Field of Invention

The present invention concerns a detergent composition. More particularly a detergent composition comprising a C16 and/or C18 ether sulfate surfactant.

Background of the Invention

Lipid esterase (lipases) are enzymes used in cleaning applications, such as laundry to hydrolase fats.

While consumers find the cleaning action of lipases useful in the wash context, consumers want to have minimal enzymes left on their garments after washing. The enzymes can adhere to the laundered garments, but also to any residual fats left on the garments.

There is thus a need for a surfactant system which minimises the amount of lipase left on laundered garments, particularly which minimises the amount of lipase left in fats on the garments after the wash.

Lauryl (C12) ether sulfates are commonly used as surfactants, particularly in laundry detergent compositions

Surprisingly replacement of lauryl ether sulfate with C16 and/or C18 ether sulfate with 7 to 15 ethoxylate groups, reduces the amount of lipase left in fats after the wash.

Summary of the Invention

The invention relates to a detergent composition comprising:

a) from 0.0005 to 0.5 wt.%, preferably from 0.005 to 0.2 wt.% of a lipid esterase

enzyme;

b) from 2 to 25 wt.%, preferably from 3 to 20 wt.%, most preferably from 4 to 15 wt.% of an alcohol ether sulfate of formula R-(OCH CH ) _n OSC> H where R is saturated or monounsaturated linear C16 and/or C18 alkyl chain and where n is from 5 to 15, preferably from 6 to 15, more preferably from 7 to 15, most preferably 7 to 12;

c) from 0.2 to 50 wt.%, preferably from 1 to 40 wt.%, more preferably from 1.5 to 30 wt.%, even more preferably from 2 to 25 wt.%, most preferably from 4 to 15 wt.% of surfactant other than the surfactant specified in (b); Preferably the weight fraction of (c) to (b) is from 0.1 to 10, more preferably from 0.1 to 5, even more preferably from 0.1 to 2.

Preferably the lipid esterase is selected from: triacylglycerol lipases, carboxylic ester hydrolases, cutinases, sterol esterases and wax-ester hydrolases and mixtures thereof.

Preferably the surfactant (c) comprises one or more surfactants selected from: anionic, nonionic or amphoteric surfactants and mixtures thereof. More preferably the surfactant comprises anionic and nonionic surfactants.

Preferably the nonionic surfactant is selected from saturated and mono-unsaturated aliphatic alcohol ethoxylate, preferably selected from Ci2to C20 primary linear alcohol ethoxylates with an average of from 5 to 30 ethoxylates, more preferably C16 to C18 with an average of from 5 to 25 ethoxylates. Preferably the total amount of nonionic surfactants in a composition of the invention ranges from 0.5 to 10 wt.%, more preferably from 1 to 8 wt.%, even more preferably from 1.5 to 6 wt.%, most preferably from 2 to 5 wt.%.

Preferably the anionic surfactant is selected from C12 to C18 alkyl ether carboxylates; citric acid ester of a C16 to C18 monoglyceride (citrem), tartartic acid esters of a C16 to C18 monoglyceride (tatem) and diacetyl tartaric acid ester of a C16 to C18 monoglyceride (datem); and water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms. Most preferably, the additional anionic surfactant comprises C16 to C18 alkyl ether carboxylates; citric acid ester of a C16 to C18 monoglyceride (citrem), tartartic acid esters of a C16 to C18 monoglyceride (tatem) and diacetyl tartaric acid ester of a C16 to C18 monoglyceride (datem) and sulfonates, for example, linear alkyl benzene sulfonate. Preferably the total amount of anionic surfactants in a composition of the invention ranges from 0.5 to 20 wt.%, more preferably from 1 to 16 wt.%, even more preferably from 1.5 to 14 wt.%, most preferably from 2 to 12 wt.%.

Preferably the composition comprises from 0.5 to 15 wt.%, more preferably from 0.75 to 15 wt.%, even more preferably from 1 to 12 wt.%, most preferably from 1.5 to 10 wt.% of cleaning boosters selected from antiredeposition polymers; soil release polymers;

alkoxylated polycarboxylic acid esters; and mixtures thereof. Preferably the antiredeposition polymers are alkoxylated polyamines; and/or the soil release polymer is a polyester soil release polymer.

Preferably the detergent composition is a laundry detergent composition, more preferably a laundry liquid detergent composition.

Preferably the laundry detergent composition comprises one or more additional enzymes from the group: proteases, amylases and cellulases.

In a second aspect the invention provides a domestic method of treating a textile, the method comprising the step of: treating a textile with an aqueous solution of 0.5 to 20 g/L of the detergent composition, preferably the laundry liquid detergent composition, of the first aspect.

In a third aspect, the invention relates to the use of an alcohol ether sulfate of formula R- (0CH ₂ CH ₂ ) _n 0S0 ₃ H where R is saturated or monounsaturated linear C16 and C18 alkyl chain and where n is from 7 to 15, preferably 8 to 12, to reduce the amount of lipase left in fats on garments after the wash.

Detailed Description of the Invention

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.

All enzyme levels refer to pure protein.

The integer n is the mole average value. wt.% relates to the amount by weight of the ingredient based on the total weight of the composition. For charged surfactants (for example anionic surfactants and the cetearyl ether sulfate (b)), wt.% is calculated based on the protonated form of the surfactant.

The formulation may be in any form for example a liquid, solid, powder, liquid unit dose. Preferably the composition is a liquid composition. The formulation when dissolved in demineralised water at 20°C preferably has a pH of 4 to 8, more preferably 6.5 to 7.5, most preferably 7.

Lipid esterase

The composition comprises from 0.0005 to 0.5 wt.%, preferably from 0.005 to 0.2 wt.% of a lipid esterase enzyme.

The terms lipid esterase and lipase are used herein synonymously.

Cleaning lipid esterases are discussed in Enzymes in Detergency edited by Jan H. Van Ee„ Onno Misset and Erik J. Baas (1997 Marcel Dekker, New York).

Cleaning lipid esterases are preferable active at alkaline pH in the range 7 to 11 , most preferably they have maximum activity in the pH range 8 to 10.5.

The lipid esterase may be selected from lipase enzymes in E.C. class 3.1 or 3.2 or a combination thereof.

Preferably the cleaning lipid esterases is selected from:

(1) Triacylglycerol lipases (E.C. 3.1.1.3)

(2) Carboxylic ester hydrolase (E.C. 3.1.1.1)

(3) Cutinase (E.C. 3.1.1.74)

(4) Sterol esterase (E.C. 3.1.1.13)

(5) Wax-ester hydrolase (E.C. 3.1.1.50)

Triacylglycerol lipases (E.C. 3.1.1.3) are most preferred.

Suitable triacylglycerol lipases can be selected from variants of the Humicola lanuginosa (Thermomyces lanuginosus) lipase. Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, 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), Bacillus lipases, 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). Suitable carboxylic ester hydrolases can be selected from wild-types or variants of carboxylic ester hydrolases endogenous to B. gladioli, P. fluorescens, P. putida, B.

acidocaldarius, B. subtilis, B. stearothermophilus, Streptomyces chrysomallus, S.

diastatochromogenes and Saccaromyces cerevisiae.

Suitable cutinases can be selected from wild-types or variants of cutinases endogenous to strains of Aspergillus, in particular Aspergillus oryzae, a strain of Alternaria, in particular Alternaria brassiciola, a strain of Fusarium, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum culmorum, or Fusarium roseum sambucium, a strain of Helminthosporum, in particular Helminthosporum sativum, a strain of Humicola, in particular Humicola insolens, a strain of Pseudomonas, in particular Pseudomonas mendocina, or Pseudomonas putida, a strain of Rhizoctonia, in particular Rhizoctonia solani, a strain of Streptomyces, in particular Streptomyces scabies, a strain of Coprinopsis, in particular Coprinopsis cinerea, a strain of Thermobifida, in particular Thermobifida fusca, a strain of Magnaporthe, in particular Magnaporthe grisea, or a strain of Ulocladium, in particular Ulocladium consortiale.

In a preferred embodiment, the cutinase is selected from variants of the Pseudomonas mendocina cutinase described in WO 2003/076580 (Genencor), such as the variant with three substitutions at I178M, F180V, and S205G.

In another preferred embodiment, the cutinase is a wild-type or variant of the six cutinases endogenous to Coprinopsis cinerea described in H. Kontkanen et al, App. Environ.

Microbiology, 2009, p2148-2157

In another preferred embodiment, the cutinase is a wild-type or variant of the two cutinases endogenous to Trichoderma reesei described in W02009007510 (VTT).

In a most preferred embodiment the cutinase is derived from a strain of Humicola insolens, in particular the strain Humicola insolens DSM 1800. Humicola insolens cutinase is described in WO 96/13580 which is hereby incorporated by reference. The cutinase may be a variant, such as one of the variants disclosed in WO 00/34450 and WO 01/92502.

Preferred cutinase variants include variants listed in Example 2 of WO 01/92502. Preferred commercial cutinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark). Suitable sterol esterases may be derived from a strain of Ophiostoma, for example

Ophiostoma piceae, a strain of Pseudomonas, for example Pseudomonas aeruginosa, or a strain of Melanocarpus, for example Melanocarpus albomyces.

In a most preferred embodiment the sterol esterase is the Melanocarpus albomyces sterol esterase described in H. Kontkanen et al, Enzyme Microb Technol., 39, (2006), 265-273.

Suitable wax-ester hydrolases may be derived from Simmondsia chinensis.

The lipid esterase is preferably selected from lipase enzyme in E.C. class 3.1.1.1 or 3.1.1.3 or a combination thereof, most preferably E.C.3.1.1.3.

Examples of EC 3.1.1.3 lipases include those described in WIPO publications WO 00/60063, WO 99/42566, WO 02/062973, WO 97/04078, WO 97/04079 and US 5,869,438. Preferred lipases are produced by Absidia reflexa, Absidia corymbefera, Rhizmucor miehei, Rhizopus deleman Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum, Fusarium heterosporum, Aspergillus oryzea, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: Humicola lanuginosa) and Landerina penisapora, particularly Thermomyces lanoginosus. Certain preferred lipases are supplied by Novozymes under the tradenames. Lipolase®, Lipolase Ultra®, Lipoprime®, Lipoclean® and Lipex® (registered tradenames of Novozymes) and LIPASE P "AMANO®" available from Areario Pharmaceutical Co. Ltd., Nagoya, Japan, AMANO-CES®, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A. and Diosynth Co., Netherlands, and other lipases such as Pseudomonas gladioli. Additional useful lipases are described in WIPO publications WO 02062973, WO 2004/101759, WO 2004/101760 and WO 2004/101763. In one embodiment, suitable lipases include the "first cycle lipases" described in WO 00/60063 and U.S. Patent 6,939,702 Bl, preferably a variant of SEQ ID No. 2, more preferably a variant of SEQ ID No. 2 having at least 90% homology to SEQ ID No. 2 comprising a substitution of an electrically neutral or negatively charged amino acid with R or K at any of positions 3, 224, 229, 231 and 233, with a most preferred variant comprising T23 IR and N233R mutations, such most preferred variant being sold under the tradename Lipex® (Novozymes).

The aforementioned lipases can be used in combination (any mixture of lipases can be used). Suitable lipases can be purchased from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham

Pharmacia Biotech., Piscataway, New Jersey, U.S.A; Diosynth Co., Oss, Netherlands and/or made in accordance with the examples contained herein.

Lipid esterase with reduced potential for odour generation and a good relative performance, are particularly preferred, as described in WO 2007/087243. These include lipoclean ® (Novozyme).

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

C16 and/or C18 ether sulfate

Alcohol ether sulfates are discussed in Anionic Surfactants: Organic Chemistry edited by H.W Stache (Marcel Dekker 1996).

The composition comprises from 2 to 25 wt.%, preferably from 3 to 20 wt.%, most preferably from 4 to 15 wt.% of a C16 and/or C18 ether sulfate.

C16 and/or C18 ether sulfates are ether sulfates of the form R ₂ -(0CH ₂ CH ₂ ) _n 0S0 ₃ H where R2 is saturated or monounsaturated linear C16 and/or C18 alkyl and where n is from 5 to 15, preferably from 6 to 15, more preferably from 7 to 15, most preferably 7 to 12.

The monounsaturation is preferably in the 9 position of the chain, and the double bond may be in a cis or trans configuration (oleyl or elaidic). The cis or trans ether sulfate CH3(CH2)7- CH=CH-(CH ₂ ) ₈ 0-(0CH ₂ CH ₂ ) _n 0S0 ₃ H, is described as C18: 1 (D9) ether sulfate. 18 is the number of carbon atoms in the chain, 1 is the number of double bonds and D9 the position of the double bond on the chain. Most preferably R2 is selected from linear C16 alkyl, linear C18 alkyl, linear C18: 1 (A9) alkyl and mixtures thereof.

Preferred examples are C16 and/or C18 ether sulfates with alkyl chains selected from a mixture of cetyl (linear C16) and stearyl (linear C18); oleyl ether sulfates and elaidic ether sulfates; and mixtures thereof.

Oleyl ether sulfates have a monounsaturated C18 chain with a cis double bond in the 9 position of the chain. Elaidic ether sulfate have a monounsaturated C18 chain with a trans double bond in the 9 position of the chain. Alcohol ether sulfates may be synthesised by ethoxylation of an alkyl alcohol to form an alcohol ethoxylate followed by sulfonation and neutralisation with a suitable alkali.

The production of the alcohol ethoxylate involves an ethoxylation reaction:

R-OH + q ethylene oxide ^R-0-(CH2CH20)q-H

Such ethoxylation reactions are described in Non-Ionic Surfactant Organic Chemistry (N. M. van Os ed), Surfactant Science Series Volume 72, CRC Press.

Preferably the reactions are base catalysed using NaOH, KOH, or NaOCH3. Even more preferred are catalyst which provide narrower ethoxy distribution than NaOH, KOH, or NaOCH3. Preferably these narrower distribution catalysts involve a Group II base such as Ba dodecanoate; Group II metal alkoxides; Group II hyrodrotalcite as described in

W02007/147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

Preferably the ethoxy distribution has greater than 70 wt.%, more preferably greater than 80 w.t% of the alcohol ethoxylate R-0-(CH2CH20)q-H in the range R-0-(CH2CH20)x-H to R- 0-(CH2CH20)y-H where q is the mole average degree of ethoxylation and x and y are absolute numbers, where x = q-q/2 and y = q+q/2.

For example when q = 10, then the greater than 70 wt.% of the alcohol ethoxylate should consist of ethoxylate with 5, 6, 7, 8, 9 10, 11 , 12, 13, 14 and 15 Ethoxylate groups.

The alkyl chain in the alcohol ether sulfate is preferably obtained from plants, preferably from a variety of plants. In this case the oil fraction is preferably extracted, the triglyceride hydrolysed to give the carboxylic acid which is reduced to give the alkyl alcohol required for the surfactant synthesis. Preferably the oil is hydrogenated to removed polyunsaturated alkyl chains such as linoleic and linoleneic acid. Preferred plant sources of oils are palm, rapeseed, sunflower, maze, soy, cottonseed, olive oil and trees. The oil from trees is called tall oil. Most preferably the oil source is rapeseed oils. Palm oil may be used but is not preferred.

Hydrogenation of oils is described in A Practical Guide to Vegetable Oil Processing (Gupta M.K. Academic Press 2017) The alkyl ether sulfate surfactants may be in salt form or acid form, typically in the form of a water-soluble sodium, potassium, ammonium, magnesium or mono-, di- or tri- C2-C3 alkanolammonium salt, with the sodium cation being the usual one chosen.

Preferably the weight fraction of saturated R (C18 alcohol ether sulfate)/(C16 alcohol ether sulfate) is from 2 to 400, more preferably 8 to 200 where, the weight of the alkyl ether sulfate is for the protonated form R -(OCH CH ) _n OSC> H.

Linear saturated or mono-unsaturated C20 and C22 alcohol ether sulfate may be present, preferably where n (the average number of moles of ethoxylation) is 6 to 14, preferably 7 to 13. Preferably the ratio of sum of (C18 alcohol ether sulfate)/(C20 and C22 alcohol ether sulfate) is greater than 10.

Surfactant other than the surfactant specified in (b)

Additional surfactants

The composition may comprise additional surfactant other than surfactants (a) and (b) such that the fraction [wt% additional surfactant]/[sum wt% of (a) and (b)] is from 0 to 0.5, preferably 0 to 0.2, most preferably 0 to 0.1.

Additional anionic surfactant

The composition may comprise additional anionic surfactant other than specified in (b) of the claims (the C16 and/or C18 ether sulfates of (b)).

Any anionic surfactant may be used. However preferred surfactants are described below. The anionic surfactants that may be added are those surfactants other than the surfactant specified in (b) of the claims (the cetearyl ether sulfates).

Examples of suitable anionic detergent compounds are selected from C12 to C18 alkyl ether carboxylates; citric acid ester of a C16 to C18 monoglyceride (citrem), tartartic acid esters of a C16 to C18 monoglyceride (tatem) and diacetyl tartaric acid ester of a C16 to C18 monoglyceride (datem); and water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms; and mixtures thereof. Citrem, tatem and datem are described in Hasenhuettl, G.L and Hartel, R.W. (Eds) Food Emulsifiers and Their Application. 2008 (Springer) and in Whitehurst, R.J. (Ed) Emulsifiers in Food Technology 2008 (Wiley-VCH).

Most preferably, the additional anionic surfactant comprises C16 to C18 alkyl ether carboxylates; citric acid ester of a C16 to C18 monoglyceride (citrem), tartartic acid esters of a C16 to C18 monoglyceride (tatem) and diacetyl tartaric acid ester of a C16 to C18 monoglyceride (datem) and sulfonates, for example, linear alkyl benzene sulfonate.

Preferably the total amount of additional anionic surfactant is 0 to 100 wt.% of the additional surfactant, preferably 30 to 90 wt.%

Preferably the total amount of additional anionic surfactant other than anionic surfactant (b) in a composition of the invention ranges from 0.5 to 20 wt.%, more preferably from 1 to 16 wt.%, even more preferably from 1.5 to 14 wt.%, most preferably from 2 to 12 wt.%.

Preferably these additional anionic surfactants are present at lower levels than the alkyl ether sulfate, preferably the weight fraction of further anionic surfactant/alkyl ether surfactant (b) is from 0 to 0.4, more preferably 0 to 0.1.

Preferably the surfactants used are saturated or mono-unsaturated. Preferably the alkyl chains are derived from natural sources.

Nonionic surfactant

Any nonionic surfactant may be used, however, preferred nonionic surfactants are described below.

Nonionic surfactants are preferably selected from saturated and mono-unsaturated aliphatic alcohol ethoxylates.

Aliphatic alcohol ethoxylates for use in the invention may suitably be selected from Cs to Cie primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol. Preferably the nonionic surfactant is saturated and mono-unsaturated aliphatic alcohol ethoxylate, preferably selected from Ci2to C20 primary linear alcohol ethoxylates with an average of from 5 to 30 ethoxylates, more preferably C16 to C18 with an average of from 5 to 25 ethoxylates. Preferably the alkyl chain is mono-unsaturated.

Mixtures of any of the above described materials may also be used.

Preferably the total amount of nonionic surfactants in a composition of the invention ranges from 0.5 to 10 wt.%, more preferably from 1 to 8 wt.%, even more preferably from 1.5 to 6 wt.%, most preferably from 2 to 5 wt.%.

Further Preferred ingredients

Cleaning Boosters

The composition preferably comprises from 0.5 to 15 wt.%, more preferably from 0.75 to 15 wt.%, even more preferably from 1 to 12 wt.%, most preferably from 1.5 to 10 wt.% of cleaning boosters selected from antiredeposition polymers; soil release polymers;

alkoxylated polycarboxylic acid esters as described in WO/2019/008036 and

WO/2019/007636; and mixtures thereof.

Antiredeposition polymers

Preferred antiredeposition polymers include alkoxylated polyamines.

A preferred alkoxylated polyamine comprises an alkoxylated polyethylenimine, and/or alkoxylated polypropylenimine. The polyamine may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25. A preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30 preferably from 15 to 25, where a nitrogen atom is ethoxylated.

Soil release polymer

Preferably the soil release polymer is a polyester soil release polymer.

Preferred soil release polymers include those described in WO 2014/029479 and WO 2016/005338. Preferably the polyester based soil release polymer is a polyester according to the following formula (I)

wherein

R ¹ and R ² independently of one another are X-(OC ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m wherein X is C _1-4 alkyl and preferably methyl, the -(OC ₂ H ₄ ) groups and the -(OC ₃ H ₆ ) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C ₃ H ₆ ), and preferably are independently of one another X- (OC2H4)n-(OC3H6)m,

n is based on a molar average number of from 12 to 120 and preferably of from 40 to 50,

m is based on a molar average number of from 1 to 10 and preferably of from 1 to 7, and

a is based on a molar average number of from 4 to 9.

Preferably the polyester provided as an active blend comprising:

A) from 45 to 55 % by weight of the active blend of one or more polyesters according to the following formula (I)

wherein

R ¹ and R ² independently of one another are X-(OC ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m wherein X is C _1-4 alkyl and preferably methyl, the -(OC ₂ H ₄ ) groups and the -(OC ₃ H ₆ ) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C ₃ H ₆ ), and preferably are independently of one another X- (OC ₂ H4)n-(OC ₃ H6)m,

n is based on a molar average number of from 12 to 120 and preferably of from 40 to 50, m is based on a molar average number of from 1 to 10 and preferably of from 1 to 7, and

a is based on a molar average number of from 4 to 9 and

B) from 10 to 30 % by weight of the active blend of one or more alcohols selected from the group consisting of ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2-butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol and butyl glycol and

C) from 24 to 42 % by weight of the active blend of water.

Alkoxylated polycarboxylic acid esters

Alkoxylated polycarboxylic acid esters are obtainable by first reacting an aromatic

polycarboxylic acid containing at least three carboxylic acid units or anhydrides derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or anhydrides derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or anhydrides derived therefrom, even more preferably trimellitic acid or trimellitic acid anhydride, most preferably trimellitic acid anhydride, with an alcohol alkoxylate and in a second step reacting the resulting product with an alcohol or a mixture of alcohols, preferably with C16/C18 alcohol.

Further Ingredients

The formulation may contain further ingredients.

Builders or Complexing Agents

The composition may comprise a builder or a complexing agent.

Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.

Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid. The composition may also contain 0-10 wt.% of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, citric acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.

More preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt.% of phosphate. Most preferably the laundry detergent formulation is not built i.e. contain less than 1 wt.% of builder.

If the detergent composition is an aqueous liquid laundry detergent it is preferred that mono propylene glycol or glycerol is present at a level from 1 to 30 wt.%, most preferably 2 to 18 wt.%, to provide the formulation with appropriate, pourable viscosity.

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.

The total amount of the fluorescent agent or agents used in the composition is generally from 0.0001 to 0.5 wt.%, preferably 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt.%.

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 fluorescers with CAS-No 3426-43-5; CAS-No 35632-99-6; CAS-No 24565-13-7; CAS-No 12224-16-7; CAS-No 13863-31-5; CAS-No 4193-55-9; CAS-No 16090- 02-1 ; CAS-No 133-66-4; CAS-No 68444-86-0; CAS-No 27344-41-8.

Most preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-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' disulphonate, 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.

Shading dye

It is advantageous to have shading dye present in the formulation. 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), Wley-VCH Weinheim 2003).

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 .

Preferred dye chromophores are azo, azine, anthraquinone, phthalocyanine and

triphenylmethane. Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged. Azine dyes preferably carry a net anionic or cationic charge.

Blue or violet Shading dyes are most preferred. Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In this regard the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 260 to 320, most preferably 270 to 300. The white cloth used in this test is bleached non-mercerised woven cotton sheeting.

Shading dyes are discussed in W02005/003274, W02006/032327(Uni lever),

W02006/032397(Unilever), W02006/045275(Unilever), WO 2006/027086(Unilever), W02008/017570(Unilever), WO 2008/141880(Unilever), W02009/132870(Uni lever),

WO 2009/141173 (Unilever), WO 2010/099997(Unilever), WO 2010/102861 (Unilever), WO 2010/148624(Unilever), W02008/087497 (P&G), WO2011/011799 (P&G), W02012/054820 (P&G), WO2013/142495 (P&G), W02013/151970 (P&G), W02018/085211 (P&G), and WO2019/075149 (P&G).

A mixture of shading dyes may be used.

The shading dye chromophore is most preferably selected from mono-azo, bis-azo and azine.

Mono-azo dyes preferably 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 WO2013/142495 and W02008/087497. A preferred example of a thiophene dye is shown below:

Bis-azo dyes are preferably sulphonated bis-azo dyes. Preferred examples of sulphonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 11 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , direct violet 66, direct violet 99 and alkoxylated versions thereof.

Alkoxylated bis-azo dyes are discussed in W02012/054058 and WO/2010/151906.

An example of an alkoxylated bis-azo dye is :

Azine dyes 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, and the phenazine dye selected from:

wherein:

X ₃ is selected from: -H; -F; -CH ₃ ; -C ₂ H ₅ ; -OCH ₃ ; and, -OC ₂ H ₅ ;

X4 is selected from: -H; -CH ₃ ; -C ₂ H ₅ ; -OCH ₃ ; and, -OC ₂ H ₅ ;

Y ₂ is selected from: -OH; -OCH2CH2OH; -CH(OH)CH ₂ OH; -OC(0)CH ₃ ; and, C(0)OCH _3. Anthraquinone dyes covalently bound to ethoxylate or propoxylated polyethylene imine may be used as described in WO2011/047987 and WO 2012/119859. The shading dye is preferably present is present in the composition in range from 0.0001 to 0.1wt %. 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 preferably a blue or violet shading dye.

Perfume

The composition preferably comprises a perfume. 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 Flavour Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavour 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.

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.

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.

Enzymes

Preferably other enzymes, such as proteases, alpha-amylases, cellulases,

peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof, may be present in the formulation.

If further enzymes are present, then preferably they are selected from: proteases, alpha- amylases, cellulases and mixtures thereof.

If present, then the level of each enzyme in the laundry composition of the invention is from 0.0001 wt.% to 0.1 wt.%.

Levels of enzyme present in the composition preferably relate to the level of enzyme as pure protein. 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 sub divisions, 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 W009/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89/06279 and protease PD138 described in (WO 93/18140). Other useful proteases may be those described in WO 92/175177, WO 01/016285, WO 02/026024 and WO 02/016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270, WO 94/25583 and WO 05/040372, and the chymotrypsin proteases derived from Cellumonas described in WO 05/052161 and WO 05/052146.

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 W009/021867, 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 Bl, US 5,679,630, US 4,760,025, US7,262,042 and WO 09/021867. 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).

The invention may use 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 WO 2009/087524, WO 2009/090576, WO 2009/107091 , WO 2009/111258 and WO 2009/148983.

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.

Adjunct Ingredients

The detergent compositions optionally include one or more laundry adjunct ingredients.

To prevent oxidation of the formulation an anti-oxidant may be present in the formulation.

The term "adjunct ingredient" includes: perfumes, dispersing agents, stabilizers, pH control agents, metal ion control agents, colorants, brighteners, dyes, odour control agent, pro perfumes, cyclodextrin, perfume, solvents, soil release polymers, preservatives,

antimicrobial agents, chlorine scavengers, anti-shrinkage agents, fabric crisping agents, spotting agents, anti-oxidants, anti-corrosion agents, bodying agents, drape and form control agents, smoothness agents, static control agents, wrinkle control agents, sanitization agents, disinfecting agents, germ control agents, mould control agents, mildew control agents, antiviral agents, antimicrobials, drying agents, stain resistance agents, soil release agents, malodour control agents, fabric refreshing agents, chlorine bleach odour control agents, dye fixatives, dye transfer inhibitors, shading dyes, colour maintenance agents, colour restoration, rejuvenation agents, anti-fading agents, whiteness enhancers, anti-abrasion agents, wear resistance agents, fabric integrity agents, anti-wear agents, and rinse aids, UV protection agents, sun fade inhibitors, insect repellents, anti-allergenic agents, enzymes, flame retardants, water proofing agents, fabric comfort agents, water conditioning agents, shrinkage resistance agents, stretch resistance agents, and combinations thereof. If present, such adjuncts can be used at a level of from 0.1% to 5% by weight of the

composition

The invention will be further described with the following non-limiting examples. Example 1

A detergent product was created containing 2.5 wt.% alkyl ether sulfate and 2.5 wt.% alcohol ethoxylate (Neodol 25-7 ex Shell) in water at pH = 7 with and without the addition of 0.01 wt.% of lipase (lipex evity ® ex Novozymes (EC 3.1.1.3))

COOP brand Lard (pig fat) was purchased from the COOP (UK), stored in a domestic refrigerator and used as supplied. A small portion of Lard was placed in a glass test tube and the Lard melted by placing in a batch of hot water. 0.070g of the melted LARD was places in a small flat-bottomed glass tube (28ml tube) and allowed to solidify in a film on the bottom. This simulates fat on the surface of the garment and fat stains on the surfaces of hard surfaces of garment such as buttons.

The detergent product was added to water to give 10ml of wash solution at pH = 7, 20° FH (French Hardness) with 0.5g/L total surfactant and 0 or 1 mg/L lipase. The detergent solution was added to the tube and the tube sealed and placed in an incubator set to 40°C with a shaker speed of 150rpm for 1 hour. After wash the sample was place in ice for 30 minutes then the wash liquor was removed, and the tube rinsed twice with 50ml of cold 24 ⁰ FH water. The experiment was done in triplicate. The samples were left overnight (18hours) then the residual lard in each tube dissolved in 5ml of toluene and the solution used to spot onto a stainless Steel MALDI plate. For each tube 2 MALDI deposition spots were made giving 6 measurements per condition. When the toluene had evaporated the MALDI Mass spectra were measured on a Bruker Autoflex using 100% laser power.

Lard hydrolysis by the lipase was measured by area of the relative area of the diglyceride peaks, DG34:1 , which is formed by hydrolysis of the lard fat triglycerdes. DGx:y refers to a diglyceride with x carbon atoms excluding the glycerol group and a total of y carbon carbon double bonds.

The RA is the relative area of each diglyceride peak which is calculated as

RA = area of diglyceride/sum of area of triglyceride (TG48: 1 to TG54: 1)

The triglyceride peaks used for the sum of area of triglycerides were TG48:1 , TG50:3, TG50:2, TG50: 1 , TG50:0, TG51 : 1 , TG51 :0, TG52:4, TG52:3, TG52:2, TG52: 1 , TG52:0, TG53:2, TG53: 1 , TG53:0, TG54:6, TG54:4, TG54:3, TG54:2, and TG54: 1. TGx:y refers to a triglyceride with x carbon atoms excluding the glycerol group and a total of y carbon carbon double bonds. Measurement were conducted immediately and 2 weeks after the wash. The solutions were stored at room temperature and checked to ensure no evaporative losses. Significant additional hydrolysis over the 2 weeks only occurs in the presence of lipase.

The Increase in RA of DG34:1 over the 2 weeks was calculated as

ARA = 100*(RA(lipase 2 weeks) - RA(lipase immediately))

95% confidence limits were calculated from the repeats.

The results are tabulated below:-

LES is lauryl ether sulfate with 2 moles of ethoxylation.

SES(10EO) and SES (2EO) is stearyl ether sulfate with an average of 10 or 2 moles of ethoxylation

An unpaired t-test, showed the DG34:1 SES(10EO) to be significantly lower than the SES(2EO) and LES(2EO).

The lipase in LES(2EO) and SES(2EO) has a greater effect after 2 weeks than the SES(10EO), indicating more enzyme was deposited in the fat than for the SES(10EO). Surprisingly the SES(10EO) formulation according to the invention has lower deposition of lipase enzyme in the residual fat on the garment than the LES(2EO) or SES(2EO).