EP3775127B1

EP3775127B1 - Cleaning composition

Info

Publication number: EP3775127B1
Application number: EP19722150.0A
Authority: EP
Inventors: Clare Ann JONES; Paul Simon Stevenson
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Priority date: 2018-05-17
Filing date: 2019-05-10
Publication date: 2022-07-20
Anticipated expiration: 2039-05-10
Also published as: CN112119147B; WO2019219531A1; EP3775127A1; BR112020023083A2; CN112119147A; AR117430A1

Description

Field of Invention

The present invention relates to a fluid cleaning composition. In particular, the invention relates to fluid cleaning compositions in the form of liquid laundry detergent compositions.

Background of the Invention

Many fluid cleaning compositions, in particular laundry liquid detergent compositions desirably contain cleaning polymers. These cleaning polymers, in particular alkoxylated polyamines and polyester-based soil release polymers are desirable to include because they provide weight efficient cleaning to the formulation. However, there is a problem with the inclusion of these polymers because they reduce the viscosity of the composition. The rheology of many fluid cleaning compositions could be improved in the eyes of the consumer. Consumers dislike fluid cleaning compositions that have a too low viscosity, there can be a perception that these compositions are not thick enough to provide adequate cleaning. Thus, there is a problem of how to improve the viscosity of fluid cleaning compositions.
One way of improving the viscosity is to include a further polymer, a thickening polymer such as a so-called HASE polymer (hydrophobically modified alkali soluble emulsion polymer). This thickening polymer boosts the rheology, especially the viscosity of the formulation.
US 2018/0044614 discloses in the claims and examples various formulations in the examples that include (a) a surfactant combination (rhamnolipid and other surfactant); (b) one or more viscosity modifiers; (c) EPEI; and (d) perfume. The viscosity modifiers are essential to the compositions of US 2018/0044614 , which are most preferentially pH greater than 7 to 13.
However, there is a need to improve the viscosity of the fluid cleaning composition, in particular laundry liquid detergent compositions to remove the need for additional thickening polymers.

Summary of the Invention

We have found that by adding rhamnolipid biosurfactant to a fluid cleaning composition, along with a betaine surfactant and by having a pH in the range in the range of from 4 to 5.5, improved rheology in terms of higher viscosity can be achieved.
In a first aspect the invention provides a fluid cleaning composition comprising:

a) from 5 to 70 wt.% of a surfactant system comprising:
1. i) at least one anionic and/or nonionic surfactant; and
2. ii) a rhamnolipid biosurfactant which is present at a level in the range of from 1 to 95 wt.%, preferably from 1 to 50 wt.%, more preferably from 2.5 to 50 wt.%, most preferably from 5 to 25 wt.% of the total surfactant in said surfactant system; and
3. iii) from 0.5 to 10 wt.% of a zwitterionic surfactant; and
b) water; and
c) from 0.1 to 15 wt.%, preferably from 0.1 to 10 wt.% of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester soil release polymer and mixtures thereof;

In a second aspect, the invention provides the use of a surfactant combination comprising a rhamnolipid biosurfactant and a zwitterionic surfactant to increase the viscosity of a fluid cleaning composition at a pH of from 4.5 to 5.5.
Preferably in the use of the second aspect, the rhamnolipid biosurfactant comprises at least 70 wt.% di-rhamnolipid, preferably at least 80 wt.% di-rhamnolipid, preferably of formula: Rha2C₈-₁₂C_8-12, where the alkyl chains may be saturated or unsaturated.

Detailed Description of the Invention

Where viscosities are measured herein, unless otherwise stated, they are measured on an Anton Paar ASC Rheometer at 25°C.
The fluid cleaning composition comprises from 5 to 70 wt.% of a surfactant system.
Preferably the fluid cleaning composition comprises from 5 to 60 wt.%, more preferably from 5 to 50 wt.%, even more preferably from 7.5 to 30 wt.%, most preferably from 7.5 to 25 wt.%, for example from 8 to 25 wt.%, or even from 8 to 20 wt.% of a surfactant system.
The surfactant system comprises at least one anionic or nonionic surfactant and a rhamnolipid biosurfactant which is present at a level in the range of from 1 to 95 wt.% of the total surfactant in said surfactant system.
Preferably the rhamnolipid is present at a level in the range of from 1 to 50 wt.% of the total surfactant in said surfactant system, more preferably from 2.5 to 50 wt.%, most preferably from 5 to 25 wt.%, for example from 7.5 to 25 wt.% of the total surfactant in said surfactant system.
The fluid cleaning compositions comprise water. Water is usually the balancing agent in the formulation, and may make up all or the bulk of the non-surfactant wt.% in the composition. Typical water inclusion levels may be from 50 to 90 wt.%, preferably from 60 to 90 wt.%, more preferably from 65 to 88 wt.%.

Rhamnolipid

The composition comprises a rhamnolipid biosurfactant.
Mono-rhamnolipids have a single rhamnose sugar ring.
Di-rhamnolipids have two rhamnose sugar rings.
In the case of rhamnolipids, throughout this patent specification, the prefixes mono- and di-are used to indicate respectively mono-rhamnolipids (having a single rhamnose sugar ring) and di-rhamnolipids (having two rhamnose sugar rings) respectively. If abbreviations are used R1 is mono-rhamnolipid and R2 is di-rhamnolipid.
The mono-rhamnolipid may be L-rhamnosyl-β-hydroxydecanoyl-β-hydroxydecanoate (RhaC₁₀C₁₀ with a formula of C₂₆H₄₈O₉) produced by P. aeruginosa.
Atypical di-rhamnolipid is L-rhamnosyl-L-rhamnosyl-β-hydroxydecanoyl-β-hydroxydecanoate (Rha2C₁₀C₁₀ with a formula of C₃₂H₅₈O₁₃).
In practice a variety of other minor components with different alkyl chain length combinations, depending upon carbon source and bacterial strain, exist in combination with the above more common rhamnolipids. The ratio of mono-rhamnolipid and di-rhamnolipid may be controlled by the production method. Some bacteria only produce mono-rhamnolipid, see US5767090 : Example 1, some enzymes can convert mono-rhamnolipid to di-rhamnolipid.
The following rhamnolipids are sources of mono- and di- rhamnolipids encompassed within the invention (C12:1, C14:1 indicates fatty acyl chains with double bonds):

Rhamnolipids produced by P. aeruginosa (mono-rhamnolipids):
Rha-C₈-C₁₀, Rha-C₁₀-C₈, Rha-C₁₀-C₁₀, Rha-C₁₀-C₁₂, Rha-C₁₀-C_12:1, Rha-C₁₂-C₁₀, Rha-C_12:1-C₁₀
Rhamnolipids produced by P. chlororaphis (mono-rhamnolipids only):
Rha-C₁₀-C₈, Rha-C₁₀-C₁₀, Rha-C₁₂-C₁₀, Rha-C_12:1-C₁₀, Rha-C₁₂-C₁₂, Rha-C_12:1-C₁₂, Rha-C₁₄-C₁₀, Rha-C_14:1-C₁₀.
Mono-rhamnolipids may also be produced from P.putida by introduction of genes rhIA and rhIB from Psuedomonas aeruginosa [Cha et al. in Bioresour Technol. 2008. 99(7):2192-9 ]
Rhamnolipids produced by P. aeruginosa (di-rhamnolipids):
Rha-Rha-C₈-C₁₀, Rha-Rha-C₈-C_12:1, Rha-Rha-C₁₀-C₈, Rha-Rha-C₁₀-C₁₀, Rha-Rha-C₁₀-C_12:1, Rha-Rha-C₁₀-C₁₂, Rha-Rha-C₁₂-C₁₀, Rha-Rha-C_12:1-C₁₂, Rha-Rha-C₁₀-C_14:1
Rhamnolipids produced by Burkholdera pseudomallei (di-rhamnolipids only):
Rha-Rha-C₁₄-C₁₄.
Rhamnolipids produced by Burkholdera (Pseudomonas) plantarii (di-rhamnolipids only):
Rha-Rha-C₁₄-C₁₄.
Rhamnolipids produced by P. aeruginosa which are initially unidentified as either mono- or di-rhamnolipids:
C₈-C₈, C₈-C₁₀, C₁₀-C₈, C₈-C_12:1, C_12:1-C₈, C₁₀-C₁₀, C₁₂-C₁₀, C_12:1-C₁₀, C₁₂-C₁₂, C_12:1-C₁₂, C₁₄-C₁₀, C_14:1-C₁₀, C₁₄-C₁₄.

Preferably, the rhamnolipid comprises at least 50 wt.% di-rhamnolipid, more preferably at least 60 wt.% di-rhamnolipid, even more preferably 70 wt.% di-rhamnolipid, most preferably at least 80 wt.% di-rhamnolipid.
Preferably the rhamnolipid is a di-rhamnolipid of formula: Rha2C₈-₁₂C_8-12. The preferred alkyl chain length is from C₈ to C₁₂, the alkyl chain may be saturated or unsaturated.

Surfactant

The fluid cleaning composition comprises at least one anionic and/or non-ionic surfactant. This means that the composition may comprises a single anionic surfactant, or a mixture of anionic surfactants, or a single nonionic surfactant, or a mixture of nonionic surfactant, or a mixture of one or more anionic surfactants with one or more nonionic surfactants.
Suitable nonionic and anionic surfactants may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 or in Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1996).
Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C₈ to C₁₈ alcohols, produced for example from tallow or coconut oil, Alkyl ether carboxylic acids; sodium and potassium alkyl C₉ to C₂₀ benzene sulphonates, particularly sodium linear secondary alkyl C₁₀ to C₁₅ benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
The anionic surfactant is preferably selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; alkyl ether carboxylates, and mixtures thereof.
More preferred anionic surfactants are selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates and mixtures thereof. Preferably the alkyl ether sulphate is a C₁₂-C₁₄ n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units. Sodium lauryl ether sulphate is particularly preferred (SLES). Preferably the linear alkyl benzene sulphonate is a sodium C₁₁ to C₁₅ alkyl benzene sulphonates. Preferably the alkyl sulphates is a linear or branched sodium C₁₂ to C₁₈ alkyl sulphates. Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyl sulphate).
Preferably the anionic surfactant comprises linear alkyl benzene sulphonates and/or alkyl ether sulphates.
Preferably two or more anionic surfactants are present, for example linear alkyl benzene sulphonate together with an alkyl ether sulphate.
The composition may comprise anionic and/or non-ionic surfactants.
Preferably the weight fraction of non-ionic surfactant to anionic surfactant is from 0 to 0.3. This means that non-ionic surfactant can be present (or it may be absent if the weight fraction is 0), but if non-ionic surfactant is present, then the weight fraction of the non-ionic surfactant is preferably at most 30% of the total weight of anionic surfactant + non-ionic surfactant.
Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are the condensation products of aliphatic C₈ to C₁₈ primary or secondary linear or branched alcohols with ethylene oxide.
If a non-ionic surfactant is present, then most preferably the non-ionic surfactant is an alcohol ethoxylate, more preferably a C₁₀-C₁₈ alcohol ethoxylate having an average of 3-10 moles of ethylene oxide, most preferably a C₁₂-C₁₅ alcohol ethoxylate having an average of 5-9 moles of ethylene oxide.
Preferably the surfactants used are saturated.

Zwitterionic surfactant

The surfactant system comprises from 0.5 to 10 wt.% of a zwitterionic surfactant. Preferably the composition comprises from 0.5 to 10 wt.%, preferably from 0.75 to 5 wt.%, most preferably from 1 to 4 wt.% of the zwitterionic surfactant, said surfactant being counted as part of the surfactant system.
The zwitterionic surfactant is preferably a betaine surfactant. Preferably the composition comprises from 0.5 to 10 wt.%, preferably from 0.75 to 5 wt.%, most preferably from 1 to 4 wt.% of a betaine surfactant, said surfactant being counted as part of the surfactant system. A preferred betaine surfactant is cocoamidopropyl betaine.
A preferred fluid cleaning composition is a liquid laundry detergent composition.
A preferred laundry detergent composition comprises:

a) from 5 to 50 wt.% of a surfactant system comprising:
1. i) at least one anionic and/or nonionic surfactant; and
2. ii) a rhamnolipid biosurfactant which is present at a level in the range of from 1 to 95 wt.%, preferably from 1 to 50 wt.%, more preferably from 2.5 to 50 wt.%, most preferably from 5 to 25 wt.% of the total surfactant in said surfactant system; and
3. iii) from 0.5 to 10 wt.% of a betaine surfactant;
b) water;
c) from 0.1 to 15 wt.%, preferably from 0.1 to 10 wt.% of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester soil release polymer and mixtures thereof;
d) from 0.1 to 2 wt.% of a perfume

₈

₁₂

_8-12

pH

The fluid cleaning compositions have a pH of from 4 to 5.5, preferably from 4.5 to 5.5.

Polymer

The composition comprises from 0.1 to 15 wt.%, preferably from 0.1 to 10 wt.% of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester soil release polymer and mixtures thereof.

Polyester soil release polymer

The composition may comprise from 0.05 to 6 wt.%, preferably from 0.1 to 5 wt.% of one or more polyester soil release polymer(s). Suitable polyester based soil release polymers are 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 C_1-4 alkyl and preferably methyl, the -(OC₂H₄) groups and the -(OC₃H₆) groups are arranged blockwise and the block consisting of the -(OC₃H₆) 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 C_1-4 alkyl and preferably methyl, the -(OC₂H₄) groups and the -(OC₃H₆) groups are arranged blockwise and the block consisting of the -(OC₃H₆) 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.

By active blend is meant that it is preformed and added to the remainder of the fluid cleaning composition, or to components which ultimately form the fluid cleaning composition.

Alkoxylated polyamine

The composition may and preferably does comprise of an alkoxylated polyamine. Suitable inclusion levels for the polymer are from 0.25 to 8 wt.%, preferably from 0.5 to 6 wt.% of an alkoxylated polyamine. Another preferred level is from 1 to 4 wt.%.
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.

Salt

Preferably the composition comprises a sodium chloride or magnesium sulfate salt.

Perfume

The composition preferably comprises a perfume. The perfume is preferably present in the range from 0.001 to 3 wt.%, more preferably 0.05 to 0.5 wt.%, even more preferably from 0.1 to 2 wt.%, most preferably 0.1 to 1 wt.%.
Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
The perfume can be provided as a free oil, or may in encapsulated form.

Other ingredients

Preferably the composition comprises an ionic salt. The salt preferably comprises any organic or inorganic cation, including without limitation cations of alkali metals Cs, Na, K, Ca, Mg etc., with anions including halide anions, more preferably Cl. Other preferred salts compise organic cations e.g. amides (- ⁺NH-R ) or ammonium cations or substituted forms thereof e.g. triethylammonium. Anions for organic cations may comprise any akyl, aryl, arylalkyl moiety which may be short, medium, long, branched, cyclic or linear.
Preferably the composition comprises from 0.01 - 5wt.% by weight of the salt. In the case of NaCl, preferably the level is in the range 0.5 - 2 wt.%
Fluid cleaning compositions may, depending on their end use further comprise any of the following as a single ingredient, or a mixture thereof: polymers, sequestrants, hydrotropes (such as glycerol or monoproylene glycol), opacifiers, preservatives, colorants (e.g. dyes and pigments), enzymes (for example proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof), further surfactants such as cationic surfactants, fatty acids, softeners, polymers for anti redeposition of soil, bleach, bleach activators and bleach catalysts, antioxidants, pH adjusting agents (such as citric acid and NaOH), pH control agents and buffers. Such other ingredients can suitably be used with the preferred fluid cleaning composition, namely a laundry liquid detergent composition.

Fluorescent Agent

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

Enzymes

One or more enzymes are preferably present in the laundry composition of the invention and when practicing a method of the invention.
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.
Contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.
Preferably the enzyme is selected from: proteases, alpha-amylases; cellulases and lipases.
Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P. fluorescens, Pseudomonas sp. strain SD 705 ( WO 95/06720 and WO 96/27002 ), P. wisconsinensis ( WO 96/12012 ), a Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus ( JP 64/744992 ) or B. pumilus ( WO 91/16422 ). Other examples are lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 and WO 97/07202 , WO 00/60063 .
Preferred commercially available lipase enzymes include Lipolase^™ and Lipolase Ultra^™, Lipex^™ and Lipoclean ^™ (Novozymes A/S).
The method of the invention may be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme which has activity towards phospholipids.
Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol. Phospholipases are enzymes which participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A₁ and A₂ which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid respectively.
Protease enzymes hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains. Examples of suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk). Serine proteases are preferred. Subtilase type serine proteases are more preferred. The term "subtilases" refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 4 (1991) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523. Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. The subtilases may be divided into 6 subdivisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in 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 WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in ( WO93/18140 ). Preferably the subsilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in US 6,312,936 B1 , 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^®, Esperase^® and Carnival^®, all could be sold as Ultra^® or Evity^® (Novozymes A/S).
The invention may be 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 .
The aqueous solution used in the method preferably has an enzyme present. The enzyme is preferably present in the aqueous solution used in the method at a concentration in the range from 0.01 to 10ppm, preferably 0.05 to 1ppm.
Suitable enzymes may be included as a blend or 2 or more enzymes.

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 .

Sequestrants

Preferably the composition comprises from 0.1 to 5 wt.%, preferably from 0.25 wt.% to 4 wt.%, more preferably from 0.5 to 2.5 wt.% of a sequestrant.
Preferred sequestrants include phosphonic acids or salts thereof.
The phosphonic acid (or salt thereof) sequestrant is preferably selected from the group consisting of: 1-Hydroxyethylidene-1,1-diphosphonic acid (HEDP); Diethylenetriaminepenta(methylenephosphonic acid) (DTPMP); Hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP); Aminotris(methylenephosphonic acid) (ATMP); Ethylenediaminetetra(methylenephosphonic acid) (EDTMP); Tetramethylenediaminetetra(methylenephosphonic acid) (TDTMP); and, Phosphonobutanetricarboxylic acid (PBTC).
The sequestrant is preferably in acid form. This means that it is a phosphonic acid.
The preferred phosphonic acid sequestrant is 1-Hydroxyethylidene-1,1-diphosphonic acid (HEDP).

Polymers

The composition may preferably comprise one or more polymers. Example polymers are carboxymethylcellulose, poly(ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
Polymers present to prevent dye deposition may be present, for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole).

Shading Dye

Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).
Shading Dyes for use in laundry compositions preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol^-1 cm^-1, preferably greater than 10000 L mol^-1 cm^-1. The dyes are blue or violet in colour.
Preferably the composition comprises a shading dye. Preferably the shading dye is present at from 0.0001 to 0.1 wt.% of the composition.
Preferred shading dye chromophores are azo, azine, anthraquinone, and triphenylmethane.
Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged. Azine preferably carry a net anionic or cationic charge. Blue or violet 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 250 to 320, most preferably 250 to 280. The white cloth used in this test is bleached non-mercerised woven cotton sheeting.
Shading dyes are discussed in WO 2005/003274 , WO 2006/032327(Unilever ), WO 2006/032397(Unilever ), WO 2006/045275(Unilever ), WO 2006/027086(Unilever ), WO 2008/017570(Unilever ), WO 2008/141880 (Unilever ), WO 2009/132870(Unilever ), WO 2009/141173 (Unilever ), WO 2010/099997(Unilever ), WO 2010/102861 (Unilever ), WO 2010/148624(Unilever ), WO 2008/087497 (P&G ), WO 2011/011799 (P&G ), WO 2012/054820 (P&G ), WO 2013/142495 (P&G ) and WO 2013/151970 (P&G ).
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 WO/2013/142495 and WO/2008/087497 . Preferred examples of thiophene dyes are shown below:

and,
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 WO2010/151906 .
An example of an alkoxylated bis-azo dye is :
Thiophene dyes are available from Milliken under the tradenames of Liquitint Violet DD and Liquitint Violet ION.
Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5, acid blue 59, 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.

The shading dye is present is present in the composition in range from 0.0001 to 0.5 wt %, preferably 0.001 to 0.1 wt%. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is a blue or violet shading dye.
A mixture of shading dyes may be used.
The shading dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine. The alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation. Preferably 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation. Preferably the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800.
An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is:

Perfumes

The composition may comprise from 0.001 to 3 wt.% of a perfume, preferably from 0.1 to 2 wt.% perfume. This suitably may be present as a free perfume oil or as an encapsulated perfume.

Misc

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.
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.

Experimental

The examples below are intended to illustrate the invention in detail without, however, limiting it thereto. Examples denoted by a letter are comparative, examples denoted by a number are according to the invention.

Example 1

This example shows the detrimental effect of the addition of the alkoxylated polyamine and polyester based soil release polymer to a fluid cleaning composition (laundry liquid), and the need to include a HASE polymer to overcome the detrimental effect on viscosity.

Table 1: Laundry liquid formulation

Ingredient	A wt.%	B wt.%	C wt.%	D wt.%
Demin water	to 100	to 100	to 100	to 100
Tinopal 5BM-GX	0.14	0.14	0.14	0.14
Neodol 25-7EO	3.06	3.06	3.06	3.06
Acusol WR (HASE thickening polymer)	0.55-0.85	0.55-0.85	0.55-0.85	0.55-0.85
TEA	6.30	6.30	6.30	6.30
LAS acid	4.07	4.07	4.07	4.07
Palmera B1231	0.60	0.60	0.60	0.60
Dequest 2010	1.05	1.05	1.05	1.05
SLES 3EO	3.06	3.06	3.06	3.06
HP20 (alkoxylated polyethyleneimine	-	-	2.17	2.17
BIT	0.04	0.04	0.04	0.04
Perfume	0.80	0.80	0.80	0.80
Salt	0.60	0.60	0.60	0.60
Citric Acid	0.70	0.70	0.70	0.70
Texcare UL50 (Polyester soil release polymer)	-	0.70	-	0.70

Formulation A has neither the polyester soil release polymer (Texcare UL50), nor the alkoxylated polyamine (HP20); formulations B and C have one or the other; formulation D has both polymers. The viscosity was measured using the Anton Paar ASC rheometer - using a Bob set-up and reporting the viscosity measured at a shear rate of 23s^-1 based upon HASE thickening polymer inclusion levels (Acusol WR) of from 0.55 to 0.85. Table 2:

HASE polymer 0.55 wt.% HASE polymer 0.65 wt.% HASE polymer 0.75 wt.% HASE polymer 0.85 wt.%

A 350 420 515 605

B 255 308 385 460

C 200 230 300 330

D 175 205 260 298
This data shows the detriment to viscosity by inclusion of the polyester soil release polymer (Texcare UL50), and the alkoxylated polyamine (HP20). It shows the HASE polymer is used to boost the viscosity.

Example 2

This example shows the improved viscosity build using rhamnolipid at low pH

Table 3: Laundry liquid formulation

Ingredient	E (wt.%)	1 (wt.%)
Demin water	to 100	to 100
Tinopal CBS-X	0.03	0.03
Sodium Hydroxide (47%)	0.30	0.30
TEA	0.89	0.89
Citric Acid (50%)	0.24	0.24
LAS acid	2.35	2.35
SLES 3EO	7.05	7.05
Cocoamidopropyl betaine	2.00	2.00
R2 - Rhamnolipid	-	1.27
HP20 (alkoxylated polyethyleneimine	-	1.00
Texcare UL50 (Polyester soil release polymer)	-	0.13
BIT	0.02	0.02
MIT	0.10	0.10
Salt	1.00	1.00
Perfume	0.45	0.45

Formulation E has neither the polyester soil release polymer (Texcare UL50), nor the alkoxylated polyamine (HP20), nor the rhamnolipid; formulation 1 has both polymers and rhamnolipid (R2 rhamnolipid at inclusion level of 10% of total surfactant. The viscosity was measured using the Anton Paar ASC rheometer- using a Bob set-up and reporting the viscosity measured at a shear rate of 23s^-1 at different pH from pH ~3 to ~6 by addition of citric acid Table 4 - Formulation E (Control) - Viscosity of E in Cps at a shear rate of 23s^-1

Formulation E (0% Rhamnolipid)

pH Viscosity (Cps)

6.93 333

5.28 64.3

4.78 55.9

4.28 50.6

3.75 48.4

Table 5 - Formulation 1 (Invention) - Viscosity of 1 in Cps at a shear rate of 23s^-1

Formulation 1 (10% Rhamnolipid replacement)

pH Viscosity (Cps)

6.94 56.5

6.04 188

5.53 377

4.92 606

4.50 633

4.01 604
This data shows the improvement in viscosity (a higher viscosity) seen by addition of rhamnolipid biosurfactant to the surfactant system at low pH (pH 4 to 5.5).

Claims

A fluid cleaning composition comprising:
a) from 5 to 70 wt.% of a surfactant system comprising:
i) at least one anionic and/or nonionic surfactant; and

ii) a rhamnolipid biosurfactant which is present at a level in the range of from 1 to 95 wt.%, preferably from 1 to 50 wt.%, more preferably from 2.5 to 50 wt.%, most preferably from 5 to 25 wt.% of the total surfactant in said surfactant system; and

iii) from 0.5 to 10 wt.% of a zwitterionic surfactant; and

b) water; and

c) from 0.1 to 15 wt.% of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester soil release polymer and mixtures thereof;
wherein the composition has a pH of from 4 to 5.5.
A fluid cleaning composition according to claim 1, wherein the composition comprises from 0.75 to 5 wt.%, most preferably from 1 to 4 wt.% of the zwitterionic surfactant, preferably the zwitterionic surfactant is a betaine, more preferably cocoamidopropyl betaine, said surfactant being counted as part of the surfactant system.
A fluid cleaning composition according to claim 1 or claim 2, comprising an anionic surfactant, wherein the anionic surfactant is selected from: linear alkyl benzene sulphonates; alkyl sulphates; alkyl ether sulphates; alkyl ether carboxylates, and mixtures thereof.
A fluid cleaning composition according to any preceding claim, wherein the anionic surfactant comprises linear alkyl benzene sulphonates and/or alkyl ether sulphates.
A fluid cleaning composition according to any preceding claim, comprising a non-ionic surfactant, wherein the non-ionic surfactant is an alcohol ethoxylate, preferably a C₁₀-C₁₈ alcohol ethoxylate having an average of 3-10 moles of ethylene oxide, more preferably a C₁₂-C₁₅ alcohol ethoxylate having an average of 5-9 moles of ethylene oxide.
A fluid cleaning composition according to any preceding claim, wherein the fluid cleaning composition comprises from 5 to 60 wt.%, preferably from 5 to 50 wt.%, more preferably from 7.5 to 30 wt.%, even more preferably from 7.5 to 25 wt.%, most preferably from 8 to 25 wt.%, for example from 8 to 20 wt.% of a surfactant system.
A fluid cleaning composition according to any one of the preceding claims, wherein the composition has a pH of from 4.5 to 5.5.
A fluid cleaning composition according to any one of the preceding claims, wherein the rhamnolipid comprises at least 50 wt.% di-rhamnolipid, preferably at least 60 wt.% di-rhamnolipid, more preferably at least 70 wt.% di-rhamnolipid, most preferably at least 80 wt.% di-rhamnolipid
A fluid cleaning composition according to claim 8, wherein the rhamnolipid comprises di-rhamnolipid of formula: Rha2C₈-₁₂C_8-12, where the alkyl chains may be saturated or unsaturated.
A fluid cleaning composition according to any preceding claim, wherein the composition comprises a sodium chloride or magnesium sulfate salt.
A fluid cleaning composition according to any preceding claim, comprising:
a) from 5 to 50 wt.% of a surfactant system comprising:
i) at least one anionic and/or nonionic surfactant; and

ii) a rhamnolipid biosurfactant which is present at a level in the range of from 1 to 95 wt.%, preferably from 1 to 50 wt.%, more preferably from 2.5 to 50 wt.%, most preferably from 5 to 25 wt.% of the total surfactant in said surfactant system; and

iii) from 0.5 to 10 wt.% of a betaine surfactant;

b) water;

c) from 0.1 to 15 wt.%, preferably from 0.1 to 10 wt.% of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester soil release polymer and mixtures thereof;

d) from 0.1 to 2 wt.% of a perfume
wherein the composition has a pH of from 4 to 5.5;
wherein the rhamnolipid biosurfactant comprises at least 70 wt.% di-rhamnolipid, preferably at least 80 wt.% di-rhamnolipid, preferably of formula: Rha2C₈-₁₂C_8-12, where the alkyl chains may be saturated or unsaturated; and

wherein the fluid cleaning composition is a liquid laundry detergent composition.
A fluid cleaning composition according to any preceding claim, wherein 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 C_1-4 alkyl and preferably methyl, the -(OC₂H₄) groups and the -(OC₃H₆) groups are arranged blockwise and the block consisting of the -(OC₃H₆) 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.
A fluid cleaning composition according to any preceding claim, wherein the alkoxylated polyamine comprises an alkoxylated polyethylenimine, and/or alkoxylated polypropylenimine, preferably the alkoxylation is ethoxylation or propoxylation or a mixture of both.
A fluid cleaning composition according to any one of preceding claims 1 to 10, 12 and 13, wherein the fluid cleaning composition is a liquid laundry detergent composition.
Use of a surfactant combination comprising a rhamnolipid biosurfactant and a zwitterionic surfactant to increase the viscosity of a fluid cleaning composition at a pH of from 4.5 to 5.5.