WO2022043042A1 - Detergent composition - Google Patents

Abstract

The invention concerns a liquid detergent composition, comprising: (a) from 1 to 50 wt.% of an alcohol ethoxylate of formula R1-(OCH2CH2)qOH, where at least 70% wt. of R1 is selected from saturated or monounsaturated linear C16 and/or C18 alkyl chains, and where q is from 4 to 20, and wherein greater than 50 wt.% of R1 is linear C18:1(Δ9) alkyl; and, (b) from 1 to 50 wt.% of linear alkyl benzene sulfonate (LAS); and/or, from 1 to 50 wt.% of C12-C14 alkyl ether sulfate; the invention also concerns a method, preferably a domestic method of treating a textile.

Description

DETERGENT COMPOSITION

Field of Invention

The present invention concerns a detergent composition. More particularly a liquid detergent composition comprising a saturated or monounsaturated C16 and/or C18 alcohol ethoxylate surfactant and a high foaming surfactant.

Background of the Invention

Laundry formulations containing C12-14 ether sulfate (C12-14 ES) surfactant and/or linear alkyl benzene sulfonate surfactant (LAS) are widely used. These surfactants are high foaming and other ingredients must be added to avert over-foaming. Over-foaming prevents washing machines from functioning properly and gives rise to the need for extra rinsing to remove the foam from the clothes, which wastes water. C12-14 alcohol ethoxylate surfactants are widely used in detergent formulation as a nonionic surfactant that can also slightly reduce foam.

There is need for more effective surfactant materials to reduce the foaming of LAS and/or C12-14 ES based laundry formulations.

Surprisingly, this problem can be solved by the use of C16/C18 alcohol ethoxylates.

Summary of the Invention

The invention relates to a liquid detergent composition comprising: a) from 1 to 50 wt.%, preferably from 2 to 25 wt.%, more preferably from 3 to 20 wt.%, most preferably from 4 to 15 wt.% of an alcohol ethoxylate of formula Ri-(OCH₂CH₂)_qOH; where at least 70% wt. of Ri is selected from saturated or monounsaturated linear C16 and/or C18 alkyl chains and where q is from 4 to 20, preferably 5 to 14, more preferably 8 to 12, and wherein greater than 50 wt.% of Ri is linear C18:1(A9) alkyl; and, b) from 1 to 50 wt.%, preferably from 1.5 to 25 wt.%, more preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of linear alkyl benzene sulfonate (LAS); and/or, from 1 to 50 wt.%, preferably from 1.5 to 25 wt.%, more preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of Ci₂-Ci4 alkyl ether sulfate. Preferably at least 75 wt.%, more preferably at least 80 wt.%, even more preferably at least 85 wt.%, even more preferably at least 90 wt.%, most preferably at least 95 wt.% of Ri is preferably selected from saturated or monounsaturated linear C16 and/or C18 alkyl chains.

Preferably the alcohol ethoxylate of formula Ri-(OCH2CH2)_qOH is monounsaturated linear, more preferably the mono-unsaturation is in the 9 position of the chain, where the carbons are counted from the ethoxylate bound chain end, more preferably the double bond is in a cis configuration.

The double bond may be in a cis or trans configuration (oleyl or elaidyl), preferably cis. The cis or trans alcohol ethoxylate CH3(CH2)7-CH=CH-(CH2)8O-(OCH2CH2)_nOH, is described as C18:1(A9) alcohol ethoxylate. This follows the nomenclature CX:Y(AZ) where X is the number of carbons in the chain, Y is the number of double bonds and AZ the position of the double bond on the chain where the carbons are counted from the OH bound chain end.

Preferably Ri is selected from linear C16 alkyl, linear C18 alkyl, linear C18:1(A9) alkyl and mixtures thereof. Preferably greater than 60 wt.% of Ri is linear C18:1(A9) alkyl.

Preferably the weight fraction of C18 alcohol ethoxylate / C16 alcohol ethoxylate is greater than 1 , more preferably from 2 to 100, most preferably 3 to 30.

Preferably the composition comprises: i) from 1.5 to 25 wt.%, preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of linear alkyl benzene sulfonate (LAS); and, ii) from 1.5 to 25 wt.%, preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of C12-C14 alkyl ether sulfate.

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 liquid detergent composition is a laundry detergent composition.

Preferably the composition comprises one or more enzymes from the group: lipases proteases, alpha-amylases, cellulases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof, more preferably lipases, proteases, alpha-amylases, cellulases and mixtures thereof, wherein the level of each enzyme in the composition of the invention is from 0.0001 wt.% to 0.1 wt.%.

In a second aspect the invention provides a method, preferably 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 liquid detergent composition, preferably the laundry liquid detergent composition, of the first aspect.

Preferably in the method the aqueous solution contains 0.1 to 1.0g/L of the surfactants of (a) and (b).

The method, preferably a domestic method taking place in the home using domestic appliances, preferably occurs at wash water temperatures of 280 to 335K. The textile is preferable soiled with sebum arising from contact with human skin.

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. wt.% relates to the amount by weight of the ingredient based on the total weight of the composition. For anionic surfactants, wt.% is calculated based on the protonated form of the surfactant.

The formulation is a liquid composition.

The formulation when dissolved in demineralised water at 20°C preferably has a pH of 3 to 10, more preferably from 4 to 8, more preferably 6.5 to 7.5, most preferably 7. The integers ‘q’ (and where used ‘m’ and ‘n’) are mole average values.

C16 and/or C18 Alcohol Ethoxylate

The alcohol ethoxylate is of the formula:

Ri-(OCH₂CH₂)_qOH where at least 70 wt.% of Ri is preferably selected from saturated or monounsaturated linear C16 and/or C18 alkyl chains and where q is from 4 to 20, preferably 5 to 14, more preferably 8 to 12, wherein greater than 50 wt.% of Ri is linear C18:1 (A9) alkyl.

Preferably at least 75 wt.%, more preferably at least 80 wt.%, even more preferably at least 85 wt.%, even more preferably at least 90 wt.%, most preferably at least 95 wt.% of Ri is preferably selected from saturated or monounsaturated linear C16 and/or C18 alkyl chains.

Preferably the alcohol ethoxylate of formula Ri-(OCH₂CH₂)_qOH is monounsaturated linear.

The mono-unsaturation is preferably in the 9 position of the chain, where the carbons are counted from the ethoxylate bound chain end. The double bond may be in a cis or trans configuration (oleyl or elaidyl), preferably cis. The cis or trans alcohol ethoxylate CHs(CH₂)7- CH=CH-(CH₂)8O-(OCH₂CH₂)_nOH, is described as C18:1(A9) alcohol ethoxylate. This follows the nomenclature CX:Y(AZ) where X is the number of carbons in the chain, Y is the number of double bonds and AZ the position of the double bond on the chain where the carbons are counted from the OH bound chain end.

Most preferably Ri is selected from linear C16 alkyl, linear C18 alkyl, linear C18:1(A9) alkyl and mixtures thereof. Preferably greater than 60 wt.% of Ri is linear C18:1(A9) alkyl.

Alcohol ethoxylates are discussed in the Non-ionic Surfactants: Organic Chemistry edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series published by CRC press.

Preferably the weight fraction of C18 alcohol ethoxylate / C16 alcohol ethoxylate is greater than 1 , more preferably from 2 to 100, most preferably 3 to 30. 018 alcohol ethoxylate’ is the sum of all the C18 fractions in the alcohol ethoxylate and 016 alcohol ethoxylate’ is the sum of all the C16 fractions in the alcohol ethoxylate. Linear saturated or mono-unsaturated C20 and C22 alcohol ethoxylate may also be present. Preferably the weight fraction of sum of ‘C18 alcohol ethoxylate’ I ’C20 and C22 alcohol ethoxylate’ is greater than 10.

Preferably the alcohol ethoxylate contains less than 15 wt.%, more preferably less than 8 wt.%, most preferably less than 4 wt.% of the polyunsaturated alcohol ethoxylates. A polyunsaturated alcohol ethoxylate contains a hydrocarbon chains with two or more double bonds.

Alcohol ethoxylates may be synthesised by ethoxylation of an alkyl alcohol, via the reaction:

Ri-OH + q ethylene oxide - Ri-O-(CH2CH2O)_q-H

The alkyl alcohol may be produced by transesterification of the triglyceride to a methyl ester, followed by distillation and hydrogenation to the alcohol. The process is discussed in Journal of the American Oil Chemists' Society. 61 (2): 343-348 by Kreutzer, II. R.

The degree of polyunsaturation in the surfactant may be controlled by hydrogenation of the triglyceride as described in: A Practical Guide to Vegetable Oil Processing (Gupta M.K. Academic Press 2017). Distillation and other purification techniques may be used.

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

Preferably the ethoxylation reactions are base catalysed using NaOH, KOH, or NaOCHs. Even more preferred are catalyst which provide narrower ethoxy distribution than NaOH, KOH, or NaOCHs. 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 narrow ethoxy distribution has greater than 70 wt.%, more preferably greater than 80 w.t% of the alcohol ethoxylate R-O-(CH2CH2O)_q-H in the range R-O-(CH2CH2O)_X-H to R-O-(CH2CH2O)_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 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.

Source of alkyl chains

The alkyl chain of C16/C18 surfactant is preferably obtained from a renewable source, preferably from a triglyceride. A renewable source is one where the material is produced by natural ecological cycle of a living species, preferably by a plant, algae, fungi, yeast or bacteria, more preferably plants, algae or yeasts.

Preferred plant sources of oils are rapeseed, sunflower, maze, soy, cottonseed, olive oil and trees. The oil from trees is called tall oil. Most preferably Palm and Rapeseed oils are the source.

Algal oils are discussed in Energies 2019, 12, 1920 Algal Biofuels: Current Status and Key Challenges by Saad M.G. et al. A process for the production of triglycerides from biomass using yeasts is described in Energy Environ. Sci. , 2019,12, 2717 A sustainable, high- performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents by Masri M.A. et al.

Non edible plant oils may be used and are preferably selected from the fruit and seeds of Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seed), Linseed, Pongamia pinnata (karanja), Hevea brasiliensis (Rubber seed), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L. (castor), Simmondsia chinensis (Jojoba), Eruca sativa. L., Cerbera odollam (Sea mango), Coriander (Coriandrum sativum L.), Croton megalocarpus, Pilu, Crambe, syringa, Scheleichera triguga (kusum), Stillingia, Shorea robusta (sal), Terminalia belerica roxb, Cuphea, Camellia, Champaca, Simarouba glauca, Garcinia indica, Rice bran, Hingan (balanites), Desert date, Cardoon, Asclepias syriaca (Milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var. vestita, Alagae, Argemone mexicana L. (Mexican prickly poppy, Putranjiva roxburghii (Lucky bean tree), Sapindus mukorossi (Soapnut), M. azedarach (syringe), Thevettia peruviana (yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, B. napus, Zanthoxylum bungeanum. Linear Alkyl Benzene Sulfonate (LAS)

Linear alkyl benzene sulfonate is the neutralised form of linear alkyl benzene sulfonic acid.

Neutralisation may be carried out with any suitable base.

Linear alkyl benzene sulfonic acid has the structure:

where x + y = 7,8,9 or 10. Preferably x + y = 8 is present at greater than 28 wt.% of the total LAS. Preferably x + y = 9 is present at greater than 28 wt.% of the total LAS. Weights are expressed as the protonated form. It may be produced by a variety of different routes. Synthesis is discussed in Anionic Surfactants Organic Chemistry edited by H.W. Stache (Marcel Dekker, New York 1996). Linear alkyl benzene sulfonic acid may be made by the sulfonation of Linear alkyl benzene. The sulfation can be carried out with concentrated sulphuric acid, oleum or sulphur trioxide. Linear alkyl benzene sulfonic acid produced by reaction of linear alkyl benzene with sulphur trioxide is preferred.

Linear alkyl benzene may be produced by a variety of routes. Benzene may be alkylated with n-alkenes using HF catalyst. Benzene may be alkylated with n-alkenes in a fixed bed reactor with a solid acidic catalyst such as alumosilicate (DETAL process). Benzene may be alkylated with n-alkenes using an aluminium chloride catalyst. Benzene may be alkylated with n-chloroparaffins using an aluminium chloride catalyst.

C12-C14 alkyl ether sulfate (C12-14 ES)

Alkyl ether sulfate synthesis is discussed in Anionic Surfactants Organic Chemistry edited by H.W. Stache (Marcel Dekker, New York 1996). Alcohol ether sulfates are produced by the sulfonation of the corresponding alcohol ethoxylate.

The alkyl ether sulfate surfactants herein are of the formula R2-(OCH2CH2)_nOSO3H wherein R2 is an unsubstituted C12, C13 and C14 saturated alkyl chain, preferably linear alkyl chain, most preferably lauryl, n is from 0.5 to 5, more preferably from 0.5 to 3.5, most preferably from 1 to 3. The integer n is the mole average value. Preferably both LAS and C12-C14 ether sulfate (C12-14 ES) are included in the detergent formulation. Preferably when both are included, the weight ratio of LAS/(C12-14ES) is from 0.2 to 5, preferably from 0.25 to 4, more preferably from 0.3 to 2, most preferably from 0.33 to 1.5.

Preferably the composition comprises: i) from 1.5 to 25 wt.%, preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of linear alkyl benzene sulfonate (LAS); and, ii) from 1.5 to 25 wt.%, preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of C12-C14 alkyl ether sulfate.

Further Preferred ingredients

Additional surfactants

The composition may comprise additional surfactant other than surfactants (a) and (b).

Additional surfactants may include further nonionic surfactants, anionic surfactants and amphoteric surfactants.

Preferably the total amount of additional surfactants other than specified as (a) and (b) in claim 1 , 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 12 wt.%, most preferably from 2 to 10 wt.%.

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

R¹ and R² independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is C1.4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OCsHe) groups are arranged blockwise and the block consisting of the -(OCsHe) groups is bound to a COO group or are HO-(C₃H6), 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

R¹ and R² independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is C1.4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OCsHe) groups are arranged blockwise and the block consisting of the -(OCsHe) groups is bound to a COO group or are HO-(C₃H6), 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 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.

Enzymes

Preferably enzymes, such as lipases, proteases, alpha-amylases, cellulases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof, may be present in the formulation. If enzymes are present, then preferably they are selected from: lipases, proteases, alphaamylases, 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.

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 218272), 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 407225, 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, WO 00/60063.

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

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 Ai 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.

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 (htp://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 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, alphaamylases 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 ^TM, 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.

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), Wiley-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(Uni lever), 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), W02018/085311 (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 WO2012/054058 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:

X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and, -OC2H5;

X4 is selected from: -H; -CH3; -C2H5; -OCH3; and, -OC2H5;

Y₂ is selected from: -OH; -OCH2CH2OH; -CH(OH)CH₂OH; -OC(O)CH₃; and, C(O)OCH₃.

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, isoguinolone, 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, alphaterpinenol, 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.

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, properfumes, 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.

Laundry detergents containing 10 wt.% of surfactant (remainder water) was added to 26° FH (degrees French Hardness) water at 293K to give 0.2g/L surfactant in water.

The detergents contained the following weight ratios:

3:1 LES(1 E0) : LAS (comparative)

3:1 :0.44 LES(1 E0) : LAS : C12-7EO (comparative)

(iii) 3:1 :0.44 LES(1E0) : LAS : C18:1-1 OEO (inventive)

C12-7EO is a lauryl alcohol ethoxylate with n average of 7 moles of ethoxylation. This is the most widely used commercial nonionic surfactant.

The number of EO units per carbon the alkyl chain is 7/12 = 0.6 (1 significant figure)

C18: 1-1 OEO is an oleyl alcohol ethoxylate with an average of 10 moles of ethoxylation (Genapol 0-100 ex Clariant).

The number of EO units per carbon the alkyl chain is 10/18 = 0.6 (1 significant figure).

The oleyl alcohol ethoxylate has the same balance of alkyl chain to EO as the lauryl alcohol ethoxylate.

LES(1 EO) is lauryl ether sulfate with 1 mole average of ethoxylation.

10ml of the solution was placed in a tube of 2.2cm diameter and stoppered. The tube was inverted 40 times to produce foam and a photograph taken of the tube. A 1mg aliquots of soil was then added in and the inversion process and photography cycle. The soil was an emulsion with a weight ratio of 5:5:1 olive oil:water:kaolin + 0.13 wt.% flour. Kaolin was purchased from Sigma-Aldrich. The height of the foam was measured as the difference between the meniscus and top of the foam. The experimental values are the average of 4 repeat tubes and are shown in the table below alongside the 95% confidence limits.

While the introduction of C12-7EO reduces the foam, surprisingly the C18:1-10EO reduces the foam significantly more.

Claims

23 CLAIMS

1. A liquid detergent composition, comprising: a) from 1 to 50 wt.%, preferably from 2 to 25 wt.%, more preferably from 3 to 20 wt.%, most preferably from 4 to 15 wt.% of an alcohol ethoxylate of formula Ri-(OCH₂CH₂)_qOH; where at least 70% wt. of Ri is selected from saturated or monounsaturated linear C16 and/or C18 alkyl chains and where q is from 4 to 20, preferably 5 to 14, more preferably 8 to 12 and, wherein greater than 50 wt.% of Ri is linear C18:1(A9) alkyl; and, b) from 1 to 50 wt.%, preferably from 1.5 to 25 wt.%, more preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of linear alkyl benzene sulfonate (LAS); and/or, from 1 to 50 wt.%, preferably from 1.5 to 25 wt.%, more preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of C12-C14 alkyl ether sulfate.

2. A detergent composition according to claim 1 , wherein at least 75 wt.%, preferably at least 80 wt.%, more preferably at least 85 wt.%, even more preferably at least 90 wt.%, most preferably at least 95 wt.% of Ri is selected from saturated or monounsaturated linear C16 and/or C18 alkyl chains.

3. A detergent composition according to claim 1 or claim 2, wherein the alcohol ethoxylate of formula Ri-(OCH₂CH₂)_qOH is monounsaturated linear, preferably the mono-unsaturation is in the 9 position of the chain, where the carbons are counted from the ethoxylate bound chain end, more preferably the double bond is in a cis configuration.

4. A detergent composition according to any preceding claim, wherein Ri is selected from linear C16 alkyl, linear C18 alkyl, linear C18:1(A9) alkyl and mixtures thereof, and preferably greater than 60 wt.% of Ri is linear C18:1(A9) alkyl.

5. A detergent composition according to any preceding claim, wherein the weight fraction of C18 alcohol ethoxylate / C16 alcohol ethoxylate is greater than 1 , more preferably from 2 to 100, most preferably 3 to 30.

6. A detergent composition according to any preceding claim, wherein the composition comprises: i) from 1.5 to 25 wt.%, preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of linear alkyl benzene sulfonate (LAS); and, ii) from 1 .5 to 25 wt.%, preferably from 2 to 20 wt.%, most preferably from 3 to 15 wt.% of C12-C14 alkyl ether sulfate.

7. A detergent composition according to any preceding claim, wherein 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.

8. A detergent composition according to claim 7, wherein the antiredeposition polymers are alkoxylated polyamines; and/or the soil release polymer is a polyester soil release polymer.

9. A detergent composition according to claim 7 or claim 8, wherein the soil release polymer is a polyester soil release polymer.

10. A detergent composition according to any preceding claim, wherein the composition is a laundry detergent composition.

11. A detergent composition according to any preceding claim, wherein the composition comprises one or more enzymes from the group: lipases, proteases, alpha-amylases, cellulases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof, preferably lipases, proteases, alpha-amylases, cellulases and mixtures thereof, wherein the level of each enzyme in the composition of the invention is from 0.0001 wt.% to 0.1 wt.%.

12. A method, preferably 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 liquid detergent composition, preferably a laundry liquid detergent composition, of any one of claims 1 to 11 , and optionally drying the textile.

13. A method, preferably a domestic method, according to claim 12, wherein in the method, the aqueous solution contains 0.1 to 1.0g/L of the surfactants of (a) and (b). A method according to claim 12 or claim 13, preferably a domestic method taking place in the home using domestic appliances, wherein the method occurs at wash water temperatures of 280 to 335K.