EP3440170B1

EP3440170B1 - Laundry detergent composition

Info

Publication number: EP3440170B1
Application number: EP17708995.0A
Authority: EP
Inventors: Stephen Norman Batchelor; Jayne Michelle Bird; Matthew Lloyd Parry
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2016-04-08
Filing date: 2017-02-20
Publication date: 2020-04-08
Anticipated expiration: 2037-02-20
Also published as: EP3440170A1; AR108173A1; WO2017174252A1; BR112018070472B1; BR112018070472A2; CN109072131A

Description

Field of the Invention

The present invention provides an alkoxylated polyethylene imine polymer and surfactant formulation for use in domestic laundry.

Background of the Invention

Domestic Laundry liquid formulation containing Linear Alkyl Benzene sulfonate surfactant and Alkyl Ether Sulfate surfactant in combination with a non-ionic surfactant are ubiquitous. To enhance cleaning performance alkoxylated polyethylene imine polymers, preferably in combination with polyethylene terephthalate soil removal polymers are added. The addition of these polymers greatly reduces the viscosity of the formulation. Effective methods to increase the viscosity of the formulation are required, which preferably enhance the cleaning performance.
WO2013/087286 (Unilever) discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
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 to its use to soften fabrics.
US 5,269,960 (The Clorox Company) discloses the use of effective amounts of alkyl ether carboxylates in liquid aqueous enzyme-containing detergents for improving phase stability and enzyme stability of said liquid detergents.
WO2017/162378 (Unilever) discloses an aqueous liquid laundry detergent composition comprising i.a.:

3.0 wt% of linear alkyl benzene sulfonate anionic surfactant,
4.5 wt% of C12 alkyl ether sulfate anionic surfactant with 1 mole equivalent of ethoxylation,
1.6 wt% of ethoxylated polyethylene imine,
4.5 wt% of oleyl ether or lauryl ether carboxylic acid anionic surfactant with 10 mole equivalent of ethoxylation, and
0.5 wt% of terephthalate polyester soil release polymer;

(i) treating a textile with from 1 g/L of an aqueous solution of the laundry detergent composition as defined previously; and,
(ii) allowing said aqueous laundry detergent solution to remain in contact with the textile for 10 minutes to 2 days then rinsing and drying the textile.

Summary of the Invention

We have found that partial or complete replacement of the non-ionic surfactant with alkyl ether carboxylic acid anionic surfactant, increases the viscosity of the formulation.
In one aspect the present invention provides an aqueous liquid laundry detergent composition comprising:

(i) from 2 to 15 wt%, preferably from 3 to 8 wt%, of linear alkyl benzene sulfonate anionic surfactant;
(ii) from 2 to 15 wt%, preferably from 3 to 8 wt%, of alkyl ether sulfate anionic surfactant with 2.5 to 3.5 mole equivalent of ethoxylation;
(iii) from 0.5 to 6 wt%, preferably 1.5 to 4 wt%, of an alkoxylated polyethylene imine, preferably ethoxylated polyethylene imine;
(iv) from 1 to 10 wt%, preferably 2 to 6 wt%, most preferably 3 to 5 wt%, of an alkyl ether carboxylic acid anionic surfactant of the following structure:

R₂-(OCH₂CH₂)_n-OCH₂-COOH,

wherein:
R₂ is selected from saturated and mono-unsaturated C10 to C26 linear or branched alkyl chains, preferably a C12 to C20 linear alkyl chains, most preferably a C16 to C18 linear alkyl chain, and wherein n is selected from: 2 to 20, preferably 7 to 13, more preferably 8 to 12, most preferably 9.5 to 10.5;
(v) from 0.1 to 3 wt%, preferably 0.4 to 2wt% of a terephthalate polyester soil release polymer;
(vi) from 0 to 4 wt%, preferably from 0 to 1wt%, of a non-ionic surfactant; and
(vii) from 0.0 to 0.2 wt%, preferably from 0.002 to 0.02 wt%, of a protease enzyme, wherein the laundry detergent composition comprises in total from 10 to 20 wt% of anionic surfactant.

In another aspect the present invention provides a domestic method of treating a textile, the method comprising the steps of:

(i) treating a textile with from 1 g/L of an aqueous solution of the laundry detergent composition; and,
(ii) allowing said aqueous laundry detergent solution to remain in contact with the textile for 10 minutes to 2 days then rinsing and drying the textile.

In the method aspects of the present invention the surfactant used is preferably as preferred for the composition aspects of the present invention.
Domestic methods are preferably conducted in a domestic washing machine or by hand washing. The temperature of the wash is preferably from 285 to 313K. The main wash time is preferably 5 to 45 minutes.
The textile is preferably an item of clothing, bedding or table cloth. Preferred items of clothing are cotton containing shirts, skirts, dresses trousers, underwear and jumpers.

Detailed Description of the Invention

Linear alkyl benzene sulfonate

Weights of Linear alkyl benzene sulfonate are calculated as the protonated form. The linear alkyl benzene sulfonate has an alkyl chain length of C8 to C15, preferably C12 to C14.
Linear alkyl benzene sulphonate (LAS) may be obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®. Another suitable route is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, preferably having 8 to 15 carbon atoms. Other synthesis routes, such as HF, may also be suitable.

Alkyl ether sulfate

Weights of alkyl ether sulfate are calculated as the protonated form, R₁-(OCH₂CH₂)_m-OSO₃H. Preferably R₁ is C10 to C22 saturate or unsaturated linear alkyl chain, more preferably a saturated C12 to C16 linear alkyl chain, most preferably C12 linear alkyl chain (lauryl).
Preferably the ratio (wt% alkyl ether sulfate)/(wt% linear alkyl benzene sulfonate) is from 0.5 to 2, more preferably 0.7 to 1.2.

Alkyl ether carboxylic acid

Weights of alkyl ether carboxylic acid are calculated as the protonated form, R₂-(OCH₂CH₂)_n-OCH₂COOH. They may be used as salt version for example sodium salt, or amine salt.
The alkyl chain, R₂, may be linear or branched, preferably it is linear.
The alkyl chain, R₂, may be aliphatic or contain one cis or trans double bond.
The alkyl chain, R₂, is preferably selected from CH₃(CH₂)₁₁, CH3(CH₂)₁₅, CH₃(CH₂)₁₇, CH₃(CH₂)₇CH=CH (CH₂)₈-.
The alkyl ether carboxylic acid is most preferably of the structure:

CH₃(CH₂)₇CH=CH(CH₂)₈(OCH₂CH₂)₁₀OCH₂COOH.
Alkyl ether carboxylic acid are available from Kao (Akypo ®), Huntsman (Empicol®) and Clariant (Emulsogen ®).
The sodium salt of the alkyl ether carboxylate may be used.

Zwitterionic surfactant

Zwitterionic surfactants are preferably absent from the formulation. Zwitterionic surfactants contain a charges group with a formal positive and a formal negative charge. In this regard, the aqueous liquid laundry detergent composition comprises less than 0.1 wt% of a zwitterionic surfactant; most preferably 0 wt% of a zwitterionic surfactant. Typical examples of zwitterionic surfactants are carbobetaines and amine oxides.

Non-ionic surfactant

The aqueous liquid laundry detergent may comprise Non-ionic surfactant, preferably an alkyl ethoxylated non-ionic surfactant.
Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, polyaryllphenols, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide. The preferred nonionic detergent compounds are the condensation products of aliphatic C₈ to C₁₈ primary or secondary linear or branched alcohols with ethylene oxide.
Most preferably, the alkyl ethoxylated non-ionic surfactant is a C₁₂ to C₁₅ primary alcohol with a mole average ethoxylation of 7EO to 9EO units.
The weight fraction of alkyl ether sulphate/non-ionic surfactant is preferably greater than 3.

Further Surfactant

The aqueous liquid laundry detergent may comprises from 0 to 4 wt% of further surfactants, for example, those described in Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1996).
Examples of suitable further anionic detergent compounds are; alkyl sulphates, especially those obtained by sulphating linear or branched C₈ to C₁₈ alcohols; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof. Soaps are particularly preferred in the aqueous liquid laundry detergent composition at levels of 0.5 to 1.5 wt%. Weights refer to protonated forms.

Alkoxylate Polyethylene Imine

The alkoxylated polyethyelene imine comprises a polyethyleneimine (PEI) backbone wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without quaternisation. Such materials may 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 available NH in the unsubstituted polyethyleneimine backbone. Y is preferably from 7 to 40 more preferably it is in the range from 16 to 26, most preferably 18 to 22. X is selected to be from about 300 to about 10000 weight average molecular weight and is preferably from 500 to 800.
The alkoxylation is preferably selected from ethoxylation or propoxylation, or a combination of the two, Ethoxylation is most preferred. The alkoxy chains may be capped with groups selected from: H; CH₃; SO₃ ^-; CH₂COO^-; PO₃ ^2-; C₂H₅; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate, most preferably H.
Most preferably the alkoxylated PEI is PEI(600)20EO.
Further examples are: PEI(600)10EO7PO; PEI(1600)19EO; and PEI80024EO16PO.
To enhance performance of the alkoxylated PEI, a co-polymer obtainable by the polymerisation of an alkene bearing a substituent sulfonate group with an alkene bearing a polyoxyalkylene chain and an alkene bearing a carboxy substituents in a weight ratio of from 5:1 to 1:5 with the alkoxylated polyethyelene imine may be added. Preferably the co-polymer is obtainable by polymerisation of 5-15wt% 3-allyloxy-2-hydroxypropane sulfonate with 30 to 45 wt% of 3-methylbut-3-en-1-ol which has been reacted with 20 to 40 moles of ethylene oxide; and 25 to 55% acrylic acid or salts thereof. Such polymers are described in WO2016/045518 (Nippon Shokubai).

Terephthalate Polyester Soil Release Polymer

Terephthalate Polyester Soil Release Polymer comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols), as described in WO2009/153184 , EP2692842 and WO2014/019903 .
Examples of Terephthalate Polyester Soil Release Polymer are the REPEL-O-TEX® line of polymers supplied by Rhodia, including REPEL-O-TEX® SRP6 and REPEL-O-TEX® SF-2. 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.
Preferred structure are -[(Z)_a-O-OC-Ar-CO-]_b and (Z)_a-O-OC-[Ar-CO-O-C₃H₆-O-OC]_b-Ar-COO-(Z)_a, where Ar is selected from 1,4 substituted phenylene and 1,3 substituted phenylene substituted in the 5 position with a sulphonates (SO₃ ^-) group; 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.
The alkoxy chains are capped with groups selected from H; CH₃; SO₃ ^-; CH₂COO^-; PO₃ ^2-; C₂H₅; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate.
Most preferably the Terephthalate Polyester Soil Release Polymer is:
wherein c is from 4 to 9; d is from 1 to 3; e is from 40 to 50.

Polymers

The composition may comprise one or more further polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
Polymers present to prevent dye deposition may be present, for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole).
Such polymers are preferably present at levels of less than 2 wt%.
A particularly preferred additional polymer is that obtained by the amination of the reaction product of a 2,2-bis-alkyl substituted 1,3 propanediol with 2 to 10 moles of an alkenyloxide, preferably selected from ethylene oxide, propylene oxide and mixtures thereof. The amination of the alkoxylate 1,3-diol may be carried out with ammonia or reductive cyanoethylation. Preferred 1,3-diol's are 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol. Such polyetheramines are described in WO2016/048674 (BASF).
The composition is preferably devoid of silicone polymers and polymers bearing quaternised N groups.

Builders and Seauestrants

The detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material. Examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, ethylene diamine tetra-acetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, and citric acid. Other examples are DEQUEST™, organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALAN™.
If utilised, the aqueous liquid laundry detergent formunation comprise from 0.1% to 2.0 wt% builder and sequesterant material. Citrate is most preferred.

Shading Dye

Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).
Shading Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol^-1 cm^-1, preferably greater than 10000 L mol^-1 cm^-1. The dyes are blue or violet in colour.
Preferred shading dye chromophores are azo, azine, anthraquinone, and triphenylmethane. Preferred mono-azo dyes contain a heterocyclic ring and are most preferably thiophene dyes. The 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
Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5, acid blue 59.
The shading dye is present is present in the composition in range from 0.0001 to 0.5 wt %, preferably 0.001 to 0.1 wt%. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is a blue or violet shading dye.
A mixture of shading dyes may be used.
The shading dye is most preferably a reactive blue anthraquinone dye, such as C.I. reactive blue 49, covalently linked to an alkoxylated polyethyleneimine. The alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation. Preferably 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation. Preferably the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800.
The inventive aqueous liquid laundry detergent composition reduces the staining on neat contact of the composition with fabric.

Protease Enzyme

Protease enzymes hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains. Examples of suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such 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 sub-group of serine protease 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 may be divided into 6 subdivisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
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; 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 chymotrypsin proteases derived from Cellumonas described in WO05/052161 and WO05/052146 .
Further examples of useful proteases are the variants described in: WO92/19729 , WO96/034946 , WO98/201 15 , WO98/201 16 , WO99/01 1768 , WO01/44452 , WO03/006602 , WO04/03186 , WO04/041979 , WO07/006305 , WO1 1/036263 , WO1 1/036264 , especially the 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 the BPN' numbering. More preferred the subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, *36D, V68A, N76D, N87S,R, *97E, A98S, S99G,D,A, S99AD, S101 G,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, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).
Most preferably the protease is a subtilisins (EC 3.4.21.62).
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; 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 Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in US 6,312,936 BI, US 5,679,630 , US 4,760,025 , US7,262,042 and WO09/021867 . Most preferably the subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
Suitable commercially available protease enzymes include those sold under the trade names 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 sold as Ultra® or Evity® (Novozymes A/S).
Those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® by Genencor International.
Those sold under the tradename 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.),
Those available from Henkel/ Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604 with the following mutations S99D + SIOI 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.
Inclusion of protease in the formulation enhances cleaning.

Further Enzymes

One or more further enzymes are preferred present in a laundry composition of the invention and when practicing a method of the invention.
Preferably the level of each enzyme in the laundry composition of the invention is from 0.0001 wt% to 0.1 wt% protein.
Preferably the further enzyme is selected from: alpha-amylases; lipases; and, cellulases, most preferably an alpha-amylase (EC number 3.2.1.1.).
Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. 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 Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P. fluorescens, Pseudomonas sp. strain SD 705 ( WO 95/06720 and WO 96/27002 ), P. wisconsinensis ( WO 96/12012 ), a Bacillus lipase, e.g. 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 ).
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 .
Preferred commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™ and Lipoclean™ (Novozymes A/S).
The method of the invention may 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 which has activity towards phospholipids.
Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol. Phospholipases are enzymes which participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A₁ and A₂ which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid respectively.
The method of the invention may be carried out in the presence of cutinase classified in EC 3.1.1.74. The cutinase used according to the invention may be of any origin. Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839 , or the Bacillus sp. strains 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.).
Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. 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). Celluclean™ is preferred.
Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618 , WO 95/10602 , and WO 98/15257 . Commercially available peroxidases include Guardzyme™ and Novozym™ 51004 (Novozymes A/S).
Further enzymes suitable for use are discussed in WO2009/087524 , WO2009/090576 , WO2009/107091 , WO2009/111258 , and WO2009/148983 .

Enzyme Stabilizers

Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g., WO 92/19709 and WO 92/19708 .
Where alkyl groups are sufficiently long to form branched or cyclic chains, the alkyl groups encompass branched, cyclic and linear alkyl chains. The alkyl groups are preferably linear or branched, most preferably linear.

Fluorescent Agent

The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
Preferred fluorescers are: sodium 2 (4-styryl-3-sulphophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2' disulophonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulphonate, and disodium 4,4'-bis(2-sulphostyryl)biphenyl.
The total amount of the fluorescent agent or agents used in the composition is preferably from 0.0001 to 0.5 wt %, more preferably 0.005 to 2 wt %, most preferably 0.05 to 0.25 wt %.
The aqueous solution used in the method has a fluorescer present. The fluorescer is present in the aqueous solution used in the method preferably in the range from 0.0001 g/l to 0.1 g/l, more preferably 0.001 to 0.02 g/l.

Perfume

The composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %, more preferably 0.05 to 0.5 wt%, most preferably from 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the 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.
Preferably the perfume comprises at least one note (compound) from: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamal; linalool; Pentanoic acid, 2-methyl-, ethyl ester; octanal; benzyl acetate; 1,6-octadien-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1,1-dimethylethyl)-, 1-acetate; delta-damascone; beta-ionone; verdyl acetate; dodecanal; hexyl cinnamic aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester;amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; alpha-irone; beta-phenyl ethyl benzoate; alpa-santalol; cedrol; cedryl acetate; cedry formate; cyclohexyl salicyate; gamma-dodecalactone; and, beta phenylethyl phenyl acetate.
Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in 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).
It is commonplace 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 perfume components.
In perfume mixtures preferably 15 to 25 wt% 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.
The International Fragrance Association has published a list of fragrance ingredients (perfumes) in 2011. (http://www.ifraorg.org/en-us/ingredients#.U7Z4hPldWzk)
The Research Institute for Fragrance Materials provides a database of perfumes (fragrances) with safety information.
Perfume top note may be used to cue the whiteness and brightness benefit of the invention.
Some or all of the perfume may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius. It is also advantageous to encapsulate perfume components which have a low CLog P (ie. those which will have a greater tendency to be partitioned into water), preferably with a CLog P of less than 3.0. These materials, of relatively low boiling point and relatively low CLog P have been called the "delayed blooming" perfume 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 iso valerate, benzyl propionate, beta gamma hexenol, camphor gum, laevo-carvone, d-carvone, cinnamic alcohol, cinamyl formate, cis-jasmone, cis-3-hexenyl acetate, cuminic alcohol, cyclal c, dimethyl benzyl carbinol, dimethyl benzyl carbinol acetate, ethyl acetate, ethyl aceto acetate, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethyl hexyl ketone, ethyl phenyl acetate, eucalyptol, eugenol, fenchyl acetate, flor acetate (tricyclo decenyl acetate), frutene (tricyclco decenyl propionate), geraniol, hexenol, hexenyl acetate, hexyl acetate, hexyl formate, hydratropic alcohol, hydroxycitronellal, indone, isoamyl alcohol, iso menthone, isopulegyl acetate, isoquinolone, ligustral, linalool, linalool oxide, linalyl formate, menthone, menthyl acetphenone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benyl acetate, methyl eugenol, methyl heptenone, methyl heptine carbonate, methyl heptyl ketone, methyl hexyl ketone, methyl phenyl carbinyl 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, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl dimethyl carbinol, prenyl acetate, propyl bornate, pulegone, rose oxide, safrole, 4-terpinenol, alpha-terpinenol, and /or viridine. It is commonplace 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 perfume components from the list given of delayed blooming perfumes given above present in the perfume.
Another group of perfumes with which the present invention can be applied are the so-called aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
The indefinite article "a" or "an" and its corresponding definite article "the" as used herein means at least one, or one or more, unless specified otherwise.
The pH of the aqueous liquid laundry detergent composition is preferably from 6.5 to 8.5, most preferably 6.8 to 7.5. The pH may be obtained by the addition of an alkali, such as NaOH, trialkyl amine or an alkanolamine.

Experimental

The following control base aqueous laundry detergent formulation was made:

Ingredient	Weight%
Linear alkyl benzene sulfonate.	5.8
C12 alkyl ether sulfate with 3 mole equivalent of ethoxylation	4.4
SRP	1.0
EPEI	3.1
triethylamine	8.8
Sequesterant Dequest™ 2010	1.5
Fatty acid (Prifac™ 5908)	0.9
Acrylic acid/acrylic ester co-polymer	0.7
Propylene glycol	2.0
perfume	0.4
Citric acid	1.0
preservative	0.2
Fluorescer (Tinopal 5BMG-X ex BASF)	0.2

The EPEI (Ethoxylated PolyEthylene Imine) used was a PEI of 600 molecular weight with 20 moles of ethoxylate per NH on the base PEI; it is available as Sokalan HP20 ex BASF.
The SRP (Soil Removal Polymer) used was:
The SRP is as described in WO2014/019903 (Unilever).
The viscosity of the formulation were measured using a Paar Physica MCR300 is a commercial stress rheometer.

The formulation was remade with the addition of non-ionic surfactant and alkyl ether carboxylate surfactant. The results are given in the table below.

	Viscosity/cP
control	140
3% non-ionic	166
3% oleyl ether carboxylate	274
3% lauryl ether carboxylate	250
3% oleyl ether carboxylate (sodium salt)	271
3% non-ionic + 3% oleyl ether carboxylate	300
3% non-ionic+3% lauryl ether carboxylate	278

The non-ionic used was a C12-C15 linear alcohol alcohol with 7 moles of ethoxylation). The oleyl ether carboxylate used has 10 moles of ethoxylation. The lauryl ether carboxylate used had 10 moles of ethoxylation.
The formulations of the examples were remade with the addition of the following enzymes: protease (Coronase ® ex Novoymes, Bagsvaerd, Danmark); and, amylase (Natalase ® ex Novoymes, Bagsvaerd, Danmark).

Claims

An aqueous liquid laundry detergent composition comprising:
(i) from 2 to 15 wt% of linear alkyl benzene sulfonate anionic surfactant;

(ii) from 2 to 15 wt% of an alkyl ether sulfate anionic surfactant with 2.5 to 3.5 mole equivalent of ethoxylation;

(iii) from 0.5 to 6 wt% of an alkoxylated polyethylene imine;

(iv) from 1 to 10 wt% of an alkyl ether carboxylic acid anionic surfactant of the following structure:

R₂-(OCH₂CH₂)_n-OCH₂-COOH,

wherein:
R₂ is selected from saturated and mono-unsaturated C10 to C26 linear or branched alkyl chains, and wherein n is selected from: 2 to 20;

(v) from 0.1 to 3 wt% of a terephthalate polyester soil release polymer;

(vi) from 0 to 4 wt% of a non-ionic surfactant; and

(vii) from 0.0 to 0.2 wt% of a protease enzyme
wherein the laundry detergent composition comprises in total from 10 to 20 wt% of anionic surfactant.
An aqueous liquid laundry detergent composition according to claim 1, wherein the ratio (wt% alkylether sulfate)/(wt% linear alkyl benzene sulfonate) is from 0.5 to 2.
An aqueous liquid laundry detergent composition according to claim 1 or 2, wherein the composition comprises from 3 to 8 wt% of an alkyl ether sulfate anionic surfactant.
An aqueous liquid laundry detergent composition according to any one of the preceding claims, wherein the composition comprises from 2 to 6 wt% of an alkyl ether carboxylic acid anionic surfactant.
An aqueous liquid laundry detergent composition according to any one of the preceding claims, wherein the composition comprises from 3 to 8 wt% of a linear alkyl benzene anionic sulfonate surfactant.
An aqueous liquid laundry detergent composition according to any one of the preceding claims, wherein the alkoxylated polyethylene imine is an ethoxylated polyethylene imine.
An aqueous liquid laundry detergent composition according to any one of the preceding claims, wherein the composition comprises from 0.4 to 2 wt% of a terephthalate polyester soil release polymer.
An aqueous liquid laundry detergent composition according to claim 7, wherein the Terephthalate Polyester Soil Release Polymer is:
wherein c is from 4 to 9; d is from 1 to 3; e is from 40 to 50.
An aqueous liquid laundry detergent composition according to any one of the preceding claims, wherein n is selected from 7 to 13 and R₂ is selected from saturated and mono-unsaturated C16 to C18 linear alkyl chain.
An aqueous liquid laundry detergent composition according to any one of the preceding claims, wherein the alkoxylated polyethylene imine has an average moles of alkoxylation (AO) per available NH in the unsubstituted polyethyleneimine backbone of from 16 to 26 and the unsubstituted polyethyleneimine backbone has a molecular weight from 500 to 800.
A domestic method of treating a textile, the method comprising the steps of:
(i) treating a textile with from 1 g/L of an aqueous solution of the laundry detergent composition as defined in any one of the preceding claims; and,

(ii) allowing said aqueous laundry detergent solution to remain in contact with the textile for 10 minutes to 2 days then rinsing and drying the textiles.