BR112018068068B1 - LIQUID AQUEOUS COMPOSITION OF DETERGENT FOR WASHING CLOTHES AND DOMESTIC METHOD OF TREATMENT OF A FABRIC - Google Patents

Abstract

The present invention provides an alkoxylated polyethyleneimine and surfactant formulation for use in home laundry.

Description

Field of Invention

[0001] The present invention provides an alkoxylated polyethyleneimine polymer and surfactant formulation for use in home laundry.

Background of the Invention

[0002] The liquid formulation for home laundry containing linear alkylbenzene sulfonate surfactant, alkyl ether sulfate surfactant and low levels of nonionic surfactant and zwitterionic surfactant is ubiquitous. To enhance cleaning performance, alkoxylated polyethyleneimine polymers, preferably in combination with polyethylene terephthalate polymer for soil removal. The addition of these polymers significantly reduces the viscosity of the formulation. Effective methods are needed to increase the viscosity of the formulation, which do not reduce the surfactant level.

[0003] Document WO2013/087286 (Unilever) discloses liquid formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant and nonionic surfactant to provide softening benefits.

[0004] WO2014/060235 (Unilever) discloses a laundry detergent composition comprising (a) nonionic surfactant, (b) anionic surfactant, (c) alkyl ether carboxylic acid or carboxylate salt thereof, and, ( d) a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine; and its use to soften fabrics.

Summary of the Invention

[0005] Surprisingly, it was found that partial or complete replacement of the anionic surfactant alkyl ether sulfate by the anionic surfactant alkyl ether carboxylic acid increases the viscosity of the formulation.

[0006] In one aspect, the present invention provides an aqueous liquid laundry detergent composition comprising: (i) from 2% to 10% by weight, preferably from 2.5% to 5% by weight, of sulfonate surfactant anionic linear alkylbenzene; (ii) from 0.5% to 4% by weight, preferably 1.5% to 2.5% by weight, of zwitterionic surfactant selected from: amine oxide and carbobetaines; (iii) from 0.1% to 4% by weight, preferably 0.5% to 2% by weight, of an alkali metal salt, preferably NaCl; (iv) from 1% to 5% by weight, preferably 1.5% to 4% by weight, of an alkoxylated polyethyleneimine, preferably ethoxylated polyethyleneimine; (v) from 1% to 10% by weight, preferably from 2% to 6% by weight, more preferably from 3% to 5% by weight of an alkyl ether carboxylic acid anionic surfactant of the following structure: R2-(OCH2CH2 )n-OCH2-COOH, wherein: R2 is selected from C10 to C26 straight or branched saturated or monounsaturated alkyl chains, preferably C12 to C20 straight alkyl chains, more preferably a C16 to C18 straight alkyl chain and wherein n is selected from: 6 to 20, preferably from 7 to 13, more preferably from 8 to 12, most preferably from 9.5 to 10.5; (vi) from 0% to 10% by weight, preferably from 2.5% to 5% by weight, of anionic surfactant alkyl ether sulfate with 0.5 to 1.5 mol equivalent of ethoxylation, preferably 0.9 to 1.2 ; (vii) from 0% to 2% by weight, preferably 0.2% to 1% by weight of a terephthalate polyester soil release polymer; (viii) from 0% to 4% by weight, preferably from 0% to 1% by weight, of a nonionic surfactant; and (ix) from 0.0% to 0.2% by weight, preferably from 0.002% to 0.02% by weight, of a protease enzyme, wherein the laundry detergent composition comprises in total from 10% to 20 % by weight of anionic surfactant.

[0007] In yet another aspect, the present invention provides a method of home treating a fabric, the method comprising the steps of: (i) treating a fabric with from 1 g/L of an aqueous solution of the liquid aqueous composition laundry detergent as defined in the first aspect of the invention; and, (ii) allowing said aqueous laundry detergent solution to remain in contact with the fabric for 10 minutes to 2 days, then rinsing and drying the fabric.

[0008] In the method aspects of the present invention, the surfactant used is preferably as preferred for the composition aspects of the present invention.

[0009] Domestic methods are preferably conducted in a domestic washing machine or by means of manual washing. The wash temperature is preferably 285 to 313 K. The main wash time is preferably 5 to 30 minutes.

[0010] The fabric is preferably an item of clothing, bedding or tablecloth. Preferred items of clothing are shirts, pants, underwear, and sweaters that contain cotton.

Detailed Description of the Invention Linear Alkylbenzene Sulfonate

[0011] Linear alkylbenzene sulfonate weights are calculated in the protonated form. Linear alkylbenzene sulfonate has an alkyl chain length of C8 to C15, preferably C12 to C14.

[0012] Linear alkylbenzene sulfonate (LAS) can be obtained by sulfonation of commercially available linear alkylbenzene (LAB); suitable LAB includes low 2-phenyl LAB such as those supplied by Sasol under the trademark Isochem® or those supplied by Petresa under the trademark Petrelab®, other suitable LAB includes high 2-phenyl LAB such as those supplied by Sasol under the trademark Hyblene®. Another suitable route is the alkylbenzene sulfonate which is obtained by the DETAL catalyzed process, which preferably has 8 to 15 carbon atoms. Other synthetic routes, such as HF, may also be suitable.

Alkyl Ether Sulfate

[0013] The weights of alkyl ether sulfate are calculated in the protonated form, R1-(OCH2CH2)m-OSO3H. Preferably, R1 is a linear saturated or unsaturated C10 to C22 alkyl chain, more preferably a linear saturated C12 to C16 alkyl chain, most preferably a linear C12 alkyl chain (lauryl). The average number of moles of ethoxylation per mole of surfactant is m, m is preferably 0.5 to 1.5.

Alkyl Ether Carboxylic Acid

[0014] Alkyl ether carboxylic acid weights are calculated as the protonated form, R2-(OCH2CH2)n-OCH2COOH. These can be used as a salt version, for example sodium salt or amine salt.

[0015] The alkyl chain can be straight or branched, preferably it is straight.

[0016] The alkyl chain may be aliphatic or contain a cis or trans double bond.

[0017] The alkyl chain is preferably selected from CH3(CH2)15, CH3(CH2)17, CH3(CH2)7CH=CH(CH2)8-.

[0018] The alkyl ether carboxylic acid most preferably has the structure: CH3(CH2)7CH=CH(CH2)8(OCH2CH2)10OCH2COOH.

[0019] Carboxylic acid alkyl ether is available from Kao (Akypo®), Huntsman (Epicol®) and Clariant (Emulsogen®). zwitterionic surfactant

[0020] The zwitterionic surfactant contains a C8 to C16 linear aliphatic alkyl chain and a positively and negatively charged atom within the surfactant molecule. Preferred zwitterionic surfactants are betaine and amine oxides.

[0021] The amine oxide is preferably of the structure:

[0022] Preferably, R3 is C12-C14, more preferably C12 (lauryl). Amine oxides are available from Huntsman, for example, Empigen® OB.

[0023] The betaine is preferably a carbebetaine. Carbobetaine is preferably selected from the structures:

[0024] Preferably, R4 is C12-C14, more preferably C12 (lauryl). Betaines are available from Huntsman, eg Empigen® BB. Cocoamidopropyl betaine (CAS No. 61789-40-0) is most preferred.

[0025] The zwitterionic is most preferably a carbebetaine. non-ionic surfactant

[0026] The aqueous liquid laundry detergent may comprise nonionic surfactant, preferably an alkyl ethoxylated nonionic surfactant.

[0027] Suitable non-ionic detergent compounds that can be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids or amides, especially ethylene, either alone or with propylene oxide. Preferred nonionic detergent compounds are the condensation products of linear or branched primary or secondary C8 to C18 aliphatic alcohols with ethylene oxide.

[0028] Preferably, the alkyl ethoxylated nonionic surfactant is a C8 to C18 primary alcohol with a molar average ethoxylation of 7 to 9 EO units.

[0029] Preferably, the fraction (wt% nonionic surfactant)/(wt% anionic surfactant) is 0 to 0.2, more preferably 0 to 0.05. Most preferably, the formulation does not contain a non-ionic surfactant.

Other Surfactants

[0030] The aqueous liquid laundry detergent may comprise from 0 to 4% by weight of other surfactants, for example those described in Surface Active Agents Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of McCutcheon's Emulsifiers and Detergents published by the Manufacturing Confectioners Company or in Tenside-Taschenbuch, H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 or in Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1996).

[0031] Examples of suitable additional anionic detergent compounds are: alkyl sulfates, especially those obtained by sulfated C8 to C18 linear or branched alcohols, soaps; alkyl ester (preferably methyl) sulfonates, and mixtures thereof.

alkoxylated polyethyleneimine

[0032] The alkoxylated polyethyleneimine comprises a column in which the modification of the polyethyleneimine column intends to leave the polymer without quaternization. These materials can be represented as PEI(X)YAO, where X represents the molecular weight of the unmodified PEI and Y represents the average moles of alkoxylation (AO) per NH available on the unsubstituted polyethyleneimine column. Y is preferably from 7 to 40, but preferably is in the range from 16 to 26, more preferably 18 to 22. X is selected to be from approximately 300 to approximately 10,000 average molecular weight and is preferably approximately 600.

[0033] The alkoxylation is preferably selected from ethoxylation or propoxylation, or a combination of the two, with ethoxylation being more preferred. The alkoxy chains can be limited to groups selected from: H; CH3; SO3-; CH2COO-; PO32-; C2H5; n-propyl, i-propyl; n-butyl; t-butyl; It is

sulfosuccinate, more preferably H.

[0034] More preferably, the alkoxylated PEI is PEI(600)20EO. Dirt Release Polyester Terephthalate Polymer

[0035] The polyester terephthalate polymer for dirt release comprises polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols), as described in WO2009/153184, EP2692842 and WO2014/019903.

[0036] Examples of Polyester Terephthalate Polymer for Dirt Release are the REPEL-O-TEX® line of polymers supplied by Rhodia, including REPEL-O-TEX® SRP6 and REPEL-O-TEX® SF-2.

[0037] Other suitable soil release polymers include TexCare® polymers, including TexCare® SRA-100, TexCare® SRA-300, TexCare® SRN-100, TexCare® SRN-170, TexCare® SRN-240, TexCare® SRN -300 and TexCare® SRN-325, all supplied by Clariant.

[0038] Preferred structures are -[(Z)a-O-OC-Ar-CO-]b and (Z)a-O-OC-[Ar-CO-O-C3H6-O-OC]b-Ar-CO-O- (Z)a, wherein Ar is selected from 1,4-substituted phenylene and 1,3-substituted phenylene in the 5-position by a sulfonate group (SO3-); Z is selected from ethoxy, propoxy and mixtures of ethoxy and propoxy; a is from 5 to 100 and b from 2 to 40. C3H6 is i-propyl.

[0039] The alkoxy chains are closed with groups selected from H; CH3; SO3-; CH2COO-; PO32-; C2H5; n-propyl, i-propyl; n-butyl; t-butyl; and sulfosuccinate.

em que c é de 4 a 9; d é de 1 a 3; e é de 40 a 50.[0040] More preferably, the polyester terephthalate soil release polymer is:

wherein c is from 4 to 9; d is from 1 to 3; and it's 40 to 50.

polymers

[0041] The composition may comprise one or more of the following polymers. Examples are carboxymethylcellulose, poly(ethylene glycol), (poly)vinyl alcohol, polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.

[0042] Polymers may be present to prevent dye deposits, for example, poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide) and poly(vinylimidazole).

[0043] These polymers are preferably present at levels of less than 0.5% by weight.

[0044] The composition is preferably devoid of silicone polymers and polymers bearing quaternized N groups.

Complexing and sequestering agents

[0045] The detergent compositions may optionally also contain relatively low levels of complexing agent or organic detergent sequestering material. Examples include alkali metal, citrates, succinates, malonates, carboxymethylsuccinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts, salts of oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, alkyl or alkenylsuccinic acid, nitrilotriacetic acid and citric acid. Other examples are DEQUEST™, organic phosphonate-type sequestering agents available from Monsanto, and alkane hydroxy phosphonates.

[0046] Other suitable organic complexing agents include higher molecular weight polymers and copolymers known to exhibit complexing properties. For example, these materials include suitable polyacrylic acid, polymaleic acid and polyacrylic/polymaleic acid copolymers and their salts, such as those marketed by BASF under the name SOKALAN™.

[0047] If used, the aqueous liquid laundry detergent formulation comprises from 0.1% to 2.0% by weight of complexing agent and sequestering material. Citrate is most preferred.

Toning Dye

[0048] The dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zürich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).

[0049] Toning dyes for use in laundry detergents preferably have a maximum absorption extinction coefficient in the visible range (400 to 700 nm) greater than 5000 L mol-1 cm-1, preferably greater than 10000 L mol-1 1cm-1. The dyes are blue or violet in color.

[0050] Preferred toner dye chromophores are azo, azine, anthraquinone and triphenylmethane.

[0051] Preferred monoazo dyes contain a heterocyclic ring and are most preferably thiophene dyes. Mono-azo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH=7. Alkoxylated thiophene dyes are discussed in WO/2013/142495 and WO/2008/087497. Preferred examples of thiophene dyes are shown below:

[0052] The azine dyes are preferably selected from sulfonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, CAS No. 72749-805, acid blue 59.

[0053] The toning dye is present in the composition in the range of 0.0001% to 0.5% by weight, preferably 0.001% to 0.1% by weight. Depending on the nature of the toning dye, there are preferred ranges depending on the effectiveness of the toning dye, which depends on the particular class and effectiveness within a particular class. As described above, the toning dye is a blue or violet toning dye.

[0054] A mixture of toning dyes can be used.

[0055] The toning dye is most preferably an anthraquinone blue reactive dye covalently linked to an alkoxylated polyethyleneimine. Alkoxylation is preferably selected from ethoxylation and propoxylation, more preferably propoxylation. Preferably, 80% to 95% by mol of the N-H groups in the polyethyleneimine are replaced with isopropyl alcohol groups by propoxylation. Preferably, the polyethyleneimine, prior to reaction with the dye and propoxylation, has a molecular weight of 600 to 1800.

[0056] An example structure of a preferred reactive anthraquinone covalently linked to a propoxylated polyethyleneimine is:

[0057] Preferred reactive anthraquinone dyes are: Reactive Blue 1; Reactive Blue 2; Reactive blue 4; Reactive blue 5; Reactive blue 6; Reactive Blue 12; Reactive blue 16; reactive blue 19; Reactive blue 24; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive Blue 44; Reactive Blue 46; Reactive Blue 47; Reactive Blue 49; Reactive blue 50; Reactive blue 53; Reactive blue 55; Reactive Blue 61; Reactive Blue 66; Reactive Blue 68; Reactive blue 69; Reactive Blue 74; Reactive Blue 86; Reactive Blue 93; Reactive Blue 94; Reactive Blue 101; Reactive Blue 103; Reactive Blue 114; Reactive Blue 117; Reactive Blue 125; Reactive Blue 141; Reactive Blue 142; Reactive Blue 145; Reactive Blue 149; Reactive Blue 155; Reactive Blue 164; Reactive Blue 166; Reactive Blue 177; Reactive Blue 181; Reactive Blue 185; Reactive Blue 188; Reactive Blue 189; Reactive Blue 206; Reactive Blue 208; Reactive Blue 246; Reactive Blue 247; Reactive Blue 258; Reactive Blue 261; Reactive Blue 262; Reactive Blue 263; and Reactive Blue 172.

[0058] Dyes are listed according to the Color Index classification (Society of Dyers and Colourists/American Association of Textile Chemists and Colorists).

Protease Enzyme

[0059] Protease enzymes hydrolyze bonds within peptides and proteins; in the context of laundry, this results in greater removal of stains containing protein or peptide. Examples of suitable protease families include aspartic proteases; cysteine proteases; glutamic proteases; asparagine peptide lyase; serine proteases and threonine proteases. These protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/). Serine proteases are preferred. Subtilase-type serine proteases are more preferred. The term "subtilases" refers to a subgroup of serine proteases according to Siezen et al., Protein Engng. 4 (1991) 719-737 and Siezen et al. Protein Science 6 (1997) 501-523. Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. The subtilases can be divided into 6 subdivisions, namely the Subtilisin family, the Termitase family, the Proteinase K family, the Lantibiotic Peptidase family, the Kexin family and the Pyrolysin family.

[0060] Examples of subtilases are those derived from bacilli, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in documents US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in WO93/18140. Other useful proteases may be those described in WO92/175177, WO01/016285, WO02/026024 and WO02/016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO89/06270, WO94/25583 and WO05/040372, and the Cellumonas-derived chymotrypsin proteases described in WO05/052161 and WO05/052146.

[0061] Other examples of useful proteases are the variants described in: WO92/19729, WO96/034946, WO98/20115, WO98/20116, WO99/011768, WO01/44452, WO03/006602, WO04/03186, WO04/041979 , WO07/006305, WO11/036263, WO11/036264, especially variants with substitutions in one or more of the following positions: 3, 4, 9, 15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 106, 118, 120, 123, 128, 129, 130, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 using BPN' numbering. More preferred subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, *36D, V68A, N76D, N87S,R, *97E, A98S, S99G,D,A, S99AD, S101G,M, R S103A, V104I, Y, N, S106A, G1 18V, R, H120D, N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V205I, L217D, N218D, M222 S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).

[0062] More preferably, the protease is a subtilisin (EC 3.4.21.62).

[0063] Examples of subtilases are those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in documents US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in WO93/18140. Preferably, the subsilisin is derived from bacilli, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in US 6,312,936 B1, US 5,679,630, US 4,760,025, US7,262,042 and WO09/021867. More preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

[0064] Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase®, all could be marketed as Ultra® or Evity® (Novozymes A/S).

[0065] Those marketed under the trade names Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® by Genencor International.

[0066] Those marketed under the trade names Maxatase®, Maxacal®, Maxapem®, Purafect®, Purafect Prime®, PreferenzTm, Purafect MA®, Purafect Ox®, Purafect OxP®, Puramax®, Properase®, EffectenzTm, FN2®, FN3®, FN4®, Excellase®, Opticlean® and Optimase® (Danisco/DuPont), Axapem™ (Gist-Brocases N.V.).

[0067] Those available from Henkel/Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604 with the following mutations S99D + SlOl R + S103A + V104I + G159S, hereinafter referred to as BLAP), BLAP R ( BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D) - all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with mutations A230V + S256G + S259N) from Kao.

[0068] The inclusion of protease in the formulation enhances cleaning.

Other enzymes

[0069] One or more other enzymes are preferably present in a laundry composition of the invention and when practicing a method of the invention.

[0070] Preferably, the level of each enzyme in the laundry composition of the invention ranges from 0.0001% by weight to 0.1% by weight protein.

[0071] Preferably, the additional enzyme is selected from: alpha-amylases; lipases and cellulases.

[0072] Suitable lipases include those of bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), for example from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a lipase from Pseudomonas, for example from P. alcaligenes or from P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1,372,034), P. fluorescens, strain of the species Pseudomonas SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a lipase from Bacillus, eg from B. subtilis ( Dartois et al. (1993), Biochemica et Biophysica Acta , 1131, 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422).

[0073] Other examples are lipase variants such as those described in WO 92/05249, WO 94/01541, EP 407 225, EP 260 105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94 /25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202, and WO 00/60063.

[0074] Preferred commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™ and Lipoclean TM (Novozymes A/S).

[0075] The method of the invention can be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme having activity towards phospholipids.

[0076] Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an external (sn-1) and intermediate (sn-2) position and esterified with phosphoric acid in the third position; phosphoric acid, in turn, can be esterified into an aminoalcohol. Phospholipases are enzymes that participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A1 and A2 which hydrolyze a fatty acyl group (at the sn-1 and sn-2 position, respectively) to form lysophospholipids; and lysophospholipase (or phospholipase B), which can hydrolyze the remaining fatty acyl group into lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid, respectively.

[0077] The method of the invention can be carried out in the presence of cutinase classified in EC 3.1.1.74. The cutinase used according to the invention can be of any origin. Preferably, the cutinases are of microbial origin, in particular of bacterial, fungal or yeast origin.

[0078] Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, for example a special strain of B. licheniformis, described in more detail in GB 1,296,839, or the strains of Bacillus species disclosed in WO 95/026397 or WO 00/ 060060. Commercially available amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™ and BAN™ (Novozymes A/S), Rapidase™ and Purastar™ (from Genencor International Inc.).

[0079] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, for example, the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila and Fusarium oxysporum, disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259, WO 96/029397 and WO 98/012307. Commercially available cellulases include Celluzyme™, Carezyme™, Celluclean™, Endolase™, Renozyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation ). CellucleanTM is preferred.

[0080] Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, for example from C. cinereus, and variants thereof as described in WO 93/24618, WO 95/10602 and WO 98/15257. Commercially available peroxidases include Guardzyme™ and Novozym™ 51004 (Novozymes A/S).

[0081] Additional enzymes suitable for use are discussed in WO2009/087524, WO2009/090576, WO2009/107091, WO2009/111258 and WO2009/148983.

Enzyme Stabilizers

[0082] Any enzyme present in the composition may be stabilized using conventional stabilizing agents, for example a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid or a boric acid derivative, for example , an aromatic borate ester, or a phenylboronic acid derivative such as 4-formylphenylboronic acid, and the composition can be formulated as described, for example, in WO 92/19709 and WO 92/19708.

[0083] When the alkyl groups are long enough to form branched or cyclic chains, these will encompass branched, cyclic and straight alkyl chains. Alkyl groups are preferably linear or branched, more preferably linear.

fluorescent agent

[0084] The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are commercially available. Typically these fluorescent agents are supplied and used in the form of their alkali metal salts, for example the sodium salts.

[0085] Preferred classes of fluorescent agents are: Distyryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, diamino stilbene disulfonic acid compounds, e.g. Tinopal DMS Pure Xtra and Blankophor (Trade Mark) HRH, and pyrazoline compounds, for example Blankophor SN.

[0086] The preferred fluorescent agents are: sodium 2-(4-styryl-3-sulfophenyl)-2H-naptol[1,2-d]triazole, 4,4'-bis{[(4-anilino-6- (N-methyl-N-2-hydroxyethyl)amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2' disodium disulphonate, 4,4'-bis{[(4-anilino-6-morpholino) disodium-1,3,5-triazin-2-yl)]amino}stilbene-2-2' disodium disulfonate and disodium 4,4'-bis(2-sulfostyryl)biphenyl.

[0087] The total amount of the fluorescent agent or agents used in the composition is preferably 0.0001% to 0.5% by weight, more preferably 0.005% to 2% by weight, most preferably 0.05% to 0.25% by weight.

[0088] The aqueous solution used in the method has a fluorescent agent present. The fluorescent agent is present in the aqueous solution used in the method, preferably in the range of 0.0001 g/L to 0.1 g/L, more preferably 0.001 g/L to 0.02 g/L.

perfume

[0089] The composition may comprise a fragrance. The fragrance is preferably in the range of 0.001% to 3% by weight, more preferably 0.05% to 0.5% by weight, most preferably 0.1% to 1% by weight. Many appropriate perfume examples are provided in CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.

[0090] Preferably, the perfume comprises at least one note (compound) of: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; cinnamal hexyl; linalool; pentanoic acid, 2-methyl-, ethyl ester; octanal; benzyl acetate; 1,6-octadiene-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1,1-dimethylethyl)-, 1-acetate; delta-damascone; beta-ionone; verdyl acetate; dodecanal; cinnamic hexyl aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester; amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; alpha-pyrone; beta-phenylethyl benzoate; alpha-santalol; cedrol; cedryl acetate; cedar shape; cyclohexyl salicylate; gamma-dodecalactone and beta-phenylethylphenyl acetate.

[0091] Useful fragrance compounds include materials of natural and synthetic origin. They include unique compounds and blends. Specific examples of these components can be found in the current literature, for example Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA).

[0092] It is common for a plurality of perfume components to be present in a formulation. In the compositions of the present invention, it is contemplated that there will be four or more, preferably five or more, more preferably six or more, or even seven or more different perfume components.

[0093] In perfume blends, preferably 15% to 25% by weight are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

[0094] The International Fragrance Association published a list of fragrance (perfume) ingredients in 2011. (http://www.ifraorg.org/en-us/ingredients#.U7Z4hPldWzk)

[0095] The Research Institute for Fragrance Materials provides a perfume (fragrance) database with safety information.

[0096] The top note of the fragrance can be used to suggest the whiteness and brightness benefit of the invention.

[0097] Some or all fragrances can be encapsulated, typical fragrance components that are advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100 to 250 degrees Celsius. It is also advantageous to encapsulate fragrance components that have a low CLog P (ie, those that will have a greater tendency to break down in water), preferably with a CLog P of less than 3.0. These relatively low boiling point, relatively low CLog P materials have been termed “late bloom” fragrance ingredients and include one or more of the following materials: allyl caproate, amyl acetate, amyl propionate, anisic aldehyde, anisole , benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl isovalerate, benzyl propionate, beta gamma hexenol, camphor gum, levo-carvone, d-carvone, cinnamic alcohol, cinnamyl formate, cis -jasmone, cis-3-hexenyl acetate, cumin alcohol, cyclal c, dimethylbenzylcarbinol, dimethylbenzylcarbinol acetate, ethyl acetate, ethyl acetate acetate, ethylamyl ketone, ethyl benzoate, ethyl butyrate, ethylhexyl ketone, ethylphenyl acetate, Eucalyptol, Eugenol, Fenchyl Acetate, Flor Acetate (Decenyl Tricycle Acetate), Fructone (Decenyl Tricycle Propionate), Geraniol, Hexenol, Hexenyl Acetate, Hexyl Acetate, Hexyl Formate, Hydrotropic Alcohol, Hydroxycitronellal, Indone, Isoamyl Alcohol , isomenthone, isopulegil acetate, isoquinolone, ligustral, linalool, linalool oxide, linalyl formate, menthone, menthylacetophenone, methylamyl ketone, methyl anthranilate, methyl benzoate, methylbenzyl acetate, methyl eugenol, methyl heptenone, methyl heptin carbonate , methylheptyl ketone, methylhexyl ketone, methylphenylcarbinyl acetate, methyl salicylate, methyl-n-methyl anthranilate, nerol, octalactone, octyl alcohol, p-cresol, p-cresol methyl ether, p-methoxy acetophenone, p-methyl acetophenone, phenoxy ethanol, phenyl acetaldehyde, phenylethyl acetate, phenylethyl alcohol, phenyl ethyl dimethyl carbinol, prenyl acetate, propyl bornate, pulegone, rose oxide, safrole, 4-terpinenol, alpha-terpinenol and/or viridine. It is common for a plurality of perfume components to be present in a formulation. In the compositions of the present invention, it is envisaged that there will be four or more, preferably five or more, more preferably six or more, or even seven or more different fragrance components from the above-provided list of late-blooming fragrances present in the fragrance. .

[0098] Another group of fragrances to which the present invention can be applied are so-called "aromatherapy" materials. These include many components also used in perfumery, including essential oil components such as Clary Sage, Eucalyptus, Geranium, Lavender, Nutmeg Flower Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.

[0099] It is preferred that the laundry treatment composition does not contain a peroxygen bleach, for example, sodium percarbonate, sodium perborate and peracid.

[0100] The indefinite article “um” or “uma” and its corresponding definite article “o(a)”, as used herein, mean at least one, or one or more, unless otherwise specified.

Experimental part

[0101] The formulations in Table I below were carried out at varying levels of salt and addition of SRP. Table I. Formulations carried out with different levels of salt and addition of SRP.

[0102] The EPEI (Ethoxylated Polyethyleneimine) used a PEI of 600 molecular weight with 20 moles of ethoxylated per NH in the base PEI; is available as Sokalan HP20, ex BASF.

[0103] The SRP (Dirt Removal Polymer) was used at a level of 0.0% by weight and 0.5% by weight. The SRP used was:

[0104] The SRP is as described in document WO2014/019903 (Unilever).

[0105] The viscosity of the formulation was measured using a Paar Physica MCR300, which is a commercially available stress rheometer.

[0106] The results are shown in Table II below for the formulation in the absence of the SRP polymer (0.0% by weight). Table II. Results for the formulation in the absence of the SRP polymer.

[0107] The inventive formulations F1 and F2 containing alkyl ether carboxylic acid have a higher viscosity than the control with sodium lauryl ether sulfate alone.

[0108] The results are shown in Table III below for formulation in the presence of SRP polymer (0.5% by weight). Table III. Results for the formulation in the presence of the SRP polymer.

[0109] The inventive formulations F1 and F2 containing alkyl ether carboxylic acid have higher viscosity than the control with sodium lauryl ether sulfate alone.

Claims (11)

1. Liquid aqueous composition of laundry detergent, characterized by comprising: (i) from 2% to 10% by weight of an anionic linear alkylbenzene sulfonate surfactant; (ii) from 0.5% to 4% by weight of zwitterionic surfactant selected from: amine oxide and carbobetaines; (iii) from 0.1% to 4% by weight alkali metal salt; (iv) from 1% to 5% by weight of an alkoxylated polyethyleneimine; (v) from 1% to 10% by weight of an alkyl ether carboxylic acid anionic surfactant of the structure: R2-(OCH2CH2)n-OCH2-COOH, wherein: R2 is selected from saturated straight or branched alkyl chains and C10 to C26 monounsaturated, preferably C12 to C20 straight alkyl chain, more preferably a C16 to C18 straight alkyl chain, and wherein n is selected from 6 to 20; (vi) from 0 to 10% by weight of an alkyl ether sulfate anionic surfactant with 0.5% to 1.5 mol equivalent of ethoxylation; (vii) from 0 to 2% by weight of a terephthalate polyester soil release polymer; (viii) from 0 to 4% by weight of a nonionic surfactant; and, (ix) from 0.0 to 0.2% by weight of a protease enzyme, wherein the laundry detergent composition comprises in total from 10% to 20% by weight of anionic surfactant. 2. Liquid aqueous composition of detergent for washing clothes, according to claim 1, characterized in that the composition comprises 1.5% to 2.5% by weight of a zwitterionic surfactant and 0.5% to 2% by weight of an alkali metal salt. 3. Liquid aqueous composition of detergent for washing clothes, according to claim 1 or 2, characterized in that the composition comprises 2.5% to 5% by weight of an anionic surfactant of alkyl ether sulfate. 4. Liquid aqueous composition of detergent for washing clothes, according to any one of claims 1 to 3, characterized in that the composition comprises from 3% to 5% by weight of an anionic surfactant of alkyl ether carboxylic acid. 5. Liquid aqueous composition of detergent for washing clothes, according to any one of claims 1 to 4, characterized in that the composition comprises from 2.5% to 5% by weight of an anionic surfactant of linear alkylbenzene sulfonate. 6. Liquid aqueous composition of detergent for washing clothes, according to any one of claims 1 to 5, characterized in that the alkoxylated polyethyleneimine is an ethoxylated polyethyleneimine. 7. Aqueous liquid detergent composition for washing clothes, according to any one of claims 1 to 6, characterized in that the composition comprises from 0.2% to 1% by weight of a polyester terephthalate polymer for the release of dirt. 8. Liquid aqueous composition of detergent for washing clothes, according to claim 7, characterized by the terephthalate polyester polymer for dirt release being:

wherein c is from 4 to 9; d is from 1 to 3; and it's 40 to 50. 9. Liquid aqueous composition of laundry detergent, according to any one of claims 1 to 8, characterized in that n is selected from 8 to 12, and R2 is selected from the saturated or monounsaturated linear alkyl chain C16 to C18. 10. Aqueous liquid laundry detergent composition, according to any one of claims 1 to 9, characterized in that the alkali metal salt is sodium chloride. 11. Domestic method of treating a fabric, characterized in that the method comprises the steps of: (i) treating a fabric with from 1 g/L of an aqueous solution of the liquid aqueous laundry detergent composition as defined in any one of claims 1 to 10; and, (ii) allowing said aqueous solution of the laundry detergent composition to remain in contact with the fabric for 10 minutes to 2 days and then washing and drying the fabric.