MX2007010725A - Detergent compositions. - Google Patents

Abstract

Detergent compositions containing high efficiency lipase enzymes and specific detergent formulations comprising a high reserve alkalinity, greater than 6.5, and a bleaching agent comprising hydrogen peroxide source and peracid or precursor thereof such that the Avox to peracid ratio is 1:1 to 35:1, enables control of diacyl peroxide formation. Preferred formulations comprise surfactants selected from alkyl benzene sulphonates in combination with alky ethoxylated sulfates or MES or non-ionic surfactants.

Description

DETERGENT COMPOSITIONS TECHNICAL FIELD The present invention relates to detergent compositions, particularly laundry detergents, and in particular detergents comprising lipolytic enzymes or lipases.

BACKGROUND OF THE INVENTION Many detergent compositions comprise bleach systems to help remove stains from washed items. These bleach systems commonly comprise a source of hydrogen peroxide, such as perborate or percarbonate. The performance of hydrogen peroxide bleaches is often improved with the use of a perishable precursor or a peracid precursor (often referred to as a bleach activator) in addition to hydrogen peroxide (or oxygen source). In use, the bleach activator reacts with an excess of hydrogen peroxide to form a peracid whitening species. Typical laundry formulations use a source of excess hydrogen peroxide. The most common bleach activator is TAED (tetraacetylethylenediamine), and the active whitening species that is formed reacting with hydrogen peroxide is peracetic acid. Other activators result in a bleaching species that has a longer carbon chain and are hydrophobic. These are desirable to produce efficient bleaching, especially in oily stains. A well-known example of these hydrophobic bleach activators is nonanoyloxybenzene sulfonate (NOBS). This bleach activator reacts to form a reactive pemonanoic acid bleaching species. However, it has been discovered that this bleaching species will react with the bleach activator itself to form a C9 diacyl peroxide; in the same way, other hydrophobic bleach activators react to form their corresponding diacyl peroxides. These species are strong whitening species and are useful in the washing process, but they are insoluble. In some types of washers, these compounds may tend to settle in the washing machine's discharge line, as the wash water drains out of the washer. In this way, strong bleaching agents can artificially concentrate in these areas and it has been proven that this can cause damage in some types of washers, in areas where the material used is vulnerable to high levels of bleach, such as drainage lines. polymer or rubber. The problem addressed by this invention is how to alleviate this problem, so that the benefits of hydrophobic bleaches can be achieved while, at the same time, minimizing or avoiding damage to the washing equipment.

Lipase enzymes have been used in detergents since the late 1980s to eliminate fat stains by breaking down these stains into triglycerides. Until relatively recently, the commercially available major lipase enzymes, such as Lipolase (trade name of Novozymes), acted particularly effectively at the lower moisture levels of the drying phase of the washing process. These enzymes tended to produce considerable cleaning only in the second wash step, since the active site of the enzyme was occupied by water during the washing process, so that the decomposition of the fat was significant only in the spots that remained in the clothes washed during the drying step, and the decomposed fats were then removed in the next washing step. However, more recently lipases of higher efficiency have also been developed which also act effectively during the washing phase of the cleaning process, so that in addition to the cleaning of the second washing step, a considerable improvement in the cleaning effect was found of the first wash cycle due to the enzyme lípasa. Examples of such enzymes are described in patent WO00 / 60063 and research description IP6553D. Reference is made to such enzymes below as first wash washes. Examples of such enzymes include certain variants of Lipolase (wild Humicola lanuginosa) which must comprise one or more substitutions with positive amino acids near the N-terminal in the three-dimensional structure. The variants should further comprise an addition of peptides at the C-terminus or they must satisfy certain limitations of electrically charged amino acids at positions 90-101 and 210. The inventors of the present have discovered that using a combination of these enzymes from the first wash with a specific type of detergent formulation, allows the use of these bleach activators. hydrophobic to achieve good stain removal, while reducing any of the disadvantages discussed above.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention, there is provided a detergent composition comprising a source of hydrogen peroxide, a hydrophobic peracid or a precursor thereof having the formula R- (C = O) -L where R is an alkyl group having 6 to 14, preferably 8 to 12 carbon atoms, and L is a leaving group, and a lipase enzyme which is a polypeptide having an amino acid sequence that: (a) has at least 90% identity with the Wild lipase derived from strain DSM 4109 of Humicola lanuginosa; (b) compared to said wild-type lipase, it comprises a substitution of an electrically neutral or negatively charged amino acid on the surface of the three-dimensional structure within 15 Á of E1 or Q249 with a positively charged amino acid; and (c) comprises an addition of peptides at the C-terminus; or (d) comprises an addition of peptides at the N-terminus or (e) satisfies the following limitations: i) comprises a negative amino acid at the E210 position of said wild type; i) comprises an amino acid negatively charged in the region corresponding to positions 90-101 of said wild-type lipase; and iii) comprises a neutral or negative amino acid in a position corresponding to N94 of said wild-type lipase or has a negative or neutral electrical charge in the region corresponding to positions 90-101 of said wild-type lipase; the detergent composition has an alkalinity reserve greater than 6.5, the amount of the oxygen source and the peracid being such as to provide the detergent composition with a molar ratio of available oxygen (from the peroxide source): peracid from 1: 1 to 35: 1. In accordance with the present invention, there is also provided a detergent composition comprising a source of hydrogen peroxide, a hydrophobic bleach activator having the formula R- (C = O) -L, wherein R is an alkyl group having 6 to 14, preferably 8 to 12 carbon atoms, and L is a leaving group, a lipase enzyme produces a first washing grease removal performance better than that produced by the WT Lipolase enzyme (trademark of Novozymes), using the first fat wash test described below, and the detergent composition has an alkalinity reserve greater than 6.5, the amount of the oxygen source and the percylate being such that it provides the detergent composition with a molar ratio of oxygen available (from the peroxide source): peracid from 1: 1 to 35: 1. The WT Lipolase enzyme from Novozymes is described in U.S. Pat. no. 5,869,438, sec. no. 2.

The inventors of the present have discovered that when a first wash lipase is used in a detergent composition together with a high reserve of alkalinity and with a molar ratio of available oxygen (from the peroxide source): the peracid from 1: 1 to 35: 1, the diacyl peroxide formation is controlled so that the disadvantages of this type of hydrophobic peracid or peracid precursor are alleviated. In a preferred aspect of the invention, the detergent compositions of the invention comprise less than 15% by weight of additives selected from aluminosilicate additive (zeolite) or phosphate additive. In another preferred aspect of the invention, the compositions comprise less than 10% by weight of zeolite or phosphate additive, or even less than 5% by weight or 4% by weight of zeolite or phosphate additive.

DETAILED DESCRIPTION OF THE INVENTION Peroxide source Inorganic perhydrate salts are a preferred source of peroxide. Preferably, these salts are present at a level of 0.05 to 40% by weight, more preferably 1 to 30% by weight based on the detergent composition, or 2 to 20% by weight. Examples of inorganic salts of perborate include the perborate, percarbonate, persulfate, perfosphate and persilorate salts. Perborate, usually the monohydrate or tetrahydrate, or more particularly the percarbonate salts, are the most preferred. Usually, these are the alkali metal salts, preferably the sodium salts. The inorganic salts of perborate are usually incorporated in the detergent compositions of the invention as a crystalline solid, which can optionally be coated to achieve better storage stability. Suitable coatings comprise the inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof; or organic materials, such as waxes, oil or fatty soaps.

Hydrophobic peracid or peracid precursor Suitable compounds include compounds of the formula R- (C = O) OOM or R- (C = O) -L wherein R is an alkyl group, optionally branched, having from 6 to 14 carbon atoms, more preferably from 8 to 12 carbon atoms; M is a counter ion, preferably sodium, potassium or hydrogen; and L is a leaving group. Preferred leaving groups are benzoic acid and derivatives thereof, in particular benzene sulfonate. Suitable examples include decanoyloxybenzoic acid or its salts, the sodium or potassium salts of dodecanoyl benzene sulfonate, decanoyl oxybenzene sulfonate, 3,5,5-trimethyl hexanoyl oxybenzenesulfonate, or even more preferred nonanoyl oxobenzene sulfonate (NOBS). The peracid or peracid precursor is generally present in the composition in an amount of 0.5 to 10% by weight, preferably of 0. 5 to 5% by weight, preferably from 0.5 to 4%, by weight based on the detergent composition. Optionally, in addition to the hydrophobic percidate or peracid precursor, a peracid or hydrophilic peracid precursor may also be incorporated into the detergent compositions of the invention. These include materials of the formulas presented above for the hydrophobic peracids / precursors, but the R group comprises less than 6 carbon atoms, preferably less than 4. A preferred example is TAED. If present, it will generally be present in amounts of no greater than 7% by weight, generally in amounts of 0.1 to 5% by weight. The amounts of the hydrogen peroxide source and the peracid or peracid precursor are selected such that the molar ratio of available oxygen (from the peroxide source) to peracid is from 1: 1 to 35: 1. Preferred molar ratios are from 2: 1 to 10: 1, or even 3: 1 or even 5: 1 to 8: 1. Enzyme lipase The reference lipase used in this invention is the wild type lipase derived from strain DSM 4109 of Humicola lanuginosa. This is described in European patents EP258068 and EP305216 and has the amino acid sequence shown at positions 1-269 of SEC. with ID no. 2 of U.S. Pat. no. 5,869,438 (appended hereto). In this specification, the reference lipase is also known as Lipolase.

Substitution with positive amino acid The lipase of the invention comprises one or more (for example, 2-4, in particular two) substitutions of an electrically neutral or negatively charged amino acid near E1 or Q249 with a positively charged amino acid, preferably R. Substitution is found on the surface of the three-dimensional structure within 15 Á of E1 or Q249, for example, in any of positions 1-11, 90, 95, 169, 171-175, 192-211, 213-226, 228 -258, 260-262. The substitution can be found within 10 A of E1 or Q249, for example, in any of positions 1-7, 10, 175, 195, 197-202, 204-206, 209, 215, 219-224, 230-239 , 242-254. The substitution can be found within 15 A of E1, for example, in any of positions 1-11, 169, 171, 192-199, 217-225, 228-240, 243-247, 249, 261-262. The substitution is most preferably within 10 A of E1, for example, in any of positions 1-7, 10, 219-224 and 230-239. In this manner, some preferred substitutions are S3R, S224R, P229R, T231R, N233R, D234R and T244R.

Addition of peptides at the C-terminus The lipase may comprise an addition of peptides attached to the C-terminus L269. The addition of peptides improves the performance of the first wash in a variety of detergents. The addition of peptides preferably consists of 1-5 amino acids, for example, 2, 3 or 4 amino acids. The amino acids of the peptide addition will be listed 270, 271, etc. The peptide addition can consist of electrically neutral amino acids (eg hydrophobic), eg, PGL or PG. In an alternative embodiment, the addition of hydrophobic lipase peptides) and amino acid C, and lipase consists of a substitution of an amino acid with C at a suitable site to form a disulfide bridge with the C of the addition of peptides. Examples are: 270C bound to G23C or T37C 271C bound to K24C, T37C, N26C or R81 C 272C bound to D27C, T35C, E56C, T64C or R81 C.

Amino Acids in Positions 90-101 and 210 The lipase used in the invention preferably satisfies certain limitations in the electrically charged amino acids at positions 90-101 and 210. In this manner, amino acid 210 can be negative. E210 may be unchanged or may have the E210D / C / Y substitution, in particular E210D.

The lipase may comprise a negatively charged amino acid in any of positions 90-101 (in particular 94-101), for example, in position D96 or E99. In addition, the lipase may comprise a neutral or negative amino acid at the N94 position, ie, N94 (neutral or negative), for example, N94N / D / E. In addition, the lipase can have a negative or neutral net electric charge in the region 90-101 (in particular 94-101), ie, the number of negative amino acids is equal to or greater than the number of positive amino acids. In this way, the region can remain unchanged from Lipolase, having two negative amino acids (D96 and E99) and one positive (K98), and having a neutral amino acid at position 94 (N94), or the region can be modified by one or more substitutions. Alternatively, two of the three amino acids N94, N96 and E99 may have a negative or unchanged electrical charge. In this way, the three amino acids may be unchanged or they may be changed by a conservative or negative substitution, ie, N94 (neutral or negative), D (negative) and E99 (negative). The examples are N94D / E and D96E. In addition, one of the three can be replaced to increase the electric charge, that is, N94 (positive), D96 (neutral or positive) or E99 (neutral or positive). Examples are N94K / R, D96I / L / N / S / W or E99N / Q / K / R / H. As discussed in WO00 / 60063, replacement of a neutral amino acid with a negative one (N94D / E) can improve the yield in an anionic detergent. Substitution of a neutral amino acid with a positive amino acid (N94K / R) can provide a variant lipase in good yield, both in an anionic detergent and in an anionic / nonionic detergent (a detergent with eg 40-70% anionic total surfactant). A substitution of Q249R / K / H or a substitution of R209 with a neutral or negative amino acid (for example, R209P / S) may be useful. Optionally, the lipase may comprise the G91A substitution. Optionally, the lipase may comprise substitutions of one or more additional amino acids. These substitutions can be made, for example, in accordance with principles known in the industry, for example, the substitutions described in patents WO92 / 05249, WO94 / 25577, WO95 / 22615, WO97 / 04079 and WO97 / 07202. Specific examples of suitable combinations of substitutions are presented in the bridge pages of tables 4 and 5 of WO00 / 60063. The nomenclature for amino acid modifications is as described in patent WO00 / 60063. Preferred lipase enzymes are described in WO00 / 60063, with Lipex (registered trade name of Novozymes), a variant of Humicola lanuginosa (Thermomyces lanuginosus) (Lipolase, registered trade name of Novozymes) with the T231 mutations being the most preferred. R and N233R. The enzyme lipase incorporated in the detergent compositions of the present invention is generally present in a amount of 10 to 20,000 LU / g of the detergent composition, or even of 100 to 10,000 LU / g. The LU unit for the activity of the lipase is defined in patent WO99 / 42566. The dosage of the lipase in the wash solution is generally 0.01 to 5 mg / L of active lipase protein, more generally 0.1 to 2 mg / L as protein enzyme. The enzyme lipase can be incorporated into the detergent composition in any suitable manner, usually in the form of a non-dusty granulated material, a stabilized liquid or a protected enzyme particle, for example, coated.

First Litter Wash Test It can be determined if any specific lipase enzyme provides better performance in the lard removal in the first wash than WT Lipolase (from Novozymes, described in U.S. Patent No. 5,869,438 , sequence number 2), comparing the performance results of WT Lipolase with the results of the performance of the specific enzyme lipase according to the following test: The washing performance of the lipolytic enzymes is tested in a wash cycle test carried out in a meter of the degree of cleanliness (Terg-O-Tometer or TOM) regulated with thermostat followed by laying in rope for drying. The conditions of the experiment are the following: Washing liquor: 1000 mL per glass Fabric samples: 7 flat cotton cloth samples (9X9 cm) (supplied by Warwick-Equest) per glass Stain: Pork lard colored red with Sudan red dye (Sígma) (0J5 mg of Sudan red / g of lard). 50 μL of pork lard / Sudan red heated at 70 ° C in the center of each cloth sample is applied. After the application of the stain, the fabric samples are heated in an oven at 75 ° C for 25 minutes and this is stored overnight at room temperature. Water to prepare the wash liquor: 3.2 mM of Ca 27Mg2 + (in a ratio of 5: 1) Detergent: 5 g / L of the detergent composition A.

Detergent composition A: 0.300 g / L alkyl sulfate (AS; C14.16) 0.650 g / L ethoxylated alcohol (AEO; C12.14, 6EO) 1,750 g / L zeolite P 0.145 g / L Na2C03 0.020 g / L Sokalan CP5 (BASF) 0.050 g / L CMC (carboxymethylcellulose) 5 g / L of the detergent composition A are mixed in deionized water with added hardness (3.2 mM Ca27Mg2 + (5: 1)) and the pH is artificially adjusted to a pH of 10.2 adding NaOH. The enzyme lipase is added.

Lipolytic enzyme concentration: 0 and 12500 LU / I Washing time: 20 minutes Washing temperature: 30 ° C Rinsing: 15 minutes in tap tap water Drying: overnight at ambient conditions (around 20 ° C, 30 -. 30 -40% RH). Evaluation: Reflectance was measured at 460 nm. The percentage of lard removed is determined as: Delta reflectance (dR) defined as: (R (Fabric samples washed in lipase detergent) -R (Fabric samples washed in non-lipase detergent) The reflectance (which can also be referred to as remission) is measured in an EIrepho 2000 Datacolor device that illuminates the sample with 2 xenon flash lamps and measures the amount of reflected light so that what is totally white corresponds to a reflectance of 100% and what is totally black corresponds to a reflectance of 0%. When comparing the results of the lard removal by the presence of the enzyme, the lipase enzymes that provide better performance than WT Lipolase ™ are suitable for use in the compositions of the present invention.

Reserve alkalinity As used herein, the term "reserve alkalinity" is a measure of the buffering capacity of the detergent composition (g / NaOH / 100 g of detergent composition) determined by titrating a 1% solution (p / p) of detergent composition with hydrochloric acid at a pH of 7.5, that is, for the purpose of calculating the reserve alkalinity as defined herein: Reserve alkalinity (at a pH of 7.5) as alkaline% in NaOH / 100 g of product = T x M x 40 x Vol 10 x Weight x aliquot T = title (mL) at a pH of 7.5 M = Molarity of HCl = 0.2 40 = Molecular weight of NaOH Vol = Total volume (ie 1000 mL) W = Product weight (10 g) Aliquot = (100 mL) A 10 g sample is obtained, weighed to an accuracy of two decimal places, of a fully formulated detergent composition. The sample must be obtained using a Pascal sampler in a powder cabinet. Place the 10 g sample in a plastic cup and add 200 mL of deionized water free of carbon dioxide. Stir using a magnetic stirrer on a stir plate at 15.7 rad / sec (150 rpm) until completely dissolved and for at least 15 minutes.

The contents of the beaker are transferred to a one-liter volumetric flask and brought to a liter with deionized water. Mix well and take an aliquot of 100 ml ± 1 ml using a 100 ml pipette immediately. The pH and temperature of the sample are measured and recorded using a pH meter that can read up to ± 0.01 pH units, with stirring, making sure that the temperature is 21 ° C +/- 2 ° C. Titrate while stirring with 0.2M hydrochloric acid until the pH measures exactly 7.5. The used milliliters of hydrochloric acid are recorded. The average title of three identical repetitions is taken. The calculation described above is carried out to calculate the reserve alkalinity (RA) at a pH of 7.5. The RA of the detergent compositions of the invention will be greater than 6.5 and preferably greater than 7.5. The RA will be greater than 8 or even greater than 9.5 or greater. The RA can be up to 20 or higher. Adequate reserve alkalinity may be provided, for example, through one or more alkali metal silicates (excluding crystalline layered silicate), usually amorphous silicate salts, generally in a sodium-alkali metal salt ratio of 1.2 to 2.2. , usually sodium carbonate, bicarbonate or sesquicarbonate. STPP and persalts such as perborates and percarbonates also contribute to alkalinity. Damping is necessary to maintain an alkaline pH during the washing process to counteract the acidity of the dirt, particularly the fatty acids released by the enzyme lipase.

The detergent composition preferably comprises from 0% by weight to 50% by weight of silicate salt, more generally from 5 to 30% by weight of silicate salt or from 7 to 20% by weight of silicate salt, usually sodium silicate. To provide the desired reserve alkalinity, the detergent compositions of the invention may comprise a carbonate salt, generally from 1% by weight to 70% by weight or from 5% by weight to 50% by weight or from 10% by weight to 30% by weight. % by weight, carbonate salt. The preferred carbonate salts are sodium carbonate or sodium bicarbonate or sodium sesquicarbonate. The carbonate salt can be incorporated in whole or in part in the detergent composition by means of a mixed salt, such as burkeite. A very preferred carbonate salt is sodium carbonate. Preferably, the composition may comprise 5% by weight to 50% by weight of sodium carbonate or from 10 to 40% by weight or even from 15 to 35% by weight of sodium carbonate. It may also be desirable for the composition to comprise from 1% by weight to 20% by weight of sodium bicarbonate or even from 2 to 10 or 8% by weight. If it comprises zeolite, it may be desirable that the weight ratio of sodium carbonate or sodium silicate to the zeolite additive be at least 5: 1, preferably at least 10: 1 or at least 15: 1 or at least 20: 1 or even at least 25: 1 The carbonate salt, or at least part of it, is usually in particulate form, generally with a weighted average particle size in the range of 200 to 500 micrometers However, it you may prefer that the carbonate salt or at least part of it be in particulate and micronized form, which normally has a weighted average particle size within the range of 4 to 40 microns. This is especially preferred when the carbonate salt, or at least part thereof, is in the form of a coparticulate mixture with a detergent surfactant, such as an alkoxylated anionic detergent surfactant. In order to provide the required reserve alkalinity, preferably the levels of carbonate or silicate salts, generally sodium carbonate and sodium silicate, will be from 10 to 70% by weight or from 10 or even from 15 to 50% by weight , based on the total weight of the composition.

Additives According to the present invention, preferably the amount of strong additive selected from the phosphate or zeolite additive is less than 15% by weight, based on the total weight of the detergent composition, preferably below 10% by weight, or even below 8 or 5 or 4 or 3 or 2% by weight. In another preferred aspect of the invention, the total level of weak additives selected from layered silicate (SKS-6), citric acid, citrate salts and nitrilotriacetic acid or its salts, is below 15% by weight, more preferably below 8% by weight, more preferably below 4% by weight or even below 3 or 2% by weight, based on the total weight of the detergent composition. Normally, the level of each of the stratified silicate salt layers, citric acid, citrate salts and nitrilotriacetic acid or salts thereof will be below 10% by weight or even below 5% by weight, based on the total weight of the composition.

Surfactant A particularly preferred auxiliary component of the compositions of the invention is a surfactant. Preferably, the detergent composition comprises one or more surfactants. Generally, the detergent composition comprises (by weight of the composition) from 0% to 50%, preferably 5% and more preferably 10 or even 15% by weight to 40% or 30% or 20% of one or more surfactants. Preferred surfactants are anionic, nonionic, cationic, zwitterionic, amphoteric, and mixtures thereof.

Anionic Surfactants Suitable anionic surfactants generally comprise one or more entities selected from the group comprising carbonate, phosphate, phosphonate, sulfate, sulfonate, carboxylate and mixtures thereof. The anionic surfactant may be one or mixtures of more than one of C8.18 alkyl sulphates and C8-18 alkyl sulfonates. The anionic surfactants incorporated alone or in mixtures in the compositions of the present invention are also C8.18 alkyl sulphates or C8.18 alkylsulfonates, optionally condensed with 1 to 9 moles of alkylene oxide by mol C8.18 alkyl sulfate or C8.18 alkylsulfonate. The alkyl chain of C8.18 alkyl sulphates or C8.18 alkyl sulfonates may be linear or branched; Preferred branched alkyl chains comprise one or more branched portions which are C1-6 alkyl groups. More specifically, suitable anionic surfactants include the C10-C20 branched chain, straight chain and random chain primary alkyl sulfates (AS), which usually have the following formula: CH3 (CH) xCH2-OSO3- M + wherein, M is hydrogen or a cation that provides a charge neutrality, the preferred cations are the sodium and ammonium cations, wherein x is an integer of at least 7, preferably at least 9; C10-C18 secondary alkyl sulfates (2,3), which usually have the following formulas: wherein, M is hydrogen or a cation that provides charge neutrality, cations that include sodium and ammonium cations are preferred, wherein x is an integer of at least 7, preferably at least 9, and is an integer of at least 8, preferably at least 9; C10-C18 alkyl alkoxy carboxylates; branched half chain alkyl sulfates, as described in more detail in US patents num. 6,020,303 and 6,060,443; modified alkylbenzene sulfonate (MLAS) as described in more detail in the patents WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548 and mixtures thereof. Preferred anionic surfactants are alkylbenzene sulfates of C8.18 or alkylbenzene sulfonates of C8.18. The alkyl chain of sulfates alkylbenzene sulfates of C8.18 or alkylbenzene sulphonates of C8.18 may be linear or branched; preferred branched alkyl chains comprise one or more branched entities which are C alkyl groups, ^. Other preferred anionic surfactants are selected from the group comprising: C8.18 alkenyl sulfates, C8.18 alkenyl sulfonates, C8.18 alkenyl benzene sulphates, C8.18 alkenyl benzene sulphonates, C8.18 alkyl dimethylbenzene sulfate, C8.18 alkyl dimethylbenzene sulfonate. .18, fatty acid ester sulfonates, dialkyl sulfosuccinates, and combinations thereof. Other anionic surfactants useful herein include esters of alpha-sulfonate fatty acids, which typically contain from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; 2-acyloxy-alkane-1-sulfonic acid and its salts, which typically contain from about 2 to 9 carbon atoms in the acyl group and from about 9 to 23 carbon atoms in the alkane portion; Alpha-olefin sulfonates (AOS), which typically contain from about 12 to 24 carbon atoms; and beta alkoxy alkane sulfonates, which typically contain from about 1 to 3 carbon atoms in the alkyl group and of about 8 to 20 carbon atoms in the alkane portion. Also useful are the sulfonation products of fatty acid esters containing an alkyl group generally of 10 to 20 carbon atoms. Those of CM are preferred, most preferably methyl ester sulfonates. Methyl ester sulfonates (MES) of C16.18 are preferred. The anionic surfactants may be in salt form. For example, the anionic surfactant (s) may be an alkali metal salt of any of the foregoing. The preferred alkali metals are sodium, potassium and mixtures thereof. The preferred anionic detergent surfactants are selected from the group comprising: linear or branched, substituted or unsubstituted alkyl sulfates of C12.18; linear or branched, substituted or unsubstituted alkyl benzene sulphonates of C10.13, preferably linear alkylbenzenesulfonates of C10.13; and mixtures of them. Even more preferred are linear C10.13 alkylbenzene sulphonates. Even with the utmost preference are linear alkyl benzene sulphonates of C10.13 which are preferably obtained by the sulfonation of commercially available linear alkylbenzenes (LAB); Suitable LABs include low 2-phenyl LAB, such as those supplied by Sasol under the trade name Isochem® or those supplied by Petresa under the trade name Petrelab®, other suitable LABs, the high 2-phenyl LAB, such as those supplied by Sasol under the trade name Hyblene®.

It may be preferred that the anionic detergent surfactant be structurally modified in such a way that it causes the anionic detergent surfactant to be more calcium tolerant and that it is likely to precipitate less of the wash liquor in the presence of free calcium ions. This structural modification could be the introduction of a methyl or ethyl entity near the head group of the anionic detergent surfactant, since this can lead to an anionic detergent surfactant more tolerant to calcium due to the steric hindrance of the head group, which can reduce the affinity of the anionic detergent surfactant to form complexes with the free calcium cations in such a way that precipitation is caused outside the solution. Other structural modifications include the introduction of functional portions, such as an amine moiety, into the alkyl chain of the anionic detergent surfactant; this can lead to an anionic detergent surfactant more tolerant to calcium, because the presence of a functional group in the alkyl chain of an anionic detergent surfactant can minimize the undesirable physiochemical property of the anionic detergent surfactant to form a smooth crystalline structure in the presence of Free calcium ions in the wash solution. This may reduce the tendency of the anionic detergent surfactant to precipitate out of the solution.

Anionic Alkoxylated Surfactants The composition may comprise an alkoxylated anionic surfactant. When said surfactant is present, its concentration generally ranges from 0.1% by weight to 40% by weight, generally from 0.1 by weight to 10% by weight, based on the total detergent composition. It may be preferred that the composition comprises from 3% to 5% by weight of alkoxylated anionic detergent surfactant, or it may be preferred that the composition comprises from 1% to 3% by weight of alkoxylated anionic detergent surfactant. Preferably, the alkoxylated anionic detergent surfactant is a linear or branched, substituted or unsubstituted alkoxylated alkylsulphate of C12.18 having an average degree of alkoxylation of 1 to 30, preferably 1 to 10. Preferably, the anionic alkoxylated detergent surfactant is a straight or branched, substituted or unsubstituted alkyl ethoxylated sulfate of C12.18 having an average degree of ethoxylation of from 1 to 10. Most preferably, the alkoxylated anionic detergent surfactant is an unsubstituted, linear C12-18 alkyl ethoxylated sulfate which has an average degree of ethoxylation of 3 to 7. The alkoxylated anionic detergent surfactant may also increase the activity of the non-alkoxylated anionic detergent surfactant by causing the non-alkoxylated anionic detergent surfactant to be less precipitated out of the solution in the presence of free calcium cations. Preferably, the weight ratio of the non-alkoxylated anionic detergent surfactant to the alkoxylated anionic detergent surfactant is less than 5: 1, is less than 3: 1, is less than 1.7: 1, or less than 1.5: 1. This proportion gives a performance Optimal maintenance of whiteness in combination with a good profile of tolerance to hardness and a good foam profile. However, it may be preferred that the weight ratio of the non-alkoxylated anionic detergent surfactant relative to the alkoxylated anionic detergent surfactant is greater than 5: 1, or greater than 6: 1, or greater than 7: 1, or even greater than 10. :1. This ratio provides optimal grease dirt cleaning performance in combination with a good hardness tolerance profile and a good foam profile. Suitable anionic alkoxylated detergent surfactants are: Texapan LEST ™ by Cognis; Cosmacol AES ™ by Sasol; BES151 ™ by Stephan; Empicol ESC70 / U ™; and mixtures of them.

Nonionic detergent surfactant The compositions of the invention may comprise a nonionic surfactant. When present, generally, it may be present in amounts of 0.5% by weight to 20, more generally 0.5 to 10% by weight, based on the total weight of the composition. The composition may comprise from 1% by weight to 7% by weight or from 2% by weight to 4% by weight, of a nonionic detergent surfactant. The inclusion of non-ionic detergent surfactant in the composition contributes to providing a good overall cleaning profile, especially when washed at high temperatures such as 60 ° C or more. The nonionic detergent surfactant can be selected from the group comprising C12-C18 alkyl ethoxylates, such as Shell's NEODOL® non-ionic surfactants; C6-C12 alkylphenol alkoxylates wherein the Alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C12-C18 alcohol and C6-C12 alkylphenol condensates with block polymers of ethylene oxide / propylene oxide, such as Pluronic® from BASF; branched chain medium alcohols of C14-C22, BA, as described in more detail in U.S. Pat. no. 6,150,322; C14-C22 half-chain branched alkyl alkoxylates, BAEX wherein x = from 1 to 30, as described in more detail in U.S. Pat. num. 6,153,577, 6,020,303 and 6,093,856; the alkyl polysaccharides, as described in more detail in U.S. Pat. no. 4,565,647, specifically the alkyl polyglycosides, as described in more detail in U.S. Pat. num. 4,483,780 and 4,483,779; the polyhydroxy fatty acid amides, as described in more detail in U.S. Pat. no. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; poly (oxyalkylated) alcohol surfactants coated with ether, as described in more detail in U.S. Pat. no. 6,482,994 and WO 01/42408; and mixtures of them. The nonionic detergent surfactant could be an alkyl polyglycoside or an alkyl ethoxylated alcohol. Preferably, the nonionic detergent surfactant is a linear or branched, substituted or unsubstituted C8.18 alkyl ethoxylated alcohol having an average degree of ethoxylation of 1 to 50, more preferably 3 to 40. Nonionic surfactants having A degree of ethoxylation of 3 to 9 may also be particularly useful. Nonionic surfactants that have a value of HLB (lipophilic hydrophilic balance) from 13 to 25 such as the alkyl ethoxylated alcohols of C8.18 having an average degree of ethoxylation of 15 to 50 or even 20 to 50 may also be preferred nonionic surfactants in the compositions of the invention. Examples of the latter nonionic surfactants are Lutensol AO30 and similar materials disclosed in WO04 / 041982. These can be beneficial given that they have good dispersing properties of lime from soaps. The nonionic detergent surfactant not only provides a higher dirt cleaning performance but can also increase the activity of the anionic detergent surfactant by making it less likely that the anionic detergent surfactant will precipitate out of the solution in the presence of free calcium cations . Preferably, the weight ratio of non-alkoxylated anionic detergent surfactant relative to the nonionic detergent surfactant is in the range of less than 8: 1, or less than 7: 1, or less than 6: 1 or less than 5: 1 , preferably from 1: 1 to 5: 1, or from 2: 1 to 5: 1 or even from 3: 1 to 4: 1.

Cationic Detergent Surfactant In one aspect of the invention, the detergent compositions are free of cationic surfactants. However, the composition can optionally comprise from 0.1% by weight to 10 or 5% by weight, of a cationic detergent surfactant. However, when present, the composition preferably comprises 0.5% by weight to 3% by weight, or still from 1% to 3% by weight, or even from 1% by weight to 2% by weight, of a cationic detergent surfactant. This is the optimum level of cationic detergent surfactant to provide good cleaning performance. Suitable cationic detergent surfactants are alkyl pyridinium compounds, alkyl quaternary ammonium compounds, quaternary alkyl phosphonium compounds and ternary alkyl sulfonium compounds. The cationic detergent surfactant may be selected from the group comprising: alkoxylated quaternary ammonium surfactants (AQA), as described in more detail in U.S. Pat. no. 6,136,769; dimethyl hydroxy ethylammonium quaternary surfactants, as described in more detail in U.S. Pat. no. 6,004,922; polyamine cationic surfactants, as described in more detail in patents WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; ester cationic surfactants, as described in more detail in U.S. Pat. num. 4,228,042, 4,239,660, 4,260,529 and 6,022,844; amino surfactants, as described in more detail in U.S. Pat. no. 6,221, 825 and WO 00/47708, specifically amido propyldimethylamine; and mixtures of them. Preferred cationic detergent surfactants are quaternary ammonium compounds having the following general formula: (R) (R1) (R2) (R3) N + X- wherein, R is a linear or branched, substituted or unsubstituted C6-18 alkyl or alkenyl entity, R and R2 are independently selected from the methyl or ethyl entities, R3 is a hydroxyl, hydroxymethyl or hydroxyethyl entity, X is an anion which provides a charge neutrality, preferred anions include halides (such as chloride), sulfate or sulfonate. The preferred cationic detergent surfactants are quaternary monoalkyl monohydroxyethylammonium chlorides of C6.18. The most preferred cationic detergent surfactants are monoalkyl monohydroxyethyldimethylammonium quaternary chloride of C8.10, monoalkyl monohydroxyethyldimethylammonium chloride of C10.12 and monoalkyl monohydroxyethyldimethylammonium chloride of C10. Cationic surfactants such as Praepagen HY (trade name of Clariant) may be useful and may also be useful as foam enhancers. The cationic detergent surfactant provides a higher cleaning performance of oily dirt. However, the cationic detergent surfactant can increase the tendency of any non-alkoxylated anionic detergent surfactant to precipitate out of the solution. Preferably, the cationic detergent surfactant and any non-alkoxylated anionic detergent surfactant are separated in the detergent composition of the invention; for example, if the cationic surfactant is present, preferably the cationic surfactant and any anionic surfactant, in particular a non-alkoxylated anionic surfactant, will be present in the composition in separate particles. This minimizes any effect that the cationic detergent surfactant may have on an unwanted precipitation of the anionic detergent surfactant and furthermore ensures that the resulting wash liquor is not cloudy when it comes into contact with the water. If the cationic surfactant is present, preferably the weight ratio of the non-alkoxylated anionic detergent surfactant to the cationic detergent surfactant is in the range of 5: 1 to 25: 1, more preferably 5: 1 to 20: 1 or 6: 1 to 15: 1 or from 7: 1 to 10: 1 or even from 8: 1 to 9: 1. Typically, the detergent composition comprises from 1 to 50% by weight of anionic surfactant, more generally from 2 to 40% by weight. Alkylbenzenesulfonates are preferred anionic surfactants. Preferred compositions of the present invention comprise at least two different surfactants comprising at least one selected from a first group, the first group comprising an alkylbenzene sulfonate surfactant and MES; and at least one selected from a second group, the second group comprises an alkoxylated anionic surfactant, MES, and non-ionic alkoxylated surfactant and alpha-olefin sulfonates (AOS). A particularly preferred combination comprises alkylbenzene sulfonate, preferably LAS in combination with MES. Another particularly preferred combination comprises alkylbenzene sulfonate, preferably LAS with an alkoxylated anionic surfactant, preferably C8.18 alkoxylated alkoxylated sulfate having an average degree of alkoxylation of 1 to 10. A particularly preferred third combination comprises alkylbenzenesulfonate, preferably LAS in combination with an alkoxylated nonionic surfactant, preferably C8.18 alkyl ethoxylated alcohol having a degree of alkoxylation of 15 to 50, preferably 20 to 40. The weight ratio of the surfactant of the first group with respect to the weight ratio of the surfactant of the second group is generally from 1: 5 to 100: 1, preferably from 1: 2 to 100: 1 or from 1: 1 to 50: 1 or even to 20: 1 or 10: 1. The levels of the surfactants are as described above in the specific classes of surfactants. The presence of AE3S or MES in the system is preferred due to its exceptional tolerance to hardness and its ability to disperse the calcium soaps that form the lipase during washing. In another embodiment, the surfactant in the detergent compositions of the invention comprises at least three surfactants, at least one of each first and second groups defined above and in addition a third surfactant, preferably also of the first or second groups defined above. The detergent compositions of the invention may surprisingly contain relatively low levels of surfactant and still perform good cleaning due to the dirt removal functionality provided by the lipase, whereby the general level of surfactant may be less than 12% by weight or 10% by weight or 8% by weight, based on the total weight of the composition. In a preferred embodiment of the invention, the detergent composition also comprises a foam enhancer, typically in amounts of 0.01 to 10% by weight, preferably in amounts of 0.02 to 5% by weight, based on the total weight of the composition. Suitable foam enhancers include the fatty acid amides, fatty acid alkalonamides, betaines, sulfobetaines and amine oxides. Particularly preferred materials are cocamidopropyl betaine, cocomonoethanolamide and amine oxide. A suitable amine oxide is Admox 12, supplied by Albemarle.

Calcium Soap Dispersants In view of the fact that lipase enzymes release dirt into the wash water, it may be particularly preferred that the detergent compositions of the invention further comprise anti-revertant polymers, such as the polymeric polycarboxylates described below. Additionally or alternatively, cellulose ethers such as carboxymethylcellulose (CMC) are also useful. A suitable CMC is Tylose CR1500 G2, marketed by Clariant. Suitable polymers are also marketed by Andercol, Colombia, under the trademark Textilan. It is particularly preferred to include additives that have the functionality of dispersing lime from the soap, such as the above-mentioned MES, AES, polymers or highly ethoxylated nonionic surfactants which exhibit excellent dispersion of soap lime such as Acusol 460N (Rohm & Haas). The list of calcium soap dispersants suitable documents are provided in the following references and documents cited therein. WO9407974 (P &G), WO9407984 (P &G), WO9407985 (P &G), WO9504806 (P &G), WO9703379 (P &G), U.S. Pat. no. 6770610 (Clariant), EP0324568 (Rohm &Haas), EP0768370 (Rohm &Haas), M.K.

Nagarajan and W.F. Masler, "Cosmetics and Toiletries" (Cosmetics and Toiletries), 1989, 104, p. 71-73, W. M. Linfield, Tenside Surf. Det, 1990, 27, pgs. 159-161, R.G. Bistline et al., J. Am. Oil Chem. Soc, 1972, 49, p. 63-69 It has been found that the presence of a stain release polymer is particularly advantageous to further strengthen the stain removal and the development cleansing benefits, particularly in synthetic fibers. Modified cellulose ethers such as methyl hydroxyethyl cellulose (MHEC), for example, such as that marketed by Clariant as Tylose MH50 G4 and Tylose MH300 G4, are preferred. Polyester-based stain-removing polymers are particularly preferred since they can also be effective as calcium soap dispersants. Some examples of suitable materials are Repel-o-Tex PF (supplied by Rhodia), Texcare SRA100 (supplied by Clariant) and Sokalan SR100 (BASF) The formulations may contain one or more enzymes in addition to the first washing process, for example, protease, amylase, cellulase (particularly endoglucanase), pectate lysase or mannanase.

The detergent compositions of the invention can be in any convenient form, such as solids such as powdered solids or granules, tablets, sticks, or liquids that can be aqueous or non-aqueous, gels or liquid gels. Either of these forms can be partially or totally encapsulated. However, the present invention relates particularly to solid detergent compositions, particularly granular compositions. When the detergent compositions of the invention are solid, conventionally the surfactants are incorporated into agglomerates, extruded products or spray dried particles together with solid materials, usually additives, and these may be mixed to produce a fully formulated detergent composition according to the invention. When present in granulated form, the detergent compositions of the present invention are preferably those having a general bulk density ranging from 350 to 1200 g / l, more preferably from 450 to 1000 g / l or even from 500 to 900 g. / l. Preferably, the detergent particles of the detergent composition in granular form have an average particle size of 200 μm to 2000 μm, preferably 350 μm to 600 μm. Generally, the detergent compositions of the invention will comprise a mixture of detergent particles including combinations of agglomerates, spray dried powders or dry aggregate materials, such as bleaching agents, enzymes, etc.

In one aspect of the invention, the detergent compositions herein comprise an anionic surfactant of the aforementioned list which is a non-alkoxylated anionic detergent surfactant and which is preferably incorporated into the detergent composition in particulate form, such as by means of an agglomerate , a spray-dried powder, an extruded product or in the form of a globule, noodle, needle or scale. Spray dried particles are preferred. If it is an agglomerate, the agglomerate preferably comprises at least 20% by weight of the agglomerate of a non-alkoxylated anionic detergent surfactant, more preferably from 25% by weight to 65% by weight, by weight of the agglomerate of a surfactant non-alkoxylated anionic detergent. It may be preferred that part of the non-alkoxylated anionic detergent surfactant is in the form of a spray-dried powder (for example, a blown powder), and that part of the non-alkoxylated anionic detergent surfactant is in the form of a non-spray-dried powder (for example, an agglomerate, or an extruded material, or a flake such as a linear alkyl benzene sulphonate flake; suitable linear alkyl benzene sulphonate flakes are supplied by Pilot Chemical under the trade name F90®, or by Stepan under the trade name Nacconol 90G ®). This is especially preferred when it is desired to incorporate high levels of non-alkoxylated anionic detergent surfactant into the composition. Any alkoxylated anionic detergent surfactant may be incorporated in the detergent compositions of the invention by means of a spray-dried particle of a non-spray-dried powder such as an extruded or agglomerated product, preferably an agglomerate. Non-spray dried particles are preferred when it is desired to incorporate high levels of alkoxylated anionic detergent surfactant into the composition. Any nonionic detergent surfactant, or at least a portion thereof, may be incorporated into the composition in the form of a liquid spray, wherein the nonionic detergent surfactant, or at least a portion of it in liquid form (e.g. , in the form of a hot melt) is sprayed on the rest of the composition. The nonionic detergent surfactant, or at least a portion thereof, may be included in a particulate for incorporation into the detergent composition of the invention and the nonionic detergent surfactant, or at least a part of it, can be added dry to the rest of the composition. The nonionic surfactant, or at least part thereof, may be in the form of a mixture of coparticulate with a solid carrier material such as carbonate salt, sulfate salt, burkeite, silica or any mixture thereof. Any nonionic detergent surfactant, or at least a portion thereof, may be in a co-articulated mixture with an alkoxylated anionic detergent surfactant, a non-alkoxylated anionic detergent surfactant or a cationic detergent surfactant. The anionic detergent surfactant or at least part thereof is in the form of an agglomerate or an extruded product, either with an alkoxylated anionic detergent surfactant, a non-alkoxylated anionic detergent surfactant or a cationic detergent surfactant.

The cationic detergent surfactant, if present, may be included in the composition by incorporation into a particulate such as a spray-dried powder, an agglomerate, an extruded product, or in the form of a noodle, needle or flake, or any combination thereof. these. Preferably, the cationic detergent surfactant, or at least part of it, is in the form of a spray-dried powder or an agglomerate.

Optional detergent auxiliaries Optionally, the detergent ingredients may include one or more detergent additives or other materials to improve or contribute to the cleaning performance, the treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition. The usual detergent auxiliaries of the detergent compositions include the ingredients set forth in U.S. Pat. no. 3,936,537, Baskerville et al. and in the Great Britain patent application no. 9705617.0 issued to Trinh et al., Published September 24, 1997. Such auxiliaries are included in the detergent compositions according to their conventional use industry, generally from 0% by weight to approximately 80% by weight of the detergent ingredients, preferably from about 0.5 wt% to about 20 wt% and may include color specks, foam intensifiers, suds suppressors, anti-stain or anti-corrosion agents, soil suspending agents, soil release agents, colorants, fillers, brighteners optical, germicidal, alkaline sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, solvents, solubilizing agents, chelating agents, clay, antiredeposit agents / stain removal agents, polymeric dispersing agents, processing aids, fabrics softening components, static control agents, agents bleaching agents, whitening activators, bleach stabilizers, dye transfer inhibitors, flocculants, fabric softeners, foam suppressors, fabric integrity agents, perfumes, bleaching agents, photobleaching agents, alkali metal sulphate salts, sulphamic acid, complexes of sulfamic acid and sodium sulfate, etc., and combinations of these. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition or component, as well as on the precise nature of the washing operation in which they will be used. Preferred zwitterionic surfactants comprise one or more quatemized nitrogen atoms and one or more parts selected from the group comprising: carbonate, phosphate, sulfate, sulfonate and combinations thereof. The preferred zwitterionic surfactants are alkylbetaines. Other preferred zwitterionic surfactants are the alkylamine oxides. Cationic surfactants that are complexes comprising a cationic surfactant and an anionic surfactant may also be included. The molar ratio of the cationic surfactant to the anionic surfactant in the complex is generally greater than 1: 1 so that the complex has a net positive charge.

The compositions of the invention may comprise bleach boosters. The preferred bleach boosters are selected from the group comprising: zwitterionic mines, imino anionic polyols, quaternary oxazyridinium salts and combinations thereof. The preferred bleach boosters are selected from the group comprising: aryliminium zwitterions, aryliminium polyions, and combinations thereof. Suitable bleach builders are described in U.S. Pat. num. 360,568, 5,360,569 and 5,370,826. A preferred additional ingredient is an antiredeposit agent. Preferably, the detergent composition comprises one or more antiredeposition agents. The preferred antiredepositing agents are the polymeric cellulose components and most preferably the carboxymethylcelluloses. A preferred additional ingredient is a chelant. Preferably, the detergent composition comprises one or more chelating agents. Preferably, the detergent composition comprises (by weight of the composition) from 0.01% to 10% chelant or 0.01 to 5% by weight or 4% by weight or 2% by weight. Preferred chelants are selected from the group comprising hydroxyethane dimethylene phosphonic acid, ethylene diamine tetramethylene phosphonic acid, diethylene triamine pentaacetate, ethylenediamine tetraacetate, diethylene triamine pentamethylphosphonic acid, ethylene diamine disuccinic acid and combinations thereof. A preferred additional ingredient is a dye transfer inhibitor. Preferably, the detergent composition comprises one or more dye transfer inhibitors. Dye transfer inhibitors are generally polymeric components that trap dye molecules and retain them when suspended in the wash liquid. Preferred inhibitors are selected from the group comprising: polyvinylpyrrolidones, polyvinylpyridine N-oxides, polyvinylpyrrolidone-polyvinylimidazole copolymers and combinations thereof. Preferred auxiliary components include other enzymes. Preferably, the detergent composition comprises one or more additional enzymes. Preferred enzymes are selected from the group comprising: amylases, arabinosidases, carbohydrases, cellulases, chondroitinases, cutinases, dextranases, esterases, β-glucanases, glucoamylases, hyaluronidases, keratanases, laccases, ligninases, lipoxygenases, malanases, mannanases, oxidases, pectinases, pentosanas, peroxidases, phenoloxidasas, phospholipases, proteases, pullulanases, reductasas, tanasas, transferasas, xilanasas, xiloglucanasas, and combinations of these. Additional preferred enzymes are selected from the group comprising amylases, carbohydrases, cellulases, proteases, and combinations thereof. A preferred auxiliary component is a fabric integrity agent. Preferably, the detergent composition comprises one or more agents for preserving tissue integrity. Fabric integrity agents are typically polymeric components that are deposited on the surface of the fabric and prevent damage thereto during the washing process. The preferred fabric integrity agents are celluloses hydrophobically modified. This type of celluloses reduces the abrasion of the fabrics, improves the interaction between the fibers and reduces the loss of dye from the fabric. A preferred hydrophobically modified cellulose is described in WO99 / 14245. Other fabric integrity agents are polymeric or oligomeric components preferably obtained by means of a process comprising the step of condensing imidazole and epichlorohydrin. A preferred auxiliary component is a salt. Preferably, the detergent composition comprises one or more salts. The salts can function as an alkalinity agent, buffers, additives, coaditives, scale inhibitors, fillers, pH regulators, stabilizers and combinations thereof. Normally, the detergent composition comprises (by weight of the composition) from 5% to 60% salt. Preferred salts are alkali metal salts of aluminate, carbonate, chloride, bicarbonate, nitrate, phosphate, silicate, sulfate and combinations thereof. Other preferred salts are the alkaline earth metal salts of aluminate, carbonate, chloride, bicarbonate, nitrate, phosphate, silicate, sulfate and combinations thereof. Especially preferred salts are sodium sulfate, carbonate, bicarbonate, silicate and sulfate and combinations thereof. The alkali metal or alkaline earth metal salts optionally can be anhydrous. A preferred additional ingredient is a soil release agent. The detergent composition comprises one or more soil release agents. Soil release agents are typically polymeric compounds that modify the surface of the fabric and impede the redeposition of the dirt in it. Preferred soil release agents are copolymers, preferably block copolymers comprising one or more terephthalate units. Preferred soil release agents are copolymers synthesized from dimethylterephthalate, 1,2-propylglycol and methyl-coated polyethylene glycol. Other preferred soil release agents are the ammonically coated polyesters. It may be desired that the compositions of the invention comprise at least 0.1% by weight, or at least 0.5% by weight, or at least 2 or 3% by weight, or even at least 5% by weight of polymeric polycarboxylates., up to levels of 30% by weight or 20% by weight or 10% by weight. Preferred polymeric polycarboxylates include polyacrylates and copolymers of maleic acid and acrylic acid. Suitable polycarboxylates are the Sokalan CP, PA and HP series (BASF) such as Sokalan CP5, PA40 and HP22, and the Alcosperse (Aleo) polymer series such as Alcosperse 725, 747, 408, 412 and 420. It can also be preferring that the composition comprises a dirt dispersant, for example, having the formula: bis ((C2H50) (C2H40) n) (CH3) -N + -CxH2) (- N + - (CH3) -bis ((C2H50) (C2H40) n) wherein, n has a value of 20 to 30, and x has a value of 3 to 8. Other suitable soil dispersants are sulfonated or sulphated soil dispersants having the formula: sulfonated or sulfated bis ((C2H5O) (C2H4O) n) (CH3) -N + -CxH2x-N + - (CH3) - bis ((C2H5O) (C2H4O) n) wherein, n = from 20 to 30, and x = from 3 to 8. Preferably, the composition comprises at least 1% by weight, or at least 2% by weight, or at least 3% by weight of soil dispersants.

Softening System The detergent compositions of the invention may comprise softening agents to soften with washing such as clay and optionally with a flocculant and enzymes. A more detailed specific description of the suitable detergent components can be found in WO97 / 11151.

Washing Method The invention also includes methods for washing textiles comprising contacting the textiles with an aqueous solution comprising the detergent composition of the invention. The invention can be particularly beneficial at low water temperatures, such as below 30 ° C or below 25 ° C or 20 ° C. Generally, the aqueous wash solution will comprise at least 100 ppm or at least 500 ppm of the detergent composition.

EXAMPLES The following are examples of the invention.

Claims (1)

NOVELTY PE THE INVENTION CLAIMS 1. - A detergent composition comprising a source of hydrogen peroxide, a hydrophobic peracid or a precursor thereof having the formula R- (C = O) -L, wherein R is an alkyl group having from 6 to 14, preferably from 8 to 12 carbon atoms, and L is a leaving group, and a lipase enzyme which is a polypeptide having an amino acid sequence that: (a) has at least 90% identity with the wild type derived from the strain DSM 4109 Humicola lanuginosa; (b) compared to wild-type lipase, it comprises a substitution of an electrically neutral or negatively charged amino acid on the surface of the three-dimensional structure within 15A of E1 or Q249 with a positively charged amino acid; and (c) comprises a peptide addition at the C-terminus; or (d) comprises a peptide addition at the N-terminus or (e) satisfies the following limitations: i) comprises a negative amino acid at the E210 position of the wild-type lipase; I) comprises a negatively charged amino acid in the region corresponding to positions 90-101 of the wild-type lipase; and ii) comprises a neutral or negative amino acid at a position corresponding to N94 of the wild-type lipase or has a negative or neutral electrical charge in the region corresponding to positions 90-101 of the wild-type lipase; The detergent composition has an alkalinity reserve greater than 6.5, the amount of oxygen available (from the peroxide source) and the peracid or precursor thereof is such as to provide the detergent composition with a molar ratio of available oxygen (from the peroxide source): peracid from 1: 1 to 35: 1. 2. The detergent composition according to claim 1, further characterized in that it has a reserve alkalinity greater than 8, or greater than 9. 3. The detergent composition according to claim 1 or claim 2, further characterizing it has an available oxygen ratio: peracid from 2: 1 to 8: 1. 4. The detergent composition according to any preceding claim, further characterized in that the hydrophobic bleach activator comprises nonanoyloxybenzenesulfonate. 5. The detergent composition according to any preceding claim, further characterized in that it comprises from 0.1 to 40% by weight of an alkoxylated alkylsulfate surfactant or from 0.1 to 40% by weight of C 1 alkyl ester sulphonate, preferably sulfonated methyl ester (MES), preferably in combination with alkylbenzene sulfonate in an amount of 5 to 40% by weight. 6. The detergent composition according to any preceding claim, further characterized in that it comprises a foam enhancer in an amount of 0.05 to 2% by weight, preferably selected from fatty acid amides, fatty acid alkanolamides, betaines, sulfobetaines, and amine oxides or mixtures of them

1. The detergent composition according to any preceding claim, further characterized in that it comprises from 0.05 to 5, preferably from 0.1 to 1% by weight of tetraacetylethylenediamine (TAED). 8. The detergent composition according to any preceding claim, further characterized in that it is a solid detergent composition, preferably granular. 9. A washing process comprising washing textile articles in an aqueous solution comprising the detergent composition according to any of the preceding claims. 10.- The washing process in accordance with the claim 9, further characterized in that the aqueous solution is at a temperature below 30 ° C.