invention actually include random or block copolymers in which one type of monomer is an amine N-oxide and the other type of monomer is an amine N-oxide or not. The amine oxide units in the polyamine N-oxides have a PK _a <10, preferably a PK _a <7, more preferably a PK _a <6.

Polyamine oxides are available in virtually any degree of polymerization. The degree of polymerization is not critical so long as the material has the required water solubility and dye-suspending abilities.

Typically, its average molecular weight is from 500 to 1,000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole N-vinylpyrrolidone polymer used in the present invention has an average molecular weight of 5,000-1,000,000, preferably 5,000-200,000.

Highly preferred polymers for use in the detergent compositions of the present invention include polymers selected from N-vinylimidazole N-vinylpyrrolidone copolymers, wherein said polymers have an average molecular weight of 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.

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

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

N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties without adversely affecting the cleaning performance of formulated detergent compositions.

The N-vinylimidazole N-vinylpyrrolidone copolymer of the present 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 can also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, most preferably from about 5,000 to about 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) were purchased. Other suitable polyvinylpyrrolidones commercially available from the company BASF include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones well known to those skilled in the detergent art (see e.g. EP-A-262,897 and EP-A-256,696) .

d) polyvinyl oxazolidinone

The detergent compositions herein can also employ polyvinyl oxazolidones as polymeric dye transfer inhibiting agents. The polyvinyloxazolidinone has an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, most preferably from about 5,000 to about 15,000.

e) Polyvinyl imidazole

The detergent compositions herein can also employ polyvinylimidazole as a polymeric dye transfer inhibiting agent. The polyvinylimidazole has an average molecular weight of about 2,500 to about 400,000, preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000, most preferably about 5,000 to about 15,000.

f) Cross-linked polymers

A cross-linked polymer is a polymer whose backbone is interconnected to some extent; these linkages can be chemical or physical, and there can be reactive groups on the backbone or on the branches. Cross-linked polymers have been described in Journal of Polymer Science, Vol. 22, pp. 1035-1039.

In one embodiment, the crosslinked polymers are prepared in such a way that they form a three-dimensional rigid structure that is capable of trapping the dye in the pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymer entraps the dye by swelling. Such crosslinked polymers are described in co-pending patent application 94870213.9.

cleaning method

The compositions of the present invention may be used in essentially any washing or cleaning method, including soaking methods, pretreatment methods and methods with a rinse step in which a separate rinse aid composition may be added.

The methods described herein involve contacting the fabrics with a wash solution in the usual manner and as exemplified below.

The method of the invention is suitably carried out during the washing process. The cleaning method is preferably carried out at a temperature of 5°C to 95°C, especially at a temperature of 10°C to 60°C. The pH of the treatment solution is preferably 7 to 12.

The following examples are intended to illustrate the compositions of the present invention and are not intended to limit or otherwise define the scope of the invention.

In detergent compositions, enzyme levels are expressed by weight of pure enzyme based on the total composition, and unless otherwise stated, detergent components are expressed by weight of the total composition. The abbreviated component symbols have the following meanings: LAS: linear C _11-13 sodium alkylbenzene sulfonate TAS: tallow alkyl sodium sulfate CxyAS: C _1x -C _1y alkyl sodium sulfate CxySAS: C _1x -C _1y Secondary (2,3) Sodium Alkyl Sulfate CxyEz: Mainly linear C _1x -C _1y primary alcohols condensed on average z moles of ethylene oxide CxyEzS: C _1x -C _1y alkanes condensed on average z moles of ethylene oxide Sodium Hydroxyl Sulfate QAS: R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄ QAS1 : R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) , R ₂ =C ₈ -C ₁₁ APA: C _8-10 amidopropyl dimethylamine nonionic form: surfactant C with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 ₁₃ - _C15 mixed ethoxylated/propoxylated fatty alcohol Neodol: C14-C15 linear primary alcohol ethoxylate sold by Shell Chemical STS: sodium tosylate CFAA: _C12- C ₁₄ Alkyl N-Methyl Glucamide TFAA: C ₁₆ -C ₁₈ Alkyl N-Methyl Glucamide TPKFA: C ₁₂ -C ₁₄ Topped Whole Fraction Fatty Acid DEQA: Chlorinated Di(Tallow Oxygen Ethyl)dimethylammonium DEQA(2): Di(soft tallow oxyethyl)hydroxyethylmethylammonium methylsulfate DTDMAMS: Ditallowdimethylammonium methylsulfate SDASA: Ratio 1: Stearyldimethylamine of 2: triple pressed stearic acid silicate: Amorphous sodium silicate (SiO ₂ :Na ₂ O ratio = 1.6-3.2) Zeolite A: Formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ 27H ₂ O hydrated sodium aluminosilicate, primary particle size

0.1 to 10 microns (weight expressed on anhydrous basis) NaSKS-6: crystalline layered silicate of formula δ-Na ₂ Si ₂ O ₅ Citrate: trisodium citrate dihydrate, activity 86.4 %, particle size distribution at 425

-850 micron citric acid : Anhydrous citrate borate : Sodium borate carbonate : Anhydrous sodium carbonate bicarbonate with a particle size between 200-900 microns : Anhydrous carbonic acid with a particle size distribution between 400-1200 microns Sodium Hydrogen Sulfate : Anhydrous Sodium Sulfate Magnesium Sulfate : Anhydrous Magnesium Sulfate STPP : Sodium Tripolyphosphate TSPP : Tetrasodium Pyrophosphate MA/AA : 4:1 Acrylate/Maleate Random Copolymer, average molecular weight approx.

                                                                                                                                                           

10000AA: sodium polyacrylate polymer with _an average molecular weight _of 4500 PB1: _anhydrous sodium _perborate monohydrate with nominal formula _NaBO2.H2O2 PB4: sodium _perborate with nominal formula _{NaBO2.3H2OH2O2} Tetrahydrate percarbonate: Anhydrous sodium percarbonate of nominal formula _2Na2CO3 · _{3H2O2 NaDCC} : _Sodium dichloroisocyanurate TAED: Tetraacetylethylenediamine NOBS: Nonane in sodium salt form Acyloxybenzenesulfonate NACA: (6-Nonanoylaminocaproyl)oxybenzenesulfonate OBSDTPA: Diethylenetriaminepentaacetic acid HEDP: 1,1-Hydroxyethanediphosphonic acid DETPMP: available from Monsanto Diethylenetriamine sold under the trade name Dequest 2060

Penta(methylene)phosphonate EDDS: Ethylenediamine-N,N'-disuccinic acid in sodium salt form, (S,S) isomer MnTACN: Manganese 1,4,7-trimethyl-, 1,4,7-Triazacyclononane Photoactivated: Sulfonated Phthalocyanine Zinc Bleach Encapsulated with Dextrin-Soluble Polymer Photoactivated: Sulfonated Phthalocyanine Encapsulated with Dextrin-Soluble Polymer Aluminum phthalocyanine bleach 1 Phospholipase: Phospholipid sold under the tradename ^Lecitase® by Novo Nordisk A/S

Enzyme and/or Phospholipase A2 Glutathione sold by Sigma: Glutathione transferase sold by Sigma under the trade names G6636 and/or G8642 S-transferase acid-thiol linkage: sold by Sigma or Boehringer Mannheim Fatty Acid Acyl Ligase CoA Synthetase and/or Fatty Acid Acyl ACP Synthetase Desaturase: Fatty Acid ACP Desaturase Esterification Compound: Sold by Sigma or Boehringer Mannheim CoA Energy: Sold by Sigma or Boehringer Mannheim ATP for sale

(ATP) electron donor: ferredoxin, NADPH, ferredoxin: NADPH series proteases: produced by Novo Nordisk A/S under the trade names of Savinase, Alcalase,

Durazym and marketed by Gist Brocades under the trade names Maxacal,

Proteolytic enzymes sold by Maxapem, and in patents WO91/06637 and/

or the protease amylase described in WO95/10591 and/or EP251446: described in WO94/18314, WO96/05295 by Genencor

Trade name Purafact Ox Am ^R and marketed by Novo Nordisk A/S under the trade name

Amylolysis sold by ^Termamyl® , ^Fungamyl® and ^Duramyl®

Enzymes, and those amylolytic enzymes lipases described in WO 95/26397: trade names Lipolase, Lipolase by Novo Nordisk A/S

Ultra and Lipomax sold by Gist Brocades under the trade name Lipomax

  Cellulase enzymes: marketed by Novo Nordisk A/S under the trade names Carezyme, Celluzyme

and/or cellulase sold by Endolase 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 : Vinylimidazole and ethylene Copolymer of pyrrolidone, average molecular weight

For 20000 brightener 1: 4,4'-bis(2-sulfostyrene) biphenyl disodium brightener 2: 4,4'-bis(4-phenylamino-6-codelino-1 ,3,5-triazin-2-yl)stilbene

- 2,2'-disodium disulfonate polysiloxane: a mixture of a polydimethylsiloxane foam control agent and a siloxane-oxygen defoamer copolymer as a dispersant, the foam control agent with the weight of the dispersant

The ratio is 10:1-100:1 Foam suppressor: 12% polysiloxane/silicon dioxide, 18% stearyl alcohol, 70% granular starch

    Powder Sunscreens : Water-based monostyrene latex blend by BASF

Aktiengesellschaft sells under the trade name Lytron 621 SRP1 : Anionic group-terminated poly-terminated SRP2 : Diethoxylated poly(1,2-propylene terephthalate) short-block poly

Compound QEA: Di((C ₂ H ₅ O)(C ₂ H ₄ O) _n )(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -(CH ₃ ) di

((C ₂ H ₅ O)-(C ₂ H ₄ O)) _n , wherein n=20-30PEI: polyethyleneimine, the average molecular weight is 1800, and the average ethoxylation degree is

7 ethyleneoxy residues per nitrogen SCS : Sodium cumene sulfonate HMWPEO : High molecular weight polyoxyethylene PEGx : Polyethylene glycol, molecular weight xPEO : Polyoxyethylene, average molecular weight 5000 TEPAE : Tetraethylenepentamine Ethoxylate Example 1

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

II III IV V Vila 8.0 8.0 8.0 2.0 6.0 6.0TAS-0.5-0.5 1.0 0.1C46 (s) AS 2.5------7.0 4.5 5.5C68AS 2.0 7.0--C25E5-3.4 10.0 4.66 4.6C25E7 3.4 3.4 1.0--C25E3S--2.0 5.0 4.5QAS-0.8--qas1--0.8 0.5 1.0 Burle A 18.1 18.0 14.1 18.0 18.1 Citric acid--2.5-2.5 carbonate 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0. 27.0 10.0 10.0 13.0NA-SKS-6--10.0-10.0 Silicate 1.4 1.4 3.0 0.3 0.5 0.3 Citrate-1.0-3.0-Sulfate 26.1 26.1 6.0-Magnestes 0.3-0.2-0.2ma /AA 0.3 0.3 4.0 1.0 1.0cmc 0.2 0.2 0.2 0.2 0.4 0.4pb4 9.0 5.0---18.0 18.0TAed 1.5 0.4 1.5-3.9 4.2naca-OBS--Detpmp 0.25 0.25 0.25 0.25 0.25----0.2-0.2edds-0.25 0.4-0.5 0.5cFaa-1.0-2.0 -Hedp 0.3 0.3 0.3 0.4 0.4QEA--0.2-0.5 phospholipase 0.05 0.001 0.3 0.03 protease 0.009 0.009       0.01      0.04      0.05      0.03淀粉酶          0.002      0.002       0.002     0.006     0.008     0.008纤维素酶        0.0007     -           -         0.0007    0.0007    0.0007脂肪酶          0.006      -           -         0.01      0.01      0.01光活化的        15         15          15        -         20        20漂白剂(ppm)PVNO/PVPVI      -          -           - 0.1-increase agent 1 0.09 0.09 0.09-0.09 0.09 spice 0.3 0.3 0.4 0.4 0.4 0.5 0.5 0.5-0.3 0.3 density grams/liters 850 850 850 mini and a small number of components up to the most up to the maximum number 100% Example 2

The following granular laundry detergent compositions especially suitable for European washing machine conditions were prepared according to the present invention:

II III IV V vid 5.5 7.5 5.0 5.0 6.0 7.0TAS 1.25 1.9-0.8 0.4 0.3C24AS/C25AS-2.2 5.0 5.0 2.25E3S-0.8 1.5 3.0C45E7--3.0TFAA-2.0--C25E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5 -          5.5          -         -         -         -QAS             0.8        -            -         -         -         -QAS1                -         0.7       1.0        0.5      1.0       0.7STPP                19.7      -         -          -        -         -沸石A               -         19.5      25.0       19.5     20.0      17.0NaSKS-6/柠檬酸      -         10.6      -          10.6     -         -(79∶ 21) NA-SKS-6-9.0-10.0 10.0 carbonate 6.1 21.4 9.0 10.0 10.0 18.0 Bxyfndromicar-2.0 7.0 5.0-2.0 silicate 6.8-0.3 0.5-citrate-4.0 4.0-sulfate sulfate Salt 39.8-5.0-12.0 Magnesium sulfate-0.2 0.2 0.2 -ma/AA 0.5 1.6 3.0 4.0 1.0cmc 0.2 0.4 1.0 1.0 0.4 0.4 5.0 12.7---18.0 15.0TAed 0.5 0.5 3.1-5.0 -NACA-OBS 1.0 3.5--2.5DetPMP 0.25 0.3 0.3 0.2Hedp-0.3-0.3 0.3 0.3QEA-1.0 1.0 1.05 0.05 1.05 0.01 0.09 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.053 0.053 0.03 05.053 0.03 0.03 0.05.05.05.0 0.09 0.09 0.09 0.05 0.05 0. 05 0. 05 0. 05-.脂肪酶              0.003     0.003     0.006      0.006    0.006     0.004纤维素酶            0.0006    0.0006    0.0005     0.0005   0.0007    0.0007淀粉酶              0.002     0.002     0.006      0.006    0.01      0.003PVNO/PVPVI          -         -         0.2        0.2      -         -PVP                 0.9       1.3       -          -        -         0.9SRP 1               -         -         0.2        0.2      0.2       -光Activated 15 27-20 20 bleach (PPM) Light activation 15----bleach (2) (PPM) whitening agent 1 0.08 0.2-0.09 0.15 white agent 2-0.04-------------------- Fast 0.3 0.5 0.4 0.3 0.4 0.3 Siliconoxane removal agent 0.5 2.4 0.3 0.5 0.3 2.0 density gram/liter 750 750 750 750 trace and a small number of components up to 100 % Example 3

The following detergent compositions especially suitable for European washing machine conditions were prepared according to the invention:

I II II III III IV Blown powder

LAS 6.0 5.0 11.0 6.0

TAS 2.0 - - - 2.0

Zeolite A 24.0 - - 20.0

STPP - 27.0 24.0 -

Sulfates 4.0 6.0 13.0 -

MA/AA 1.0 4.0 6.0 2.0

Silicate 1.0 7.0 3.0 3.0

CMC 1.0 1.0 0.5 0.6

Brightener 1 0.2 0.2 0.2 0.2

                                                                               towards

DETPMP 0.4 0.4 0.2 0.4

spray on

Whitening agent 0.02 - - 0.02

C45E7 - - - - - 5.0

C45E2 2.5 2.5 2.0 -

C45E3 2.6 2.5 2.0 -

Spices 0.5 0.3 0.5 0.2

Silicone defoamer 0.3 0.3 0.3 - dry additive

QEA - - - - - 1.0

EDDS 0.3 - - -

Sulfate 2.0 3.0 5.0 10.0

Carbonate 6.0 13.0 15.0 14.0

Citric Acid 2.5 - - - 2.0

QAS 1 0.5 - - - 0.5

Na-SKS-6 10.0 - - -

Percarbonate 18.5 - - -

PB4 - 18.0 10.0 21.5

TAED 2.0 2.0 - 2.0

NACA-OBS 3.0 2.0 4.0 -

Phospholipase 0.1 0.3 0.05 0.008

Protease 0.03 0.03 0.03 0.03

                                                          

                                                                         

Brightener 1 0.05 - - - 0.05

Trace and Minor Components Up to 100% Example 4

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

I I II II III III IV IV V V VI Blown powder

LAS 23.0 8.0 7.0 9.0 7.0 7.0

TAS - - - - - - - 1.0 -

C45AS 6.0 6.0 5.0 8.0 - -

C45AES - 1.0 1.0 1.0 -

C45E35 - - - - - - - - 2.0 4.0

Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0

MA/AA - 0.5 - - - - 2.0

MA/AA 1 7.0 - - - - - -

AA - 3.0 3.0 2.0 3.0 3.0

Sulfates 5.0 6.3 14.3 11.0 15.0 19.3

Silicate 10.0 1.0 1.0 1.0 1.0 1.0

Carbonate 15.0 20.0 10.0 20.7 8.0 6.0

PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0

DTPA - 0.9 0.5 - 0.5

Brightener 2 0.3 0.2 0.3 - 0.1 0.3 Spray on

C45E7 - 2.0 - - - 2.0 2.0

C25E9 3.0 - - - - - - - -

C23E9 - - - 1.5 2.0 - 2.0

Fragrance 0.3 0.3 0.3 2.0 0.3 0.3 Agglomerates

C45AS - 5.0 5.0 2.0 - 5.0

LAS - 2.0 2.0 - - - 2.0

Zeolite A - 7.5 7.5 8.0 - 7.5

Carbonate - 4.0 4.0 5.0 - 4.0

PEG 4000 - 0.5 0.5 - - - 0.5 Minor components (water, etc.) - 2.0 2.0 2.0 - 0 Additives 2.0

                                         - 

Citric Acid - - - - - - - 2.0 -

PB4 - - - - - - - 12.0 1.0

PB1 4.0 1.0 3.0 2.0 -

Percarbonate - - - - - - - 2.0 10.0

Carbonate - 5.3 1.8 - 4.0 4.0

NOBS 4.0 - 6.0 - 0.6

Methylcellulose 0.2 - - - - - - - -

Na-SKS-6 8.0 - - - - -

STS - - - 2.0 - 1.0 -

cumenesulfonic acid - 1.0 - - - - 2.0

Phospholipase 0.05 0.1 0.09 0.005 0.05 0.01

Protease 0.02 0.02 0.02 0.01 0.02 0.02

Lipase 0.004 - 0.004 - 0.004 0.008

                                                                                                        

  Cellulase 0.0005 0.0005 0.0005 0.0007 0.0005 0.0005

PVPVI - - - - - - - 0.5 0.1

PVP - - - - - - - 0.5 -

PVNO - - - 0.5 - 0.3 -

QEA - - - - - - - 1.0 -

SRP 1 0.2 0.5 0.3 - 0.2 - Polysiloxane defoamer 0.2 0.4 0.2 0.4 0.1 -

Magnesium Sulfate - - - 0.2 - 0.2 - Trace and Minor Components Up to 100% Example 5

The following bleach-free detergent compositions according to the invention, especially for washing colored clothes, were prepared:

I II II III Blown powder

Zeolite A 15.0 15.0 -

Sulfate - 5.0 -

LAS 3.0 3.0 -

DETPMP 0.4 0.5 -

CMC 0.4 0.4 -

MA/AA 4.0 4.0 - Agglomerates

C45AS - - - - 11.0

LAS 6.0 5.0 -

TAS 3.0 2.0 -

Silicate 4.0 4.0 -

Zeolite A 10.0 15.0 13.0

CMC - - - - 0.5

MA/AA - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2.0

Carbonate 9.0 7.0 7.0

spray on

Spices 0.3 0.3 0.5

C45E7 4.0 4.0 4.0

C25E3 2.0 2.0 2.0 dry additive

MA/AA - - - - 3.0

Na-SKS-6 - - - - 12.0

Citrate 10.0 - 8.0

Bicarbonate 7.0 3.0 5.0

Carbonate 8.0 5.0 7.0

PVPVI/PVNO 0.5 0.5 0.5

Phospholipase 0.05 0.0005 0.3

Protease 0.03 0.02 0.05

                                                        

                                                                           

                                                                                     

    Polysiloxane Defoamer                                                                      

Sulfate-9.0-density (gram/liter) 700 700 700 trace and a small number of components up to 100 % Example 6

The following detergent compositions according to the invention were prepared:

                                                                                                                                                                                                                   ,

Zeolite A 30.0 22.0 24.0 10.0

Sulfate 10.0 5.0 10.0 7.0

MA/AA 3.0 - - -

AA - - 1.6 - 2.0 -

MA/AA 1 - 12.0 - 6.0

LAS 14.0 10.0 9.0 20.0

C45AS 8.0 7.0 9.0 7.0

C45AES - - 1.0 - 1.0 -

Silicate - 1.0 0.5 10.0

Soap - - 2.0 - -

Brightener 1 0.2 0.2 0.2 0.2

Carbonate 6.0 9.0 10.0 10.0

PEG 4000 - 1.0 1.5 -

                                                             

C25E9 - - - - - - 5.0

C45E7 1.0 1.0 - -

C23E9 - - 1.0 - 2.5 -

Fragrances 0.2 0.3 0.3 - Dry Additives

Carbonate 5.0 10.0 18.0 8.0

PVPVI/PVNO 0.5 - - 0.3 -

Phospholipase 0.01 0.3 0.05 0.1

Protease 0.03 0.03 0.03 0.02

Lipase 0.008 - - 0.008

Amylase 0.002 - - 0.002

    Cellulase 0.0002 0.0005 0.0005 0.0002

NOBS - 4.0 - 4.5

PB1 1.0 5.0 1.5 6.0

Sulfate 4.0 5.0 - 5.0

SRP1 - 0.4 -

                                                                                                              

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

I II II III Blown powder

Zeolite A 20.0 - 15.0

                                                                            

Sulfates - - - - 5.0

Carbonate - - - - 5.0

TAS - - - - 1.0

LAS 6.0 6.0 6.0

C68AS 2.0 2.0 -

Silicate 3.0 8.0 -

MA/AA 4.0 2.0 2.0

CMC 0.6 0.6 0.2

Brightener 1 0.2 0.2 0.1

DETPMP 0.4 0.4 0.1

STS - - - - 1.0

spray on

C45E7 5.0 5.0 4.0

                                                                                 

Spices 0.2 0.2 0.3 dry additives

QEA - - - - 1.0

Carbonate 14.0 9.0 10.0

PB1 1.5 2.0 -

PB4 18.5 13.0 13.0

TAED 2.0 2.0 2.0

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 1.0

    Photoactivated Bleach                                                                                                                

Na-SKS-6 - - - - 3.0

Phospholipase 0.01 0.3 0.001

Protease 0.03 0.03 0.007

                                                                         

                                                                                     

                                                                             

Sulfate 10.0 20.0 5.0 density (gram/liter) 700 700 700 trace and a small number of components up to 100 % Example 8

The following detergent compositions according to the invention were prepared:

I II II III Blown powder

Zeolite A 15.0 15.0 15.0

Sulfate - 5.0 -

LAS 3.0 3.0 3.0

                                                                                          

DETPMP 0.4 0.2 0.4

                                                                                                     

CMC 0.4 0.4 0.4

MA/AA 4.0 2.0 2.0 Agglomerates

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0 Spray on

Spices 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C25E3 2.0 - Dry Additive

Citrate 5.0 - 2.0

Bicarbonate - 3.0 -

Carbonate 8.0 15.0 10.0

TAED 6.0 2.0 5.0

PB1 14.0 7.0 10.0

PEO - - - - 0.2

                                               

Phospholipase 0.001 0.05 0.01

Protease 0.03 0.03 0.03

                                                                         

                                                                               

‎

                                                                     

Sulfate-3.0-density (gram/liter) 850 850 850 trace and a small number of components up to 100 % Example 9

The following detergent compositions according to the invention were prepared:

II III IVLAS 18.0 14.0 20.0QAS 0.7 1.0-0.7TFAA-1.0 -C23E56.5-1.0 -C45E7-1.0 -C45E3S 1.0 1.0 -STPP 32.0 18.0 22.0 Silicate 9.0 9.0 8.0 carbonate 11.0 7.5 10.0 5.0 bicarbonate-7.5-PB1 3.0 1.0 -PB4-1.0 -NOBS 2.0 1.0 -Detpmp-1.0 -DTPA 0.5-0.2 0.3SRP 1 0.3 0.1MA/AA 1.5 2.0 0.5cmc 0.8 0.4 0.4 0.2PEI-0.4-Sulfate 20.0 10.0 20.0 30.0 Magnesium sulfate 0.2-0.4 0.9 Phosphorase 0.003 0.03 0.5 1.1 Proteinase 0.03 0.03 0.02 0.008 0.007-0.004 lipoase 0.004-0.002-fibinase 0.003-1 0.0001 Light-activated bleach 30ppm 20ppm 20ppm-10PPM spice 0.3 0.3 0.2 whitening agent 1/2 0.05 0.08 0.1 trace and a small number of components up to 100 % up to 100 %

Example 10

Prepare according to the following liquid detergent formulations of the present invention (content is given by weight, and enzyme is by pure

enzyme expression):

II III IV VLAS 11.5 8.8-3.9 -C25E2.5S-3.0 18.0-16.0C45E2.25S 11.5 3.0-15.7 -C23E9-2.7 1.8 1.0C23E7 3.2--5.2-3.1TPKFA 1.6-2.0 0.5 2.0 2.0 Citric acid (50 %) 6.5 1.2 2.5 4.4 2.5 calcium 0.1 0.06 0.1-0.5 0.06 0.1 0.05 0.05SCS 4.0 1.0 3.0 1.2-Borate 0.6-3.0 2.0 2.9 Sodium hydroxide 1.75 1.75 1.0.0 3.666 4.2 2.91, 2-propylene glycol 3.3 2.0 8.0 7.9 5.3 MSIA 3.0 1.5 1.3 2.5 0.8tepae 1.6-1.3 1.2 1.2 Phosphoridase 0.05 0.1 0.002 1.0 Proteinase 0.03 0.03 0.02 Lipsease-0.002-0.00.--4 4-----------------------------------------------4 4 4 4 4 -Vender enzyme-0.0002 0.0005 0.0001SRP 1 0.2-0.1 -DTPA-0.3 -PVNO-0.3-0.2 White agent 1 0.2 0.07 0.1-polysilicine alkane reducing agent 0.04 0.1 0.1 0.1 micro amount components and water

Example 11

Prepare according to the following liquid detergent formulations of the present invention (content is given by weight, and enzyme is by pure

enzyme expression):

II III IVLAS 10.0 13.0 9.0 -C25AS 4.0 1.0 2.0 10.0C25E3S 1.0-3.0C25E7 6.0 8.0 13.0 2.5TFAA-4.5APA-TPKFA 2.0-13.0 7.0 Citizens 2.0 1.0 1.5 Twelve Carbonat/ Carbonat/ Carbonat/ Fourteen carbonine base amber 12.0 10.0--Caizi fatty acid 4.0 2.0 1.0-ethanol 4.0 4.0 7.0 2.01, 2-propane 4.0 4.0 2.0 7.0 single ethanlamine--5.0-8.0-TEPAE 0.5-0.5 0.2DetPMP 1.0 1.0 1.0 0.5 1.0 phospholidase 0.1 0.05 0.1 0.002 protease 0.02 0.02 0.01 0.008 lipase-0.002-0.002 amylase 0.004 0.01 0.008 cellulose enzyme-0.002 glutathione metastase 0.01 0.01-acids-0.03-0.03-0.03 -0.003 Essence compounds-0.3-0.03 Energy-0.25-0.03 Remoothing Aponerase-0.06 0.05 Supply Electronics System-0.008 0.005SRP 2. 0.3 0.1 Boron 0.1 0.2 1.0 2.0 Calcium oxide — 0.02--1- 0.4--0 0.1 0.3-0.1 Optical agent 0.5 0.4-0.3NAOH up to PH 8.0 8.0 7.6 7.7 trace components and water implementation example 12 Preparation according to the following liquid detergent composition (the content is the weight of the weight given, enzymes are expressed as pure enzymes):

II III IVLAS 250--C25AS-13.0 18.0 15.0C25E3S-2.0 2.0 4.0C25E7-4.0TFAA-6.0 8.0APA 3.0 1.0 -TPKFA-15.0 11.0 Cither Fourteen carbonite base amber 15.0--cauliflower fatty acid 1.0-3.5-ethanol 7.0 2.0 2.01, 2-propylene glycol 6.0 8.0 10.0 13.0 single ethanlamine-9.0tepae-0.3detpmp 2.0 1.2 1.0-phospholidase 1.0 0.5 0.03 0.001 protease 0.08 0.02 0.01 0.02 lipase-0.003 0.003 amylase 0.04 0.01 0.01 0.01 glutathye toastase-0.01-cellulose enzyme-0.004 0.003-sulfolol connecting enzyme 0.03 0.3-ester chemical 0.3 compound 0.3 3.0-Energy 0.3 3.0-Saturase 0.05---supply electronic system 0.005---SRP 2--0.2 0.1 Boron 1.0 1.5 2.5 2.5 Palatom Earth 4.0 4.0-1 0.2 0.3-Foam 0.4 0.4 ---0.8 0.7--NAOH up to PH 8.0 7.5 8.0 8.2 trace components and water implementation example 13

Prepare according to the following liquid detergent composition of the present invention (content is given by weight, and enzyme is by pure

enzyme expression):

IILAS 27.6 18.9C45AS 13.8 5.9C13E8 3.0 3.1 Citic acid 5.4 5.4 5.4 Sodium hydroxide 0.4 3.6 Calcium Pacilitate 0.2 sodium methyl acid-0.5 ethanol 16.5 8.01, 2-propylexol 5.9 5.5 dhabenzine sulfonic acid 1.5 0.8 protease 0.05 0.02 phospholipase 0.1 0.01peg-0.7 white agent 2 0.4 0.1 spice 0.5 0.3 trace components and water implementation example 14

The following granular fabric detergent compositions with softening capabilities throughout the wash were prepared according to the present invention:

IIC45AS-10.0LAS 7.6 -C68AS 1.3 -C45E7 4.0-C25E3-5.0 Coconut methaxyl hydroxyl hydroxylceamium chloride 1.4 1.0 citrate 5.0 3.0NA-SKS-6-11.0 Biite A 15.0ma/AAA/AA 4.0 4.0DetPMP 0.4 0.4pb1 15.0-Passive carbonate-15.0taed 5.0 5.0 green soil 10.0hmwpeo-0.1 phospholipidase 0.001 protease 0.02 0.01 lipase 0.03 0.005 fiberase 0.001-silicone 3.0 5.0 carbon carbon Acid salt 10.0 10.0 foaming agent 1.0 4.0cmc 0.2 0.1 water/small number of components up to 100 % Example 15

The following rinse-in fabric softener compositions were prepared according to the present invention: DEQA(2) 20.0 Phospholipase 0.05 Cellulase 0.001 HCL 0.03 Antifoam 0.01 Blue Dye 25 ppm CaCl _0.20 Fragrance 0.90 Microingredients and Water up to 100 % Example 16

The following fabric softener and dryer added fabric conditioner compositions according to the present invention were prepared:

II III IV VDEQA 2.6 19.0--DEQA (2)---51.8dtmams-26.0 -SDASA-70.0 40.2IV = 0 Harm acid 0.3----Neodol 45-13.0 13.0 --0.02 0.02----1.0-phospholipase 0.1 0.001 0.05 0.5 spice 1.0 1.0 0.75 1.5 glycopers S-20--15.4 Glycerin Monatotharine Crystal-0.38-polysilicine oxide bubble agent 0.01 0.01--electrolyte-0.---3.0-dye 10PPM 25PPM 0.01-water and a small number of components 100 % 100 %--- Example 17

Prepare according to the following laundry bar detergent composition of the present invention (content is given by weight, and enzyme is by pure

enzyme expression):

II III VI VI Vi Vi VLAS-19.0 15.0 21.0 6.75 8.8 -C28AS 30.5--15.75 11.2 22.5 May Cinnamin 2.5 9.0-----1.25 1.25 1.25 carbonate 20.0 20.0 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 calcium carbonate 27.5 39.0 35.0-40.0-40.0 Sulfate 5.0 5.0 3.0 3.0 3.0-5.0TSPP 5.0-5.0 -Stpp 5.0 10.0-7.0 8.0 10.0-10.0--10.0---- 10.0-- 5.0--DETPMP-0.7 0.6 0.7 0.7 0.7 0.7cmc-1.0 1.0 1.0 1.0-1.0 talc-10.0 15.0 10.0--silicate-4.0 5.0 3.0--PVNO 0.03 — 0.02- 0.02- -MA/AA 0.0-0.2 0.4 0.5 0.4sRP 1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.01 0.05 0.001 0.03. 0009 0.05 0.01 amylase-0.01-0.002-0.004-0.003 0.003- -0.003 lipase-0.002-0.002----cellulose enzyme-.0003-.0003 .0002 -PEO-0.2 — 0.2 0.3-0.3 spice 1.0 0.5 0.3 0.2 0.4-0.4 magnesium-3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0---0.15 0.1 0.15---0.1 Light activated-15.0 15.0 15.0-15.0 bleach (PPM) Entrobets 18 Preparation based on the liquid hard surface cleaning composition according to the following invention:

I II III Phospholipase 0.1 0.005 0.03 Amylase 0.01 0.002 0.005 Protease 0.05 0.01 0.02EDTA ^* 0.05 0.05 0.05 Citrate 2.9 2.9 2.9 LAS 0.5 0.5 0.5C12AS Sulfate 0.5 5C10 Salt20.5(Ethoxy)3 E6.5 Nonionic Surfactant 7.0 7.0 7.0 Fragrance 1.0 1.0 1.0 Hexyl Carbitol ^** 1.0 1.0 1.0SCS 1.3 1.3 1.3 Water Balance to 100% ^* Tetrasodium ethylenediamine diacetate ^** Diethylene glycol monohexyl Ether ^*** All formulations are adjusted to pH 7-12. Example 19

Prepare the following spray-on composition for cleaning hard surfaces and removing household mildew according to the present invention: Phospholipase 0.08 Amylase 0.01 Protease 0.01 Sodium Octyl Sulfate 2.0 Sodium Lauryl Sulfate 4.0 Sodium Hydroxide 0.8 Silicate 0.04 Butyl Carbitol ^* 4.0 Fragrance 0.35 Water/minor components up to 100% ^* Diethylene glycol monobutyl ether

Claims (12)

Claims 1. A laundry or hard surface cleaner detergent composition comprising a phospholipase. 2. A detergent composition according to claim 1, wherein the phospholipase is selected from EC 3.1.1.4 phospholipase A2, EC 3.1.1.5 lysophospholipase and/or mixtures thereof. 3. The detergent composition according to claim 1-2, wherein said phospholipase is present in an amount of 0.0001%-2%, preferably 0.001%-1%, more preferably 0.05%-0.5% by weight of the total composition % pure enzyme. 4. A detergent composition according to any preceding claim, further comprising an anionic surfactant. 5. A detergent composition according to any preceding claim, further comprising a dispersant. 6. A detergent composition according to any preceding claim, further comprising another detergent enzyme, preferably selected from the group consisting of lipase, amylase, protease, enzymes that increase the water solubility of stains/soils containing saturated fatty acids, and / or mixtures thereof. 7. A detergent composition according to claim 6, wherein said enzyme increasing the water solubility of stains/soils containing saturated fatty acids is selected from the group consisting of acid-thiol ligase, desaturase, glutathione S-transferase and / or mixtures thereof. 8. A detergent composition according to any preceding claim, wherein the phospholipase is alkaline. 9. A detergent additive comprising a phospholipase. 10. A fabric softening composition comprising a phospholipase and a cationic surfactant comprising two long chains. 11. Use of a phospholipase in a laundry detergent composition for cleaning fabrics and/or removing fabric stains and/or maintaining fabric whiteness and/or soft texture and/or fabric color appearance and/or inhibiting fabric dye transfer. 12. Use of a phospholipase in a hard surface cleaner detergent composition for cleaning hard surfaces such as floors, walls, bathroom tiles and the like.