KR20070103764A - 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

The present invention relates to detergent compositions, in particular laundry detergents, in particular detergents comprising lipase or lipase enzymes.

Many detergent compositions include a bleaching system that aids in stain removal of the article being cleaned. These bleaching systems usually include a source of hydrogen peroxide, such as perborate or percarbonate. The performance of hydrogen peroxide bleach is often enhanced by the use of peracids or peracid precursors (often referred to as bleach activators) which may be preformed in addition to hydrogen peroxide (or oxygen source). In use, the bleach activator reacts with excess hydrogen peroxide to form peracid bleach species. In conventional laundry formulations an excess of hydrogen peroxide source is used.

The most common bleach activator is TAED (tetra acetyl ethylene diamine), the active bleach species formed upon reaction with hydrogen peroxide is peracetic acid. Other active agents have longer carbon chains and generate bleaching species that are hydrophobic. These are particularly preferred for effective bleaching against oily stains.

One well known example of such a hydrophobic bleach activator is nonanoyl oxybenzene sulfonate (NOBS). This bleach activator reacts to form the reactive bleach species peronanoic acid. However, this bleaching species reacts with the bleach activator itself to di-C ₉ It has been found that it forms an acyl peroxide, in which other hydrophobic bleach activators react to form the corresponding diacyl peroxide. These species are powerful bleaching species and are useful in the washing process but are insoluble. In some types of washing machines, these compounds may tend to settle in the washing tank of the washing machine when the washing water is drained from the washing machine. Thus, strong bleach may be unnaturally concentrated in these areas, and in some types of washing machines over time the above areas such as polymers and / or rubber wash basins (where the materials used in these areas are susceptible to high levels of bleach) It has been found that damage to the washing machine may be caused.

The problem addressed by the present invention is how to alleviate the above problems to achieve the effect of hydrophobic bleach while minimizing or preventing damage to the cleaning equipment.

Lipase enzymes have been used in detergents since the late 1980s for the removal of fatty contaminants by decomposition of fatty contaminants into triglycerides.

Relatively recently, major commercial lipase enzymes such as Lipolase (Novozymes) worked particularly effectively at lower moisture levels during the drying step of the washing process. These enzymes tend to exhibit significant cleaning only in the second washing step because the active site of the enzyme is occupied by water during the washing process, resulting in pronounced lipolysis only in contaminants remaining in the garments washed during the drying step. This is because the degraded fat is then removed in the next washing step. However, more recently, high efficiency lipases which also work effectively during the washing step of the cleaning process, in which a significant improvement in the cleaning effect due to the lipase enzyme as well as the cleaning in the second washing step can be seen in the first washing cycle. Was developed. Examples of such enzymes are as described in WO 00/60063 and Research Disclsoure IP6553D. Such enzymes are referred to below as first washing lipases. Examples of such enzymes include certain variants of lipolase (wild-type Humicola lanuginosa) that must include one or more substitutions with positive amino acids near the N-terminus of the three-dimensional structure. Include. The variant must additionally comprise a peptide addition at the C-terminus and / or meet certain restrictions on the electrically charged amino acids at positions 90-101 and 210. The inventors have found that the use of these first wash enzymes and certain types of detergent formulations make it possible to use these hydrophobic bleach activators to achieve good stain removal while at the same time reducing all of the disadvantages indicated above. .

Definition of Invention

According to the invention, a hydrogen peroxide source; Hydrophobic peracids of the formula R— (C═O) —L, wherein R is an alkyl group having 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms, and L is a leaving group; or a precursor thereof; And (a) greater than or equal to 90% identity with wild-type lipases derived from DSM 4109 from Fumicola ranuginosa strain, and (b) compared to the wild-type lipases, at the surface of a three-dimensional structure within 15 ms of E1 or Q249. And a neutral or negatively charged amino acid substituted with a positively charged amino acid, (c) comprising a peptide addition at the C-terminus, and (d) a peptide addition at the N-terminus (e) i) a negative amino acid at position E210 of the wild-type lipase, ii) a negatively charged amino acid in a region corresponding to positions 90-101 of the wild-type lipase, iii) N94 of the wild-type lipase Restrictions that contain a neutral or negative amino acid at a position corresponding to and / or have a net charge that is negative or neutral at a region corresponding to positions 90-101 of the wild-type lipase A detergent composition comprising a lipase enzyme, which is a polypeptide having an amino acid sequence, wherein the reserve alkalinity exceeds 6.5 and the amount of available oxygen and peracid and / or precursor thereof (from the peroxide source) is (peroxide). Detergent compositions are provided, the amounts of providing a molar ratio of available oxygen: peracid (from a source) in a ratio of 1: 1 to 35: 1.

According to the invention, a hydrogen peroxide source; Hydrophobic bleach activators of the formula R- (C═O) -L, wherein R is an alkyl group having 6 to 14 carbon atoms, preferably 8 to 12, and L is a leaving group; And a lipase enzyme that produces a first wash lard removal performance that is superior to that produced by WT repolarase (trade name, Novozymes) using the RAD first wash test described below. Is greater than 6.5 and an amount is provided such that the amount of oxygen source and peracid is such that the molar ratio of available oxygen: peracid (from the peroxide source) is 1: 1 to 35: 1 in the detergent composition. .

WT repolarase from Novozymes is described in SEQ ID NO: 2 in US Pat. No. 5,869,438.

We found diacyl peroxide formation when the first rinse lipase is used in detergent compositions with high preliminary alkalinity and a molar ratio of available oxygen: peracid (from peroxide source) of 1: 1 to 35: 1. Found that the disadvantages of this type of hydrophobic peracid or peracid precursor are adjusted to alleviate.

In a preferred embodiment of the invention, the detergent composition of the present invention comprises less than 15% by weight of an enhancer selected from aluminosilicate (zeolite) enhancers and / or phosphate enhancers. In a more preferred aspect of the invention, the composition comprises less than 10%, or even less than 5% or 4% by weight of zeolite and / or phosphate enhancer.

Peroxide Source

Inorganic perhydrate salts are the preferred source of peroxides. Preferably, these salts are present at a level of from 0.05 to 40% by weight, more preferably from 1 to 30% by weight, or from 2 to 20% by weight, based on the detergent composition. Examples of inorganic perhydrate salts include perborate, percarbonate, persulfate, superphosphate and persilicate. Most preferred are perborate, generally monohydrate or tetrahydrate, or more particularly percarbonate. These are generally alkali metal salts, preferably sodium salts. Inorganic perhydrate salts are usually incorporated into the detergent compositions of the present invention as crystalline solids, which may optionally be coated, for example, to improve storage stability. Suitable coatings include inorganic salts such as alkali metal silicates, carbonates or borate salts, or mixtures thereof, or organic materials such as waxes, oils or fatty soaps.

Hydrophobic Peracid  or Peracid  Precursor

Suitable compounds are compounds of formula R- (C = O) OOM or R- (C = O) -L, wherein R is an optionally branched alkyl group having 6 to 14 carbon atoms, more preferably 8 to 12, and M is Counter ions, preferably sodium, potassium or hydrogen, and L is a leaving group. Preferred leaving groups are benzoic acid and its derivatives, in particular benzene sulfonate.

Suitable examples include decanoyl oxybenzoic acid or salts thereof, sodium or potassium salt of dodecanoyl oxybenzene sulfonate, decanoyl oxybenzenesulfonate, 3,5,5-trimethyl hexanoyloxybenzene sulfonate, or even more preferably Nonanoyloxybenzene sulfonate (NOBS).

The peracid or peracid precursor is generally present in the composition in an amount of 0.5 to 10% by weight, preferably 0.5 to 5% by weight, preferably 0.5 to 4% by weight, based on the detergent composition.

Optionally, in addition to hydrophobic peracid or peracid precursors, hydrophilic peracid or peracid precursors may also be incorporated into the detergent compositions of the present invention. These include materials of the formula given above for hydrophobic peracids / precursors, but the R groups have less than 6 carbon atoms, preferably less than 4. Preferred example is TAED. If present, it will generally be present in an amount of at most 7% by weight, generally 0.1 to 5% by weight.

The amount of hydrogen peroxide and the amount of peracid or peracid precursor are selected such that the molar ratio of available oxygen to peracid (from the peroxide source) is 1: 1 to 35: 1. Preferred molar ratios may be from 2: 1 to 10: 1, or 3: 1 or even 5: 1 to 8: 1.

Lipase  enzyme

The reference lipase used in the present invention is a wild type lipase derived from Humicola ranuginosa strain DSM 4109. It has the amino acid sequence described here in European Patent No. 258068 and European Patent No. 305216 and exemplified at positions 1-269 of SEQ ID NO: 2 of US Pat. No. 5869438. In this specification, reference lipases are also referred to as repolarases.

Substitution by Positive Amino Acids

The lipases of the present invention are capable of replacing one or more (e.g., 2-4, in particular 2) with a positively charged amino acid, preferably R, in an amount of an electrically neutral or negatively charged amino acid in the vicinity of E1 or Q249. Include.

The substitution may be carried out at the surface of the three-dimensional structure within 15 ms of E1 or Q249, for example positions 1-11, 90, 95, 169, 171-175, 192-211, 213-226, 228-258, 260-262 Present at any of these positions.

The substitution is within 10 ms of E1 or Q249, for example any of the positions 1-7, 10, 175, 195, 197-202, 204-206, 209, 215, 219-224, 230-239, 242-254 It may be present at the position of.

The substitution may be present at any of the positions 1-11, 169, 171, 192-199, 217-225, 228-240, 243-247, 249, 261-262, within 15 ms of E1. .

The substitution is most preferably present within 10 ms of E1, for example at any of the 1-7, 10, 219-224 and 230-239 positions.

Thus, some preferred substitutions are S3R, S224R, P229R, T231R, N233R, D234R and T244R.

Peptide addition at the C-terminus

Lipases may also include peptide additions attached to the C-terminal L269. Peptide addition improves first wash performance in various detergents.

Peptide addition preferably consists of 1-5 amino acids, for example 2, 3 or 4 amino acids. Amino acid of the peptide addition will be numbered 270, 271 and the like.

Peptide addition may consist of electrically neutral (eg hydrophobic) amino acids such as PGL or PG. In alternative embodiments, the lipase peptide addition consists of neutral (eg, hydrophobic) amino acids and amino acid C, and the lipase replaces the amino acid with C at a suitable position to form a disulfide bridge with C of the peptide addition. It involves doing. Examples are as follows:

270C connected to G23C or T37C

271C connected to K24C, T37C, N26C, or R81C

272C connected to D27C, T35C, E56C, T64C or R81C.

Amino acids at positions 90-101 and 210

Lipases used in the present invention preferably meet certain restrictions on amino acids electrically charged at positions 90-101 and 210. Thus, amino acid 210 may be negative. E210 may not change or may have a substitution E210D / C / Y, in particular E210D.

Lipase may comprise a negatively charged amino acid at any of the 90-101 (particularly 94-101) positions, eg, at the D96 and / or E99 positions.

Lipases may also comprise neutral or negative amino acids at the N94 position, ie N94 (neutral or negative), for example N94N / D / E.

In addition, the lipase may have a negative or neutral net charge in the 90-101 (particularly 94-101) region, ie the number of negative amino acids is equal to or greater than the number of positive amino acids. Thus, the region may have two negative amino acids (D96 and E99) and one positive amino acid (K98) and may not change from a repolarase having a neutral amino acid at position 94 (N94), or the region may have one or more substitutions It may be modified by.

Alternatively, two of the three amino acids N94, N96 and E99 may have a negative or unchanged charge. Thus, all three amino acids may be unchanged or may be changed by conservative or negative substitutions, ie N94 (neutral or negative), D (negative) and E99 (negative). Examples are N94D / E and D96E. One of the three may also be a substitution, ie N94 (positive), D96 (neutral or positive) or E99 (neutral or positive) to increase the charge. Examples are N94K / R, D96I / L / N / S / W or E99N / Q / K / R / H.

As discussed in WO 00/60063, substitution of a neutral amino acid with a negative amino acid (N94D / E) may improve the performance of the anionic detergent. Substitution of neutral amino acids with positive amino acids (N94K / R) is a mutant lipase that has excellent performance in both anionic detergents and anionic / nonionic detergents (for example 40-70% of the total surfactants are anionic surfactants). May be provided. Substitution of substitutions Q249R / K / H and / or R209 with neutral or negative amino acids (eg, R209P / S) may be useful. Lipases may optionally also include a substitution G91A.

Lipases may optionally also include substitution of one or more additional amino acids. Such substitutions may, for example, be made according to principles known in the art, for example in WO 92/05249, WO 94/25577, WO 95/22615, WO 97 / The substitutions described in 04079 and WO 97/07202 may be used. Specific examples of suitable combinations of substitutions are given in pages 4 and 5, which are tabular surfaces in WO 00/60063. Naming for amino acid modifications is as described in WO 00/60063.

Preferred lipase enzymes are described in WO 00/60063, the most preferred of which is Lipex (registered trademark of Novozymes), which has the Fumico lanuginosa (with mutations T231R and N233R). Thermomyses lanuginosus) lipase (lipolase, a trademark of Novozymes).

Lipase enzymes incorporated into the detergent compositions of the present invention are generally present in amounts of 10 to 20000 LU or even 100 to 10000 LU per gram of detergent composition. LU units for lipase activity are defined in WO 99/42566. The lipase dosage in the wash solution is typically 0.01 to 5 mg / L of active lipase protein, more typically 0.1 to 2 mg / L as enzyme protein.

Lipase enzymes may be incorporated into the detergent composition in any convenient form, generally in the form of non-dusting granules, stabilized liquids or protected, eg coated enzyme particles.

lard  First wash test

Whether any particular rapase enzyme provides a better first wash lard removal performance than WT repolarase (obtained from Novozymes, described in SEQ ID NO: 2 of US Pat. No. 5869438) according to the following test The performance results of the lipase can be determined by comparing the performance results of the specific lipase enzyme.

The washing performance of the lipolytic enzymes is investigated in a one cycle washing test and subsequent line-drying performed in a thermo-static washing tester (Terg-O-Tometer, TOM). The experimental conditions are as follows:

Wash solution: 1000 ml per beaker

Specimens: 7 flat cotton specimens (9 × 9 cm) per beaker (available from Warwick-Equest)

Blot: lard (0.75 mg Sudan red / g lard) colored red by Sudan red dye (Sigma). 50 μl of the lard / mean red heated to 70 ° C. is applied to the center of each specimen. After staining, the specimen is heated in an oven at 75 ° C. for 25 minutes and then stored overnight at room temperature.

Water for Washing Liquid Preparation: 3.2mM Ca ^{2 +} / Mg ^{2 +} (ratio of 5: 1)

Detergent: 5 g / L detergent composition A.

Detergent Composition A:

Alkyl sulfates _{(AS; C 14 -16) 0.300g} / ℓ

Alcohol ethoxylate (AEO; C _{12 -14} , 6EO) 0.650 g / l

Zeolite P 1.750 g / ℓ

Na ₂ CO ₃ 0.145 g / ℓ

Sokalan CP5 (BASF) 0.020 g / ℓ

CMC (carboxymethyl cellulose) 0.050 g / l

A detergent composition 5g / ℓ of hardness addition of: mixing in deionized water having a ^{(3.2 mM Ca 2 + / Mg} 2 + (5 1)) and artificially adjusting the pH by the addition of NaOH to 10.2. Lipase enzyme is added.

Lipolytic enzyme concentration: 0 and 12500 LU / L

Flush time: 20 minutes

Washing temperature: 30 ℃

Rinse: 15 minutes under running tap water

Drying: overnight at room conditions (about 20 ° C., 30-40% RH).

Evaluation: The reflectance was measured at 460 nm.

The percentage of lard removed is determined as follows:

Delta reflectance (dR), defined as:

R (sample washed with lipase-free detergent)-R (sample washed with lipase-free detergent)

Reflectance (also referred to as relaxation) is a datacolor that measures the amount of reflected light so that the sample is illuminated with two xenon lightning lamps and that full white corresponds to 100% reflectivity and full black corresponds to 0% reflectance. Measured on an Elrepho 2000 device. Comparing the results for lard removal due to the presence of enzymes, lipase enzymes that provide better performance than WT Lipolase ™ are suitable for use in the compositions of the present invention.

Preliminary alkalinity

As used herein, the term "preliminary alkalinity" refers to a 1% (w / v) solution of detergent composition up to pH 7.5 using hydrochloric acid, ie to calculate the preliminary alkalinity as defined herein. It is a measure of the buffering capacity of the detergent composition (g / NaOH / 100g detergent composition) determined by titration:

Preliminary alkalinity (up to pH 7.5) as alkali% of g NaOH per 100 g product =

T = titration to reach pH 7.5

M = molar concentration of HCl = 0.2

40 = molecular weight of NaOH

Vol = total volume (ie 1000 ml)

W = weight of product (10 g)

Aliquots = (100 ml)

From the fully formulated detergent composition, a 10 g sample weighed precisely to two decimal places is obtained. Samples should be obtained using a Pascal sampler in a dust cabinet. 10 g of sample is added to a plastic beaker and 200 ml of carbon dioxide-free deionized water is added. Stir at 15.7 rad / s (150 rpm) using a magnetic stirrer on a stir plate for at least 15 minutes until complete dissolution. Transfer the contents of the beaker to a 1 liter volumetric flask and make 1 liter with deionized water. Mix well and immediately take 100 ml ± 1 ml aliquots using a 100 ml pipette. While stirring, while maintaining the temperature at 21 ° C. ± 2 ° C., measure and record the pH and temperature of the sample using a pH meter that can read to ± 0.01 pH units. While stirring, titrate with 0.2 M hydrochloric acid until the pH is measured to exactly 7.5. Record milliliters of hydrochloric acid used. Take an average titration of three equal repetitions. The calculations described above are performed to calculate RA up to pH 7.5.

The RA of the detergent composition of the present invention will be greater than 6.5, preferably greater than 7.5. RA may be greater than 8 or even greater than 9 or greater than 9.5. The RA may be up to 20 or more.

Suitable preliminary alkalinities include, for example, one or more alkali metal silicates (except crystalline layered silicates), usually amorphous silicates, generally sodium salts in a ratio of 1.2 to 2.2, alkali metals (usually sodium-carbonate, bicarbonate and And / or sesquicarbonate). Persalts such as STPP and perborate and percarbonate also contribute to alkalinity. Buffering is necessary to neutralize the acidity of contaminants, particularly fatty acids liberated by lipase enzymes, to maintain alkaline pH during the washing process.

The detergent composition preferably comprises 0% to 50% by weight silicate, more generally 5 to 30% by weight silicate, or 7 to 20% by weight silicate, generally sodium silicate.

In order to provide the required preliminary alkalinity, the detergent compositions of the invention may comprise carbonates, typically 1% to 70% by weight, or 5% to 50% by weight or 10% to 30% by weight of carbonate. have. Preferred carbonates are sodium carbonate and / or sodium bicarbonate and / or sodium sesquicarbonate. The carbonate may be incorporated into the detergent composition in whole or in part via a mixed salt such as Burkeite. Very preferred carbonate is sodium carbonate. Preferably, the composition may comprise 5% to 50% by weight sodium carbonate, or 10 to 40% or even 15 to 35% by weight sodium carbonate. It may also be desirable for the composition to comprise 1% to 20% by weight, or even 2 to 10 or 8% by weight of sodium bicarbonate.

When zeolite is present, it is preferred that the weight ratio of sodium carbonate and / or sodium silicate to zeolite enhancer is 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. You may.

Carbonates or at least a portion thereof are typically present in particulate form, which typically has a weight average particle size in the range of 200 to 500 μm. However, the carbonate or at least a portion thereof is in the form of finely divided particulates, which may typically be preferred to have a weight average particle size in the range of 4 to 40 μm, which means that the carbonate or at least a portion thereof is a washable surfactant, for example Particular preference is given when present in the form of a co-particulate mixture with an alkoxylated anionic washable surfactant.

In order to provide the required preliminary alkalinity, the levels of carbonates and / or silicates, typically sodium carbonate and sodium silicate, are preferably 10 to 70% by weight, or 10 or even 15 to 50% by weight, based on the total weight of the composition. would.

Enhancer

Preferably, according to the invention, the amount of potent enhancer selected from phosphate and / or zeolite enhancers is less than 15% by weight, preferably less than 10% by weight, or even 8 or 5 or 4, based on the total weight of the detergent composition. Or less than 3 or 2% by weight.

In a further preferred embodiment of the invention, the total level of weak enhancer selected from layered silicate (SKS-6), citric acid, citrate and nitrilotriacetic acid or salts thereof is less than 15% by weight, based on the total weight of the detergent composition, more It is preferably less than 8% by weight, more preferably less than 4% by weight or even less than 3 or 2% by weight. Typically, the level of each of the layered silicates, citric acid, citrate and nitrilotriacetic acid or salts thereof will be less than 10% by weight or even less than 5% or by weight based on the total weight of the composition.

Surfactants

Surfactants are very preferred auxiliary components of the compositions of the present invention. Preferably, the detergent composition contains one or more surfactants. Typically, the present detergent composition comprises from 0% to 50%, preferably 5%, more preferably 10 or even 15% to 40%, or 30%, or 20% (based on the weight of the composition). It contains one or more surfactants. Preferred surfactants are anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants and mixtures thereof.

Anionic  Surfactants

의 C₁₀-C₁₈ 2급 (2,3) 알킬 설페이트(여기서, M은 수소 또는 전하 중성을 제공하는 양이온, 바람직하게는 나트륨 및 암모늄 양이온이고, x는 7 이상, 바람직하게는 9 이상의 정수이고, y는 8 이상, 바람직하게는 9 이상의 정수이다); C₁₀-C₁₈ 알킬 알콕시 카복실레이트; 미국 특허 제6,020,303호 및 미국 특허 제6,060,443호에 상세히 기재된 바와 같은 중쇄 분지형 알킬 설페이트; 국제 공개공보 제WO 99/05243호, 제WO 99/05242호, 제WO 99/05244호, 제WO 99/05082호, 제WO 99/05084호, 제WO 99/05241호, 제WO 99/07656호, 제WO 00/23549호 및 제WO 00/23548호에 더 상세하게 기재된 바와 같은 변형된 알킬벤젠 설포네이트(MLAS) 및 이들의 혼합물을 포함한다.Suitable anionic surfactants typically comprise one or more moieties selected from the group consisting of carbonates, phosphates, phosphonates, sulfates, sulfonates, carboxylates and mixtures thereof. The anionic surfactant may be one of the C _{8 -18} alkyl sulfates and C _{8 -18} alkyl sulfonate, or a mixture of two or more of them. Further suitable anions are incorporated alone or in a mixture form in the compositions of this invention nonionic surfactants, C _{8 -18} alkyl sulfate and / or C _{8 -18} alkyl sulfonate 1 from 1 to 9 moles per mole of C _1-4 alkyl, butylene oxide and optionally fused C _{8 -18} alkyl sulfate and / or C _{8 -18} alkyl is a sulfonate. The C _{8 -18} alkyl sulfate and / or C _{8 -18} alkyl chains of the alkyl sulfonate is a linear or may be of branched, preferred branched alkyl chain comprises a C _{1 -6} alkyl group one or more branched portions. More particularly, suitable anionic surfactants include, typically by the formula _{CH 3 (CH 2) x CH} 2 -OSO 3 - M + of C ₁₀ -C ₂₀ 1-class, branched, straight-chain and random-chain alkyl sulphates (AS) (Wherein M is a cation providing hydrogen or charge neutrality, preferably sodium and ammonium cations, x is an integer of at least 7, preferably at least 9); Typically formula

Of C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates, where M is hydrogen or cations providing charge neutrality, preferably sodium and ammonium cations, x is an integer of at least 7, preferably at least 9 , y is an integer of 8 or more, preferably 9 or more); C ₁₀ -C ₁₈ alkyl alkoxy carboxylates; Heavy chain branched alkyl sulfates as described in detail in US Pat. No. 6,020,303 and US Pat. No. 6,060,443; International Publications WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656 Modified alkylbenzene sulfonates (MLAS) and mixtures thereof as described in more detail in WO 00/23549 and WO 00/23548.

Preferred anionic surfactants are C _{8 -18} alkyl benzene sulfates and / or C _{8 -18} alkyl benzene sulphonate. The C _{8 -18} alkyl benzene sulfates and / or C _{8 -18} alkyl chains of the alkylbenzene sulfonate is a linear or may be of branched, preferred branched alkyl chain comprises a C _1-6 alkyl group one or more branched portions.

Other preferred anionic surfactants are C _{8 -18} alkenyl sulfates, C _{8 -18} alkenyl sulfonates, C _{8 -18} alkenyl benzene sulphate, C _{8 -18} alkenyl benzene sulfonate, C _{8 -18} alkyl di- It is selected from alkyl sulfosuccinate, and the group consisting of a combination thereof-methyl benzene sulphate, C _{8 -18} alkyl di-methyl benzene sulphonate, fatty acid ester sulphonates, di. Other anionic surfactants useful in the present invention typically include esters of α-sulfonated fatty acids having 6 to 20 carbon atoms in the fatty acid group and 1 to 10 carbon atoms in the ester group; 2-acyloxy-alkanes-1-sulfonic acid and salts thereof, wherein the acyl group typically has about 2 to 9 carbon atoms and about 9 to 23 carbon atoms in the alkane moiety; Α-olefin sulfonates (AOS), typically having about 12 to 24 carbon atoms; And β-alkoxy alkane sulfonates which typically have about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane moiety. Sulfonated products of fatty acid esters, usually having from 10 to 20 carbon atoms in the alkyl group, are also useful. A C _{1 -4,} and most preferably a methyl ester sulfonate. The C _{16 -18} methyl ester sulfonate (MES) are preferred.

Anionic surfactants may be present in salt form. For example, the anionic surfactant (s) may be an alkali metal salt of any of those described above. Preferred alkali metals are sodium, potassium and mixtures thereof.

Preferred anionic surfactants are washability linear or branched substituted or unsubstituted of C _{12 -18} alkyl sulfates; Linear or branched, substituted or unsubstituted C _{10 -13} alkylbenzene sulfonate, preferably linear C _{10 -13} alkylbenzene sulfonate; And mixtures thereof. Very preferred are linear C _{10 -13} alkylbenzene sulfonates. Very preferred are linear C _{10 -13} alkylbenzene sulfonates obtainable, preferably obtained by sulfonating commercially available linear alkyl benzene (LAB), suitable LABs being selected from lower 2-phenyl LABs, e.g. And those supplied under the trademark Isochem® or those supplied under the trademark Petrelab® by Petresa; other suitable LABs are the higher 2-phenyl LABs, for example, by Sasol. Included under the trade name Hyblene®.

It may be desirable for the anionic washable surfactant to be structurally altered in such a way that the calcium resistance is greater and less likely to precipitate from the wash liquor in the presence of free calcium ions. This structural alteration may be the introduction of a methyl or ethyl moiety in the vicinity of the head group of the anionic washable surfactant, which is due to the steric hindrance of the head group, resulting in a greater calcium tolerant anionic washable surfactant. This may reduce the affinity of the anionic washable surfactant to form a complex with the free calcium cation in a manner that causes precipitation in solution. Other structural modifications include the introduction of a functional moiety, such as an amine moiety, in the alkyl chain of the anionic washable surfactant, whereby the presence of functional groups in the alkyl chain of the anionic washable surfactant is preferred for the anionic washable surfactant. The calcium resistance of the anionic detergent may be greater because it may minimize the physicochemical properties that it does not allow to form a flat crystal structure in the presence of free calcium ions in the wash solution. This may reduce the tendency for the anionic washable surfactant to precipitate out of solution.

Alkoxylation Anionic  Surfactants

The composition may comprise an alkoxylated anionic surfactant. Such surfactants, when present, will generally be present in an amount of from 0.1% to 40% by weight, generally from 0.1 to 10% by weight, based on the detergent composition as a whole. It may be desirable for the composition to contain 3% to 5% by weight of alkoxylated anionic washable surfactant, or the composition contains 1% to 3% by weight of alkoxylated anionic washable surfactant. It may be desirable.

Preferably, the alkoxylated anionic surfactant washability average alkoxy degree of 1 to 30, preferably a substituted or unsubstituted C _{12 -18-alkyl} alkoxylated sulfates of 1 to 10 linear or branched. Preferably, the alkoxylated anionic surfactant washability is a substituted or unsubstituted C _{12 -18-alkyl} ethoxylated sulfate, a linear or branched butoxy the degree of 1 to 10 on average. Most preferably, the alkoxylated anionic surfactant is an ethoxy washability degree of 3 to 7 is a linear unsubstituted C _{12 -18-alkyl} ethoxylated sulfate to the average.

The alkoxylated anionic washable surfactant may also increase the activity of the non-alkoxylated anionic washable surfactant by allowing the non-alkoxylated anionic washable surfactant to precipitate less from the solution in the presence of free calcium cations. Preferably, the weight ratio of non-alkoxy anionic washable surfactant to alkoxylated anionic washable surfactant is less than 5: 1, or less than 3: 1, or less than 1.7: 1, or even less than 1.5: 1. This ratio provides optimum white retention performance with good rigid resistance profile and good foaming profile. However, it may be desirable for the weight ratio of the non-alkoxy anionic washable surfactant to alkoxylated anionic washable surfactant to be greater than 5: 1, or greater than 6: 1, or greater than 7: 1, or even greater than 10: 1. have. This ratio provides an excellent stiffness resistance profile and a good foaming profile, as well as optimal cleaning ability for such contaminants. Suitable alkoxylated anionic washable surfactants include Coxnis' Texapan LEST ™; Cosmacol AESTM from Sasol; Stephan's BES151TM; Empicol ESC70 / UTM; And mixtures thereof.

Nonionic Detergency  Surfactants

The composition of the present invention may comprise a nonionic surfactant. If present, it is generally present in an amount of 0.5% to 20%, more typically 0.5 to 10% by weight, based on the total weight of the composition. The composition may comprise from 1% to 7% by weight or from 2% to 4% by weight of nonionic washable surfactant. The inclusion of nonionic washable surfactants in the composition helps to provide a good overall cleaning profile, especially when laundering at high temperatures, for example 60 ° C. or higher.

Nonionic washable surfactants include C ₁₂ -C ₁₈ alkyl ethoxylates such as Shell's NEODOL® nonionic surfactants; C ₆ -C ₁₂ alkyl phenol alkoxylates, wherein the alkoxylate units are ethyleneoxy units or propyleneoxy units or mixtures thereof; Condensates of C ₁₂ -C ₁₈ alcohols and C ₆ -C ₁₂ alkyl phenols with ethylene oxide / propylene oxide block polymers such as BASF's Pluronic®; C ₁₄ -C ₂₂ heavy chain branched alcohol, BA, disclosed in more detail in US Pat. No. 6,150,322; C ₁₄ -C ₂₂ heavy chain branched alkyl alkoxylates, BAE _x , wherein x is 1 to 30, disclosed in more detail in US Pat. No. 6,153,577, US Pat. No. 6,020,303, and US Pat. No. 6,093,856; Alkylpolysaccharides disclosed in more detail in US Pat. No. 4,565,647, specifically alkylpolyglycosides disclosed in more detail in US Pat. No. 4,483,780 and US Pat. No. 4,483,779; Polyhydroxy fatty acid amides disclosed in more detail in US Pat. No. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038 and WO 94/09099; Ether capped poly (oxyalkylated) alcohol surfactants disclosed in more detail in US Pat. Nos. 6,482,994 and WO 01/42408; And mixtures thereof.

Nonionic washable surfactants may be alkyl polyglucosides and / or alkyl alkoxylated alcohols. Preferably, the non-ionic surfactant washability ethoxy degree of 1 to 50, more preferably 3 to 40 is a linear or branched substituted or unsubstituted C _{8 -18} alkyl ethoxylated alcohol of the average terrain. Nonionic surfactants having an ethoxylation degree of 3 to 9 may also be particularly useful. Nonionic surfactants having an HLB value of 13 to 25, for example C _8-18 alkyl ethoxylated alcohols having an average ethoxylation of 15 to 50, or even 20 to 50, are also preferred nonionic surfactants in the compositions of the present invention. It may be best. Examples of these nonionic surfactants described below include Lutensol AO30 and similar materials disclosed in WO 04/041982. These may be beneficial as they have good lime soap dispersant properties.

Nonionic washable surfactants not only provide the ability to clean additional contaminants, but may also increase the activity of the anionic washable surfactant by allowing less anionic washable surfactant to precipitate out of solution in the presence of free calcium cations. Preferably, the weight ratio of non-alkoxy anionic washable surfactant to nonionic washable surfactant is less than 8: 1, or less than 7: 1, or less than 6: 1 or less than 5: 1, preferably 1: 1. To 5: 1, or 2: 1 to 5: 1, or even 3: 1 to 4: 1.

Cationic Detergency  Surfactants

In one aspect of the invention, the detergent composition does not contain cationic surfactants. However, the composition may optionally comprise 0.1% to 10% or 5% by weight of cationic washable surfactant. However, it is preferred that the composition, if present, comprises from 0.5% to 3%, or from 1% to 3%, or even from 1% to 2% by weight of cationic washable surfactant. This is the optimal level of cationic washable surfactant to provide good detergency. Suitable cationic washable surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds and alkyl tertiary sulfonium compounds. Cationic washable surfactants include alkoxylate quaternary ammonium (AQA) surfactants as disclosed in more detail in US Pat. No. 6,136,769; Dimethyl hydroxyethyl quaternary ammonium, disclosed in more detail in US Pat. No. 6,004,922; Polyamine cationic surfactants disclosed in more detail in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; Cationic ester surfactants disclosed in more detail in US Pat. No. 4,228,042, US Pat. No. 4,239,660, US Pat. No. 4,260,529 and US Pat. No. 6,022,844; Amino surfactants disclosed in more detail in US Pat. Nos. 6,221,825 and WO 00/47708, specifically amino propyldimethyl amines; And mixtures thereof. Preferred cationic surfactants washability formula ^{(R) (R 1) (} R 2) (R 3) N + X - a quaternary ammonium compound, wherein, R is a substituted or unsubstituted linear or branched C _{6 -18} Alkyl or alkenyl moiety, R ¹ and R ² are independently selected from methyl or ethyl moiety, R ³ is hydroxyl, hydroxymethyl or hydroxyethyl moiety, X is an anion providing charge neutrality, and Anions include halides (eg chloride), sulfates and sulfonates]. Preferred cationic surfactants are mono washability -C _{6 -18} alkyl mono-hydroxyethyl dimethyl quaternary ammonium is hydroxy chloride. Highly preferred cationic surfactants are the mono washability -C _{8 -10} alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride, mono _-12 -C ₁₀ alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride and mono--C ₁₀ alkyl mono -Hydroxyethyl dimethyl quaternary ammonium chloride. Cationic surfactants, such as Praepagen HY (trade name Clariant), may also be useful as suds boosters.

Cationic washable surfactants provide the ability to clean additional greasy contaminants. However, cationic washable surfactants may increase the tendency for any non-alkoxylated anionic washable surfactant to precipitate out of solution. Preferably, the cationic washable surfactant and any non-alkoxylated anionic washable surfactant are separated in the detergent composition of the present invention, for example if a cationic surfactant is present, preferably cationic and optional Anionic surfactants, especially non-alkoxylated anionic surfactants, will be present in the composition as individual particles. This minimizes any influence that any cationic washable surfactant may have on the undesirable precipitation of the anionic washable surfactant, and also ensures that the resulting wash liquid does not become cloudy upon contact with water. If a cationic surfactant is present, the weight ratio of the non-alkoxy anionic surfactant to cationic detergent is preferably 5: 1 to 25: 1, more preferably 5: 1 to 20: 1 or 6: 1 to 15: 1, or 7: 1 to 10: 1, or even 8: 1 to 9: 1.

Typically, the detergent composition comprises 1 to 50% by weight, more typically 2 to 40% by weight, of anionic surfactants. Alkyl benzene sulfonates are preferred anionic surfactants.

Preferred compositions of the present invention comprise two or more different surfactants in combination, one or more selected from the first group comprising alkyl benzene sulfonates and MES surfactants; At least one is selected from a second group comprising alkoxylated anionic surfactants, MES and alkoxylated nonionic surfactants and alpha olefin sulfonates (AOS). Particularly preferred combinations include alkyl benzene sulfonates, preferably LAS, in combination with MES. More particularly preferred combination is an alkoxylated anionic surfactant, preferably to an average alkoxy degree of 1 to 10 C _{8 -18} alkyl alkoxylated alkyl sulfates with a benzene sulfonate, preferably comprises LAS. Thirdly, particularly preferred combinations are the alkoxylated nonionic surfactant, preferably an alkoxy degree of 15 to 50, preferably from 20 to 40 - C _{8 -18} alkyl in combination with the alkyl ethoxylated alcohol sulfonate, preferably Includes LAS.

The weight ratio of surfactant selected from the first group to the surfactant selected from the second group is typically 1: 5 to 100: 1, preferably 1: 2 to 100: 1 or 1: 1 to 50: 1 or even 20 : 1 or 10: 1. The levels of surfactants are as described above for certain classes of surfactants. The presence of AE3S and / or MES in the system is desirable due to their exceptional hardness-resistance and the ability to disperse lime soaps formed during washing with lipases.

In a further aspect, the surfactant in the detergent composition of the present invention comprises at least three surfactants, i.e. at least one surfactant from each of the first and second groups defined above, and also preferably the agents defined above. Further third surfactant from one group or the second group.

The detergent compositions of the present invention may comprise surprisingly low levels of surfactants, but still exhibit good cleaning performance due to the decontamination functionality provided by lipases, such that the overall level of surfactants is the total of the composition. It may be less than 12 weight percent, or less than 10 weight percent or 8 weight percent based on weight.

In a preferred embodiment of the invention, the detergent composition also comprises a foam promoter, typically in an amount of 0.01 to 10% by weight, preferably in an amount of 0.02 to 5% by weight, based on the total weight of the composition. Suitable foaming accelerators include fatty acid amides, fatty acid alkaloneamides, betaines, sulfobetaines and amine oxides. Particularly preferred materials are cochamidopropyl betaine, cocomonoethanolamide and amine oxide. Suitable amine oxides are Admox 12 supplied by Albermarle.

Lime soap Dispersant

Since these lipase enzymes release contaminants into the wash water, it may be particularly desirable for the detergent composition of the invention to additionally comprise an anti-redeposition polymer, for example the polymeric polycarboxylate described below. In addition, or alternatively, cellulose ethers such as carboxymethyl cellulose (CMC) will be useful. Suitable CMC is Tylose CR1500 G2 sold by Clariant. Suitable polymers are also sold by Andercol, Colombia under the trade name Textilan.

Additives with lime soap dispersion functionality, for example MES, AES, high ethoxylated nonionic surfactants described above or polymers exhibiting good lime soap dispersion, for example Acusol 460N (Rohm & Haas It is particularly preferable to include)). A list of suitable lime soap dispersants is provided in the following references and documents cited herein:

International Publications WO 94/07974 (P & G), WO 94/07984 (P & G), WO 94/07985 (P & G), WO 95/04806 (P & G), WO 97/03379 ( P & G), US Patent 670610 (Clariant), European Patent 0324568 (Rom and Haas), European Patent 068370 (Rom and Haas), MK. Nagarajan and W.F. Masler, Cosmetics and Toiletries, 1989, 104, pp 71-73, W. M. Linfield, Tenside Surf. Det, 1990, 27, pp 159-161, R.G. Bistline et al, J. Am. Oil Chem. Soc, 1972, 49, pp 63-69]

It has been found that the presence of oil release polymers is particularly effective in further enhancing the stain removal and cleaning effects to be improved, especially for synthetic fibers. Preference is given to modified cellulose ethers such as methyl hydroxyethyl cellulose (MHEC) such as for example sold by Clariant as Tylos MH50 G4 and Tylos MH300 G4. Polyester based antifouling polymers are particularly preferred because they can also be effective as lime soap dispersants. Examples of suitable materials include Repel-o-Tex PF (supplied by Rhodia), Texcare SRA100 (supplied by Clariant) and socalan SR100 (Basf) have.

The formulation may comprise one or more other enzymes, such as proteases, amylases, cellulases (particularly endoglucanase), pectate lyases and / or mananases, in addition to the first washing lipase. have.

Detergent compositions of the present invention may be in any convenient form, for example a solid, for example a powder, granule or tablet solid, bar, or liquid, gel or liquid gel, which may be aqueous or non-aqueous ( liquigel). Any of these forms may be partially or fully encapsulated. However, the present invention relates in particular to solid detergent compositions, in particular granular compositions. If the detergent composition of the invention is a solid, the surfactants are usually incorporated into aggregates, extrudates or spray dried particles together with a solid material which is generally an enhancer, which produces a fully formulated detergent composition according to the invention. It may be mixed in order to. The detergent compositions of the invention when present in granular form are preferably those having a total bulk density of 350 to 1200 g / l, more preferably 450 to 1000 g / l or even 500 to 900 g / l. Preferably, the detergent particles of the detergent composition in the form of granules have a size average particle size of 200 μm to 2000 μm, preferably 350 μm to 600 μm.

Generally the detergent composition of the present invention will contain a mixture of detergent particles comprising agglomerates, spray dried powders and / or dry added substances such as bleach, enzymes and the like.

In one aspect of the invention, the detergent compositions of the invention comprise anionic surfactants which are non-alkoxylated anionic washable surfactants listed above, which preferably comprise, for example, aggregates, spray dried powders, It is incorporated into specific forms through extrudates, beads, noodles, needles, or flakes. Spray dried particles are preferred. When incorporated through the agglomerate, the agglomerate preferably contains at least 20% by weight, more preferably 25% to 65% by weight of the non-alkoxy anionic washable surfactant, based on the weight of the aggregate. Some of the non-alkoxy anionic washable surfactant is present in the form of a spray dried powder (eg blown powder) and some of the non-alkoxy anionic washable surfactant is in the form of a non-spray dry powder (eg For example, aggregates, or extrudates, or flakes, such as linear alkyl benzene sulfonate flakes; suitable linear alkyl benzene sulfonate flakes are trademarked by Pilot Chemical under the trade name F90® or by Stepan. It may be preferred to be present as Naconol 90G®. This is particularly preferred when it is desirable to incorporate high levels of non-alkoxy anionic washable surfactant into the composition.

Any alkoxylated anionic washable surfactant may be incorporated into the detergent composition of the present invention through spray dried particles of non-spray dry powder such as extrudates, aggregates, preferably aggregates. Non-spray dry particles are particularly preferred when it is desired to incorporate a high level of alkoxylated anionic washable surfactant into the composition.

Any nonionic washable surfactant or at least a portion thereof may be incorporated into the composition in the form of a liquid spray-on, and may be a nonionic washable surfactant in liquid form (eg, in the form of a hot-melt) or At least a portion thereof is sprayed onto the remaining composition. The nonionic washable surfactant or at least a portion thereof may be included in the microparticles for incorporation into the detergent composition of the present invention and the nonionic washable surfactant or at least a portion thereof may be dry-added to the remaining composition. The nonionic surfactant or at least a portion thereof may be present in the form of a co-particulate mixture with a solid carrier material, for example carbonate, sulfate salt, burkeite, silica or any mixture thereof.

Any nonionic washable surfactant or at least a portion thereof may be present in the form of a co-particulate mixture with an alkoxylated anionic washable surfactant, non-alkoxylated anionic washable surfactant or cationic washable surfactant. The nonionic washable surfactant or at least a portion thereof may be aggregated or extruded together with the alkoxylated anionic washable surfactant, non-alkoxylated anionic washable surfactant or cationic washable surfactant.

Cationic washable surfactants, when present, may be incorporated into the present compositions by incorporation into particulates such as spray dried powders, aggregates, extrudates, flakes, noodle, needles, or any combination thereof. Preferably, the cationic washable surfactant or at least part thereof is in the form of a spray dried powder or aggregate.

Any detergent supplement

Optionally, the detergent component may include one or more other detergent aids or other materials to aid or enhance the cleaning action, to treat the substrate to be cleaned, or to modify the aesthetic properties of the detergent composition. Common detergent auxiliaries for detergent compositions include the components shown in US Pat. No. 3,936,537 to Baskerville et al. And British Patent Application No. 9705617.0 to Trin et al., Published September 24, 1997. Such adjuvants are included in the detergent composition at their usual level of use as defined in the prior art, generally from 0% to about 80%, preferably from about 0.5% to about 20% by weight of the surfactant component, and colored Speckles, foam accelerators, foam inhibitors, antitarnish and / or preservatives, soil-suspending agents, antifouling agents, dyes, fillers, optical brighteners, bactericides, alkaline sources, hydro Hydrotrope, antioxidants, enzymes, enzyme stabilizers, solvents, solubilizers, chelating agents, clay contaminant removal / re-deposition agents, polymeric dispersants, processing aids, fabric softening ingredients, electrostatic modifiers, bleaching agents, bleach activators, Bleach Stabilizers, Disinfectants, Flocculants, Fabric Softeners, Foam Inhibitors, Fabric Integrity Agents, Fragrances, Whitening Agents, Photobleaching Agents, Alkali Metal Sulfate Salts, Sulfam , It includes sodium sulfate, and complexes such as sulfamic acid, and combinations thereof. The exact nature of these additional ingredients and the level of incorporation thereof will depend on the physical form of the composition or ingredient and the exact nature of the cleaning operation in which it is used.

Preferred zwitterionic surfactants include one or more quaternized nitrogen atoms and one or more moieties selected from the group consisting of carbonates, phosphates, sulfates, sulfonates and combinations thereof. Preferred zwitterionic surfactants are alkyl betaines. Another preferred zwitterionic surfactant is alkyl amine oxide. Cationic surfactants, which are complexes comprising cationic surfactants and anionic surfactants, may also be included. Typically, the molar ratio of cationic surfactant to anionic surfactant in the complex is greater than 1: 1 so that the complex has a net positive charge.

The composition of the present invention may contain a bleach promoter. Preferred bleach promoters are selected from the group consisting of zwitterionic imines, anionic imine multi-ions, quaternary oxaziridinium salts and combinations thereof. Highly preferred bleach promoters are selected from the group consisting of arylimium zwitterions, arylimium multi-ions and combinations thereof. Suitable bleach promoters are disclosed in US 360360, US 5360569 and US 5370826.

Preferred auxiliary components are re-deposition inhibitors. Preferably, the detergent composition contains one or more antideposition agents. Preferred anti-deposition agents are cellulose polymer components, most preferably carboxymethyl cellulose.

Preferred auxiliary components are chelating agents. Preferably the detergent composition contains one or more chelating agents. Preferably the detergent composition comprises 0.01% to 10% chelating agent, or 0.01 to 5% or 4% or 2% chelating agent (based on the weight of the composition). Preferred chelating agents are: hydroxyethane-dimethylene-phosphonic acid, ethylene diamine tetra (methylene phosphonic) acid, diethylene triamine penacetate, ethylene diamine tetraacetate, diethylene triamine penta (methyl phosphonic) acid, Ethylene diamine disuccinic acid and combinations thereof.

Preferred adjunct ingredients are ear salt inhibitors. Preferably, the detergent composition contains one or more otitis inhibitors. Typically, the desalination inhibitor is a polymeric component that retains the dye molecules by trapping the dye molecules and suspending them in the wash liquor. Preferred disinfection inhibitors are selected from the group consisting of polyvinylpyrrolidone, polyvinylpyridine N-oxides, polyvinylpyrrolidone-polyvinylimidazole copolymers and combinations thereof.

Preferred accessory ingredients include other enzymes. Preferably, the detergent composition contains one or more additional enzymes. Preferred enzymes are amylase, arabinosidase, carbohydrase, cellulase, chondroitinase, cutinase, dextranase, esterase, β-glucanase, gluco-amylase, hyaluronidase, Keratanase, laccase, ligninase, lipoxygenase, malanase, mannase, oxidase, pectinase, pentosanase, peroxidase, phenol oxidase, phospholipase, protease, pullulanase, reductase Selected from the group consisting of azeases, tanases, transferases, xylanases, xyloglucanases and combinations thereof. Preferred additional enzymes are selected from the group consisting of amylases, carbohydrases, cellulases, proteases and combinations thereof.

Preferred additional components are fabric preservatives. Preferably the detergent composition contains one or more fabric preservatives. Typically, fabric preservatives are polymeric ingredients that are deposited on the fabric surface to prevent fabric damage during the laundry process. Preferred fabric preservatives are hydrophobically modified celluloses. This hydrophobically modified cellulose reduces fabric wear, improves fiber-fiber interactions and reduces the loss of dyes from the fabric. Preferred cellulose modified with hydrophobicity is disclosed in WO 99/14245. Other preferred fabric preservatives are polymer components and / or oligomer components obtainable by a process comprising the condensation step of imidazole and epichlorhydrin, preferably obtained by the process.

Preferred auxiliary components are salts. Preferably the detergent composition contains one or more salts. Salts can act as alkaline imparting agents, buffers, enhancers, co-enhancers, deposition inhibitors, fillers, pH adjusters, stabilizers and combinations thereof. Typically, the present detergent composition contains 5% to 60% salt (based on the weight of the composition). Preferred salts are alkali metal salts of aluminates, carbonates, chlorides, bicarbonates, nitrates, phosphates, silicates, sulfates and combinations thereof. Other preferred salts are alkaline earth metal salts of aluminates, carbonates, chlorides, bicarbonates, nitrates, phosphates, silicates, sulfates and combinations thereof. Particularly preferred salts are sodium sulfate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulfate and combinations thereof. Optionally, the alkali metal salts and / or alkaline earth metal salts may be anhydrides.

Preferred auxiliary components are antifouling agents. Preferably the detergent composition contains one or more antifouling agents. Typically, antifouling agents are polymeric compounds that modify the fabric surface to prevent redeposition of contaminants on the fabric. Preferred antifouling agents are copolymers comprising at least one terephthalate unit, preferably block copolymers. Preferred antifouling agents are copolymers synthesized from dimethylterephthalate, 1,2-propyl glycol and methyl capped polyethyleneglycol. Another preferred antifouling agent is anionic end capped polyester.

The composition of the present invention is 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 and at most 30% by weight or at most 20% by weight or at most 10% by weight. It may be desirable to contain polycarboxylates. Preferred polymeric polycarboxylates include polyacrylates and copolymers of maleic acid and acrylic acid. Suitable polycarboxylates are small callan CP, PA and HP classes (BASF), such as small callan CP5, PA40 and HP22, and alcos polymer classes (Alco), such as Alcosperse 725, 747, 408, 412 and 420.

The composition comprises contaminant dispersants, for example the formula bis ((C ₂ H ₅ O) (C ₂ H ₄ O) n) (CH ₃ ) -N ⁺ -C _x H _2x -N ⁺ -(CH ₃ ) -bis It may also be desirable to contain a contaminant dispersant of ((C ₂ H ₅ O) (C ₂ H ₄ O) n, where n is 20 to 30 and x is 3 to 8). Other suitable contaminant dispersants include the formula sulfonated or sulfated bis ((C ₂ H ₅ O) (C ₂ H ₄ O) n) (CH ₃ ) -N ⁺ -C _x H _2x -N ⁺ -(CH ₃ ) Sulfonated or sulfated contaminant dispersant of -bis ((C ₂ H ₅ O) (C ₂ H ₄ O) n), where n is 20-30 and x is 3-8. Preferably, the composition contains at least 1 weight percent, or at least 2 weight percent, or at least 3 weight percent contaminant dispersant.

Flexible system

Detergent compositions of the invention may also comprise a softening agent for softening through washing, for example clay, optionally together with flocculants and enzymes.

Further details regarding suitable detergent components can be found in WO 97/11151.

How to wash

The present invention also includes a method for washing a fabric comprising contacting the fabric with an aqueous solution comprising the detergent composition of the present invention. The present invention may be particularly advantageous at low water temperatures, for example below 30 ° C or below 25 ° C or 20 ° C. Typically, the aqueous wash liquid will comprise a detergent composition of at least 100 ppm, or at least 500 ppm.

The following is an example of the present invention.

<110> THE PROCTER & GAMBLE COMPANY <120> Dertergent compositions <130> CM2956M <150> EP 05251269.6 <151> 2005-03-03 <160> 1 <170> KopatentIn 1.71 <210> 1 <211> 291 <212> PRT <213> Humicola lanuginosa <400> 1 Met Arg Ser Ser Leu Val Leu Phe Phe Val Ser Ala Trp Thr Ala Leu   1 5 10 15 Ala Ser Pro Ile Arg Arg Glu Val Ser Gln Asp Leu Phe Asn Gln Phe              20 25 30 Asn Leu Phe Ala Gln Tyr Ser Ala Ala Ala Tyr Cys Gly Lys Asn Asn          35 40 45 Asp Ala Pro Ala Gly Thr Asn Ile Thr Cys Thr Gly Asn Ala Cys Pro      50 55 60 Glu Val Glu Lys Ala Asp Ala Thr Phe Leu Tyr Ser Phe Glu Asp Ser  65 70 75 80 Gly Val Gly Asp Val Thr Gly Phe Leu Ala Leu Asp Asn Thr Asn Lys                  85 90 95 Leu Ile Val Leu Ser Phe Arg Gly Ser Arg Ser Ile Glu Asn Trp Ile             100 105 110 Gly Asn Leu Asn Phe Asp Leu Lys Glu Ile Asn Asp Ile Cys Ser Gly         115 120 125 Cys Arg Gly His Asp Gly Phe Thr Ser Ser Trp Arg Ser Val Ala Asp     130 135 140 Thr Leu Arg Gln Lys Val Glu Asp Ala Val Arg Glu His Pro Asp Tyr 145 150 155 160 Arg Val Val Phe Thr Gly His Ser Leu Gly Gly Ala Leu Ala Thr Val                 165 170 175 Ala Gly Ala Asp Leu Arg Gly Asn Gly Tyr Asp Ile Asp Val Phe Ser             180 185 190 Tyr Gly Ala Pro Arg Val Gly Asn Arg Ala Phe Ala Glu Phe Leu Thr         195 200 205 Val Gln Thr Gly Gly Thr Leu Tyr Arg Ile Thr His Thr Asn Asp Ile     210 215 220 Val Pro Arg Leu Pro Pro Arg Glu Phe Gly Tyr Ser His Ser Ser Pro 225 230 235 240 Glu Tyr Trp Ile Lys Ser Gly Thr Leu Val Pro Val Thr Arg Asn Asp                 245 250 255 Ile Val Lys Ile Glu Gly Ile Asp Ala Thr Gly Gly Asn Asn Gln Pro             260 265 270 Asn Ile Pro Asp Ile Pro Ala His Leu Trp Tyr Phe Gly Leu Ile Gly         275 280 285 Thr cys leu     290  

Claims (10)

Hydrogen peroxide source; Hydrophobic peracids of the formula R- (C═O) -L, wherein R is an alkyl group having 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms, and L is a leaving group; and / or a precursor thereof; And (a) greater than or equal to 90% identity with wild-type lipase derived from Fumicola ranuginosa strain DSM 4109, and (b) compared to the wild-type lipase, at the surface of a three-dimensional structure within 15 의 of E1 or Q249. And a neutral or negatively charged amino acid substituted with a positively charged amino acid, (c) comprising a peptide addition at the C-terminus, and (d) a peptide addition at the N-terminus (e) i) a negative amino acid at position E210 of the wild-type lipase, ii) a negatively charged amino acid in a region corresponding to positions 90-101 of the wild-type lipase, iii) N94 of the wild-type lipase Restrictions that include a neutral or negative amino acid at a position corresponding to and / or have a net charge that is negative or neutral at a region corresponding to positions 90-101 of the wild-type lipase As a group, detergent composition comprising a polypeptide of the lipase enzyme having the amino acid sequence of, The reserve alkalinity is greater than 6.5, and the amount of oxygen and peracid and / or precursor thereof available (from the peroxide source) is equal to the molar ratio of available oxygen to peracid (from the peroxide source) of 1: 1. To 35: 1 to provide a detergent composition. The detergent composition of claim 1, wherein the preliminary alkalinity is greater than 8 or greater than 9. The detergent composition according to claim 1 or 2, wherein the available oxygen: peracid ratio is from 2: 1 to 8: 1. The detergent composition according to any one of claims 1 to 3, wherein the hydrophobic bleach activator comprises nonanoyloxybenzene sulfonate. Any one of claims 1 to 4 according to any one of, wherein the alkoxylated alkyl sulphate surfactant, from 0.1 to 40% by weight and / or C _{1 -4} alkyl ester sulfonates, preferably methyl ester sulphonate (MES) 0.1 to 40 A detergent composition comprising 5% by weight, preferably 5-40% by weight alkyl benzene sulfonate surfactant. The amount of the foam promoter according to any one of claims 1 to 5, preferably selected from fatty acid amides, fatty acid alkanolamides, betaines, sulfobetaines, amine oxides, and mixtures thereof. Detergent composition comprising a. 7. Detergent composition according to any one of the preceding claims, comprising 0.05 to 5% by weight, preferably 0.1 to 1% by weight of tetra acetyl ethylene diamine (TAED). 8. Detergent composition according to any one of claims 1 to 7, which is solid, preferably granular. A method of washing, comprising washing a textile product in an aqueous solution comprising the detergent composition according to any one of claims 1 to 8. The washing method of Claim 9 whose temperature of aqueous solution is less than 30 degreeC.