BR112020023083A2 - fluid cleaning composition, liquid laundry detergent composition and use of a combination of surfactants - Google Patents

Abstract

  The invention provides a fluid cleaning composition comprising a) from 5 to 70% by weight of a surfactant system comprising: (i) at least one anionic and / or non-ionic surfactant; and (ii) a ramnolipid biotensoactive that is present at a level in the range of 1 to 95% by weight of the total surfactant in said surfactant system; and (iii) from 0.5 to 10% by weight of a zwitterionic surfactant; and (b) water; and (c) from 0.1 to 15% by weight of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester dirt release polymer and mixtures thereof; wherein the composition has a pH of from 3 to 6. The invention additionally provides for the use of a combination of surfactants comprising a ramnolipid biotensoative and a zwitterionic surfactant to increase the viscosity of a fluid cleaning composition at a pH of 3 to 6.

Description

Invention Patent Descriptive Report FLUID CLEANING COMPOSITION, DETERGENT COMPOSITION

FLUSH FOR LAUNDRY AND USE OF A COMBINATION OF

SURFACES Field of the Invention

[0001] The 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

[0002] Many fluid cleaning compositions, in particular liquid laundry detergent compositions desirably contain cleaning polymers. These cleaning polymers, in particular alkoxylated polyamines and polyester based dirt release polymers are desirable to be included, because they provide effective cleaning by weight 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 can be improved in the eyes of the consumer. Consumers do not like fluid cleaning compositions that have a very low viscosity, as there may be a perception that these compositions are not thick enough to provide adequate cleaning. Thus, there is a problem with how to improve the viscosity of fluid cleaning compositions.

[0003] One way to improve viscosity is to include an additional polymer, a thickener polymer such as a so-called HASE polymer (polymer in soluble alkaline hydrophobically modified emulsion). This thickening polymer improves rheology, especially the viscosity of the formulation.

[0004] US 2018/0044614 discloses in the claims and examples various formulations in the examples which include (a) a combination of surfactants (ramnolipid and other surfactant); (b) one or more viscosity modifiers; (c) EPEI; and (d) perfume. Viscosity modifiers are essential for US 2018/0044614 compositions, which are more preferably of pH greater than 7 to 13.

[0005] However, there is a need to improve the viscosity of the fluid cleaning composition, in particular liquid laundry detergent compositions by removing the need for additional thickening polymers.

Summary of the Invention

[0006] It has been found that by adding a biotinylative ramnolipid to a fluid cleaning composition, together with a betaine surfactant and having a pH in the range of 4 to 6, an improved rheology in terms of higher viscosity can be achieved.

[0007] In a first aspect, the invention provides a fluid cleaning composition comprising: a) from 5 to 70% by weight of a surfactant system comprising: i) at least one anionic and / or non-ionic surfactant; and ii) a ramnolipid biotensoactive that is present at a level in the range of 1 to 95% by weight, preferably from 1 to 50% by weight, more preferably from 2.5 to 50% by weight, even more preferably from 5 to 25 % by weight of the total surfactant in said surfactant system; and iii) from 0.5 to 10% by weight of a zwitterionic surfactant; and b) water; and c) from 0.1 to 15% by weight, preferably from 0.1 to 10% by weight of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester dirt release polymer and mixtures thereof; wherein the composition has a pH of from 3 to 6.

[0008] In a second aspect, the invention provides the use of a combination of surfactants comprising a ramnolipid biotensoative and a zwitterionic surfactant to increase the viscosity of a fluid cleaning composition at a pH of 3 to 6, preferably from 3.5 to 6, more preferably 4 to 6, even more preferably 4 to 5.75, even more preferably 4.5 to 5.5.

[0009] Preferably in the use of the second aspect, the ramnolipid biotensoactive comprises at least 70% by weight of di-ramnolipid, preferably at least 80% by weight of di-ramnolipid, preferably of the formula: Rha2C8-12C8-12, where the chains alkyl can be saturated or unsaturated. Detailed Description of the Invention

[0010] Where viscosities are measured here, unless otherwise stated, they are measured on an Anton Paar ASC rheometer at 25 ° C.

[0011] The fluid cleaning composition comprises from 5 to 70% by weight of a surfactant system. Preferably the fluid cleaning composition comprises from 5 to 60% by weight, more preferably from 5 to 50% by weight, even more preferably from 7.5 to 30% by weight, even more preferably from 7.5 to 25% by weight , for example from 8 to 25% by weight, or from 8 to 20% by weight of a surfactant system.

[0012] The surfactant system comprises at least one anionic or non-ionic surfactant and a ramnolipid biotensoative that is present at a level in the range from 1 to 95% by weight of the total surfactant in said surfactant system.

[0013] Preferably the ramnolipid is present at a level in the range of from 1 to 50% by weight of the total surfactant in said surfactant system, more preferably from 2.5 to 50% by weight, even more preferably from 5 to 25 % by weight, for example from 7.5 to 25% by weight of the total surfactant in said surfactant system.

[0014] Fluid cleaning compositions comprise water. Water is generally the balancing agent in the formulation, and can make up all or most of the weight% of non-surfactant in the composition. Typical water inclusion levels can be 50 to 90% by weight,

preferably from 60 to 90% by weight, more preferably from 65 to 88% by weight.

Ramnolipid

[0015] The composition comprises a ramnolipid biotensoative.

[0016] Mono-ramnolipids have a single ring of sugar rhamnose.

[0017] Di-ramnolipids have two rings of sugar rhamnose.

[0018] In the case of ramnolipids, throughout this patent report, the prefixes mono- and di-ramnolipids are used to indicate respectively mono-ramnolipids (having a single ring of sugar rhamnose) and di-rhamnolipids (having two rings of sugar rhamnose) respectively. If abbreviations are used R1 is mono-ramnolipid and R2 is di-ramnolipid.

[0019] The mono-ramnolipid can be L-ramnosyl-β-hydroxidecanoyl-β-hydroxidecanoate (RhaC10C10 with a formula of C26H48O9) produced by P. aeruginosa.

[0020] A typical di-ramnolipid is L-ramnosil-L-ramnosil-β-hydroxidecanoyl-β-hydroxydecanoate (Rha2C10C10 with a formula of C32H58O13).

[0021] In practice a variety of other minority components with different combinations of alkyl chain length, depending on the carbon source and bacterial strain, exist in combination with the most common ramnolipids above. The mono-ramnolipid and di-ramnolipid ratio can be controlled by the production method. Some bacteria only produce mono-ramnolipids, see US5767090: example 1, some enzymes can convert mono-ramnolipids to di-ramnolipids.

[0022] The following ramnolipids are sources of mono- and di-ramnolipids encompassed within the invention (C12: 1, C14: 1 indicates fatty acyl chains with double bonds): - Ramnolipids produced by P. aeruginosa (mono-ramnolipids): Rha -C8-C10, Rha-C10-C8, Rha-C10-C10, Rha-C10-C12, Rha-C10-C12: 1, Rha-C12-C10, Rha-C12: 1-C10.

- Ramnolipids produced by P. chlororaphis (mono-ramnolipids only): Rha-C10-C8, Rha-C10-C10, Rha-C12-C10, Rha-C12: 1-C10, Rha-C12-C12, Rha-C12: 1-C12, Rha-C14-C10, Rha-C14: 1-C10. - Mono-ramnolipids can also be produced from P. putida by the introduction of rhIA and rhIB genes from Pseudomonas aeruginosa [Cha et al. In Bioresour Technol. 2008. 99 (7): 2192-9] - Ramnolipids produced by P. aeruginosa (di-ramnolipids): Rha-Rha-C8-C10, Rha-Rha-C8-C12: 1, Rha-Rha-C10-C8, Rha-Rha-C10-C10, Rha-Rha-C10-C12: 1, Rha-Rha-C10-C12, Rha-Rha-C12-C10, Rha-Rha-C12: 1-C12, Rha-Rha-C10- C14: 1. - Ramnolipids produced by Burkholdera pseudomallei (di- ramnolipids only): Rha-Rha-C14-C14. - Ramnolipids produced by Burkholdera (Pseudomonas) plantarii (di-ramnolipids only): Rha-Rha-C14-C14. - Ramnolipids produced by P. aeruginosa that are initially not identified as mono- or di-ramnolipids: C8-C8, C8-C10, C10-C8, C8-C12: 1, C12: 1-C8, C10-C10, C12- C10, C12: 1-C10, C12-C12, C12: 1-C12, C14-C10, C14: 1-C10, C14-C14.

[0023] Preferably, the ramnolipid comprises at least 50% by weight of di-ramnolipid, more preferably at least 60% by weight of di-ramnolipid, even more preferably 70% by weight of di-ramnolipid, even more preferably at least 80 % by weight of di-ramnolipid.

[0024] Preferably the ramnolipid is a di-ramnolipid of the formula: Rha2C8-12C8-12. The preferred alkyl chain length is C8 to C12. The alkyl chain can be saturated or unsaturated.

Surfactant

[0025] The fluid cleaning composition comprises at least one anionic and / or non-ionic surfactant. This means that the composition may comprise a single anionic surfactant, or a mixture of anionic surfactants, or a single non-ionic surfactant or a mixture of non-ionic surfactants, or a mixture of one or more anionic surfactants with one or more non-ionic surfactants.

[0026] Suitable nonionic and anionic surfactants can be chosen from the surfactants described in “Surface active agents” Vol. 1, by Schwartz & Perry, Intersciense 1949, Vol. 2 by Schwartz, Perry & Bench, Intersciense 1958, in the current edition from “McCutcheon Emulsifiers and Detergents” published by the Manufacturing Confectioners Company or in the “Tenside-Taschenbuch”, H. Stache, 2nd Edition, Carl Hauser Verlag, 1981 or in anionic surfactants: organic chemistry edited by Helmut W. Stache (Marcel Dekker 1996).

[0027] Suitable anionic detergent compounds that can be used are generally water-soluble alkali metal salts of organic sulfates and sulfonates 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.

[0028] Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphonating higher C8 to C18 alcohols, produced for example from tallow or coconut oil, alkyl ether carboxylic acids; C9 to C20 alkyl sodium benzene sulfonate or potassium, particularly C10 to C15 alkyl benzene linear secondary sodium; and alkyl glyceryl ether sodium sulfates, especially those ethers of higher alcohols derived from tallow and coconut oil and synthetic alcohols derived from petroleum.

[0029] The anionic surfactant is preferably selected from: linear alkyl benzene sulfonate; alkyl sulfates; alkyl ether sulfates; alkyl ether carboxylates, and mixtures thereof.

[0030] Most preferred anionic surfactants are selected from: linear alkyl benzene sulfonate; alkyl sulfates; alkyl ether sulfates and mixtures thereof. Preferably the alkyl ether sulfate is a C12-C14 n-alkyl sulfate ether with an average of 1 to 3 EO units (ethoxylate). Sodium lauryl ether sulfate is particularly preferred (SLES). Preferably the linear alkyl benzene sulfonate is a C11 to C15 alkyl benzene sulfonate sodium. Preferably the alkyl sulfate is a linear or branched C12 to C18 alkyl sulfate. Sodium dodecyl sulfate is particularly preferred, (SDS, also known as primary alkyl sulfate).

[0031] Preferably the anionic surfactant comprises linear alkyl benzene sulfonate and / or alkyl ether sulfates.

[0032] Preferably, two or more anionic surfactants are present, for example linear alkyl benzene sulfonate together with an alkyl ether sulfate.

[0033] The composition may comprise anionic and / or non-ionic surfactants.

[0034] Preferably the weight fraction of nonionic surfactant for anionic surfactant is 0 to 0.3. This means that a nonionic surfactant may be present (or may be absent if the weight fraction is 0), but if a nonionic surfactant is present, then the weight fraction of nonionic surfactant is preferably at most 30% of the total weight of anionic surfactant + non-ionic surfactant.

[0035] Suitable non-ionic detergent compounds that can be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, alcohols, acids, aliphatic amides, especially ethylene oxide both alone or with propylene oxide. Specific non-ionic detergent compounds are the condensation products of linear or branched primary or secondary C8 to C18 aliphatic alcohols with ethylene oxide.

[0036] If a nonionic surfactant is present, then more preferably the nonionic surfactant is an alcohol ethoxylate, more preferably a C10-C18 alcohol ethoxylate having an average of 3-10 moles of ethylene oxide, even more preferably one alcohol ethoxylate C12-C15 having an average of 5-9 moles of ethylene oxide.

[0037] Preferably the surfactants used are saturated.

Zwitterionic surfactant

[0038] The surfactant system comprises from 0.5 to 10% by weight of a zwitterionic surfactant. Preferably the composition comprises from 0.5 to 10% by weight, preferably from 0.75 to 5% by weight, more preferably from 1 to 4% by weight of a zwitterionic surfactant, said surfactant being counted as part of the surfactant system.

[0039] The zwitterionic surfactant is preferably a betaine surfactant. Preferably the composition comprises from 0.5 to 10% by weight, preferably from 0.75 to 5% by weight, more preferably from 1 to 4% by weight of betaine surfactant, said surfactant being counted as part of the surfactant system.

[0040] A preferred betaine surfactant is cocoamidopropyl betaine.

[0041] A preferred fluid cleaning composition is a liquid laundry detergent composition.

[0042] A preferred laundry detergent composition comprises: a) from 5 to 50% by weight of a surfactant system comprising: i) at least one anionic and / or non-ionic surfactant; and ii) a ramnolipid biotensoactive that is present at a level in the range of 1 to 95% by weight, preferably from 1 to 50% by weight, more preferably from 2.5 to 50% by weight, even more preferably from 5 to 25 % by weight of the total surfactant in said surfactant system; and iii) from 0.5 to 10% by weight of a betaine surfactant; b) water; c) from 0.1 to 15% by weight, preferably from 0.1 to 10% by weight of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester dirt release polymer and mixtures thereof; d) from 0.1 to 2% by weight of a perfume; wherein the composition has a pH of from 3 to 6, preferably from 4 to 5.5; wherein the ramnolipid biotensoactive comprises at least 70% by weight of di-ramnolipid, preferably at least 80% by weight of di-ramnolipid, preferably of the formula: Rha2C8-12C8-12, where the alkyl chains can be saturated or unsaturated.

pH

[0043] Fluid cleaning compositions have a pH of from 3 to 6, preferably from 3.5 to 6, more preferably from 4 to 6, even more preferably from 4 to 5.75, more preferably 4.5 to 5.5.

Polymer

[0044] The composition comprises from 0.1 to 15% by weight, preferably from 0.1 to 10% by weight of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester dirt release polymer and mixtures of the themselves.

Polyester dirt release polymer

[0045] The composition may comprise from 0.05 to 6% by weight, preferably from 0.1 to 5% by weight of one or more polyester dirt releasing polymer (s). Suitable polyester based dirt release polymers are described in WO 2014/029479 and WO 2016/005338.

[0046] Preferably the polyester based dirt release polymer is a polyester according to the following formula (I)

(I) where R1 and R2 independently of each other are X- (OC2H4) n- (OC3H6) m where X is C1-4alkyl, and preferably methyl, the groups - (OC2H4) and groups - (OC3H6) are arranged in blocks and the block consisting of groups - (OC3H6) is linked to a COO group or are HO- (C3H6), and preferably are independently of each other X- (OC2H4) n- (OC3H6) m, n is, based on a molar average number, from 12 to 120 and preferably from 40 to 50, m is, based on a molar average number, from 1 to 10 and preferably from 1 to 7, and a is, based on a molar average number, from 4 to 9.

[0047] Preferably the polyester provided as an active mixture comprises: A) from 45 to 55% by weight of the active mixture of one or more polyesters according to the following formula (I) (I) in which R1 and R2 independently of each other are X- (OC2H4) n- (OC3H6) m where X is C1-4 alkyl, and preferably methyl, groups - (OC2H4) and groups - (OC3H6) are arranged in blocks and the block consisting of groups - (OC3H6 ) is linked to a COO group or are HO- (C3H6), and preferably are independently of each other X- (OC2H4) n- (OC3H6) m, n is, based on a molar mean number, from 12 to 120 and preferably from 40 to 50,

m is, based on a molar average number, from 1 to 10 and preferably from 1 to 7, and a is, based on a molar average number, from 4 to 9 and B) from 10 to 30% by weight of the active mixture 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 water mixture.

[0048] By active mixture it should be understood that it is preformed and added to the rest of the fluid cleaning composition, or to the components that ultimately form the fluid cleaning composition.

Alkoxylated polyamine

[0049] The composition can and preferably comprises an alkoxylated polyamine. Suitable inclusion levels for the polymer are 0.25 to 8% by weight, preferably 0.5 to 6% by weight of an alkoxylated polyamine. Another preferred level is 1 to 4% by weight.

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

salt

[0051] Preferably the composition comprises a salt of sodium chloride or magnesium sulfate.

perfume

[0052] The composition preferably comprises a perfume. The perfume is preferably present in the range of 0.001 to 3% by weight, more preferably 0.05 to 0.5% by weight, even more preferably from 0.1 to 2% by weight, even more preferably 0.1 to 1% in weight.

[0053] Many suitable examples of perfumes are provided in the CTFA International Buyers Guide 1992 (Cosmetic Association, Hygiene Articles and Fragrances), published by CTFA Publications and the 80th Annual Edition of the OPD 1993 Chemicals Buyers Directory, published by Schnell Publishing Co.

[0054] The perfume can be provided as a free oil or it can be in encapsulated form.

Other ingredients

[0055] Preferably the composition comprises an ionic salt. The salt preferably comprises any organic or inorganic cation, including without limitation alkali metal cations Cs, Na, K, Ca, Mg etc., with anions including halide anions, more preferably Cl. Other preferred salts comprise organic cations, e.g. amides (- + NH-R) or ammonium cations or substituted forms thereof e.g. triethylammonium. Anions for organic cations can comprise any alkyl, aryl, arylalkyl group that can be short, medium, long, branched, cyclic or linear.

[0056] Preferably the composition comprises from 0.01 - 5% by weight by weight of the salt. In the case of NaCl, the level is preferably in the range of 0.5 - 2% by weight.

[0057] Fluid cleaning compositions may, depending on their end use, additionally comprise any of the following as a single ingredient, or a mixture thereof: polymers, scavengers, hydrotropes (such as glycerol or monopropylene glycol), opacifiers, preservatives, colorants (eg dyes and pigments), enzymes (for example, proteases, alpha-

amylases, cellulases, lipases, peroxidases / oxidases, pectate lyases and mannanases or mixtures thereof), additional surfactants such as cationic surfactants, fatty acids, softeners, polymers for dirt anti-redeposition, bleach, bleach activators and bleach catalysts, antioxidants , pH adjusting agents (such as citric acid or NaOH), pH control agents and buffers. Such other ingredients can suitably be used with the preferred fluid cleaning composition, i.e. a liquid laundry detergent composition.

Fluorescent agent

[0058] The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are commercially available. Generally, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.

[0059] Preferred classes of fluorescents are: di-styryl biphenyl compounds, eg Tinopal (trademark) CBS-X, di-amino stilbene sulfonic acid compounds, eg Tinopal DMS pure Xtra and Blankophor (trademark) HRH and compounds pyrazoline, eg Blankophor SN.

[0060] Preferred fluorescents are: 2- (4-styryl-3-sulfophenyl) -2H-naphthol [1,2- d] sodium triazole, 4,4'-bis {[4-anilino-6- (N- methyl-N-2-hydroxyethyl) amino-1,3,5-triazin-2-yl)] amino} disodium sodium stylbene-2,2'-disulfonate, 4,4'-bis {[(4-anilino-6- morpholino-1,3,5-triazin-2-yl)] amino} stilbene-2,2'-disulfonate disodium and 4,4'-bis (2-sulfo-styrene) disodium biphenyl.

[0061] The total amount of the fluorescent agent or agents used in the composition is preferably from 0.0001 to 0.5% by weight, more preferably from 0.005 to 2% by weight, more preferably 0.05 to 0.25% by weight .

[0062] The aqueous solution used in the method preferably has a fluorescent present. The fluorescent is preferably present in the aqueous solution used in the method in the range of 0.0001 g / L to 0.1 g / L, more preferably 0.001 to 0.02 g / L.

Enzymes

[0063] One or more enzymes are preferably present in the laundry composition of the invention and in the practice of the method of the invention.

[0064] When present, then the level of each enzyme in the laundry composition of the invention is from 0.0001% by weight to 0.1% by weight.

[0065] Levels of enzyme present in the composition preferably refer to the level of enzyme as pure protein.

[0066] Enzymes contemplated include proteases, alpha-amylases, cellulases, lipases, peroxidases / oxidases, pectate lyases and mannanases, or mixtures thereof.

[0067] Preferably the enzyme is selected from: proteases, alpha-amylases, cellulases and lipases.

[0068] Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include Humicola lipases (Thermomyces synonym), eg H. lanuginosa (T. lanuginosus) as described in EP 258068 and EP 305216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, eg from P. alcaligenes or P. pseudoalalkigenes (EP 218272), P. cepacia (EP 331376), P. stutzeri (GB 1372034), P. fluorescens, strain of Pseudomonas sp. SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a lipase from Bacillus, eg from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422). Other examples are variants of lipase such as those described in WO 92/05249, WO 94/01541, EP 407225, EP 260105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783 , WO 95/22615, WO 97/04079 and WO97 / 07202, WO 00/60063.

Preferred commercially available lipase enzymes include

Lipolase®, and Lipolase Ultra®, Lipex® and Lipoclean® (Novozymes A / S).

[0070] The method of the invention can be carried out in the presence of phospholipase classified as EC 3.1.1.4 and / or EC 3.1.1.32. In the context of the present invention, the term "phospholipase" is to be understood as an enzyme that has activity in relation to phospholipids.

[0071] Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an external position (sn-1) and in the middle (sn-2) and esterified with phosphoric acid in the third position; phosphoric acid, in turn, can be esterified to an amino alcohol. Phospholipases are enzymes that participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A 1 and A2 that hydrolyze a fatty acyl group (at position sn-1 and sn-2, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group to lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol and phosphatidic acid respectively.

[0072] Protease enzymes hydrolyze bonds between peptides and proteins, in the context of laundry, this leads to improved removal of stains containing proteins or peptides. Examples of suitable protease families include aspartic proteases; cysteine proteases; glutamic proteases; asparagine peptide lyases; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/). Serine proteases are preferred. Serine proteases of the subtilase type are more preferred. The term "subtilase" refers to a subgroup 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 defined by having a serine at the active site, which form a covalent adduct with the substrate. Subtilases can be divided into 6 subdivisions, i.e., the Subtilisin family, the Termitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexina family and the Pyrolysin family.

[0073] 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 US 7262042 and WO 09/021867, and subtilisin lentus, substilisina Novo, subtilisina Carlsberg, Bacillus licheniformis, subtilisin BPN ', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89/06279 and protease PD 138 described in WO 93/18140. Other useful proteases can be those described in WO 92/175177, WO 01/016285, WO 02/026024 and WO 02/016547. Examples of trypsin-type proteases are trypsin (eg of porcine or bovine origin) and the Fusarium protease described in WO 89/06270, WO 94/25583 and WO 05/040372 and chymotrypsin proteases derived from Cellumonas described in WO 05/052161 and WO 05/052146.

[0074] Most preferably the protease is a subtilisin (EC 3.4.21.62).

[0075] Examples of subtilases are those derived from Bacillus like Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US 7262042 and WO 09/021867, and subtilisin lentus, substilisina Novo, subtilisina Carlsberg, Bacillus licheniformis, subtilisin BPN ', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89/06279 and protease PD 138 described in WO 93/18140. Preferably, subtilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in US 6312936 B1, US 5679630, US 4760025, US 7262042 and WO 09/021867 . More preferably, subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.

[0076] Suitable commercially available protease enzymes include those sold under the brand names Alcalase®, Blaze®, Duralase®, Duranzym®, Relase®, Relase Ultra®, Savinase®, Savinase Ultra®, Primase®, Polarzyme®, Kannase ®, Liquanase®, Liquanase Ultra®, Ovozyme®, Coronase®, Coronase Ultra®, Neutrase®, Everlase® and Esperase® and Carnival®, all can be sold as Ultra® or Evity® (Novozymes A / S).

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

[0078] Suitable amylases (alpha and / or beta) include those of bacterial or fungal origin. Chemically modified or 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 1296839 or the strain of Bacillus sp. disclosed in WO 95/026397 or WO 00/060060. Commercially available amylases are Duramyl®, Termamyl®, Termamyl Ultra®, Natalase®, Stainzyme®, Fungamyl® and BAN® (Novozymes A / S), Rapidase® and Purastar® (from Genencor International Inc.).

[0079] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases of the genus Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, eg fungal cellulase produced by Humicola insolens, Thielavia terrestris, Myceliophthora thermophila and Fusarium oxysporum disclosed at US 4435307, US 5648263, US 5691175, US 5691175, / 09259, WO 96/029397 and WO 98/012307. Commercially available cellulases include Celluzyme®, Carezyme®, Celluclean®, Endolase®, Renozyme® (Novozyme A / S), Clazinase® and Puradax HA® (Genencor International Inc.), and KAC-500 (B) ®, (Kao Corporation ). Celluclean® is preferred.

[0080] Suitable peroxidases / oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include Coprinus peroxidases, e.g. from C. cinereus and variants thereof such 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).

[0081] Additional enzymes suitable for use are discussed in WO 2009/087524, WO 2009/090576, WO 2009/107091, WO 2009/111258 and WO 2009/148983.

[0082] 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 of 0.01 to 10 ppm, preferably 0.05 to 1 ppm.

[0083] Suitable enzymes can be included as a mixture of 2 or more enzymes.

Enzyme stabilizers

Any enzyme present in the composition can be stabilized using conventional stabilizing agents, eg a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid or boric acid derivative, eg an aromatic borate ester , or a derivative of phenyl boronic acid such as 4-formylphenyl boronic acid, and the composition can be formulated as described in eg WO 92/19709 and WO 92/19708.

Kidnappers

[0085] Preferably the composition comprises from 0.1 to 5% by weight, preferably from 0.25% to 4% by weight, more preferably from 0.5 to 2.5% by weight of a scavenger.

[0086] Examples of sequestrants include phosphonic acid or salt thereof. The phosphonic acid scavenger (or salt thereof) is preferably selected from the group consisting of: 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP); diethylenetriaminopenta (methylenephosphonic) acid (DTPMP); hexamethylenediaminetetra (methylenephosphonic) acid (HDTMP); aminotris (methylenephosphonic) (ATMP); ethylenediaminetetra (methylenephosphonic) acid (EDTMP); tetramethylenediaminetetra (methylenephosphonic) acid (TDTMP); and phosphonobutanotricarboxylic acid (PBTC).

[0087] The scavenger is preferably in the acid form. This means that it is a phosphonic acid.

[0088] The preferred phosphonic acid scavenger is 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP).

Polymers

[0089] The composition can preferably comprise one or more polymers. Examples of polymers are carboxymethylcellulose, poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates, maleic / acrylic acid copolymers and methacrylic / acrylic lauryl acid copolymers.

[0090] Polymers are present to prevent dye deposition that may be present, for example poly (vinylpyrrolidone), poly (vinylpyridine-N-oxide) and poly (vinylimidazole).

Toning dye

[0091] Dyes are described in Synthesis of Color Chemistry, Properties and Applications of dyes and organic pigments (H. Zollinger, Wiley VCH, Zürich, 2003) and, Chemistry of Industrial Dyes, Properties and Applications (K Hunger (ed), Wiley-VCH Weinheim 2003).

[0092] Toning dyes for use in laundry compositions preferably have an extinction coefficient at maximum absorption in the visible range (400 to 700nm) of more than 5000 L mol -1cm-1, preferably more than 10000 L mol-1cm-1 . The dyes are blue or violet in color.

[0093] Preferably the composition comprises a toning dye. Preferably, the toning dye is present from 0.0001 to 0.1% by weight of the composition.

Preferred toning dye chromophores are azo, azine, anthraquinone and triphenylmethane.

[0095] Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry an anionic liquid charge or are uncharged. Azine preferably carries an anionic or cationic liquid charge. Blue or violet toning dyes are deposited on the fabric during the washing or rinsing step of the washing process providing a visible tone to the fabric. In this context, the dye gives a blue or violet color to a white fabric with a shade angle of 240 to 345, more preferably 250 to 320, more preferably 250 to 280. The white fabric used in this test was a non-mercerized cotton sheet targeted.

[0096] Toning dyes are described 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).

[0097] Mono-azo dyes preferably contain a heterocyclic ring and are more preferably thiophene dyes. The mono-azo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH = 7. Alkoxylated thiophene dyes are described in WO 2013/142495 and WO 2008/087497. Preferred examples of thiophene dyes are shown below:

and,

[0098] Bis-azo dyes are preferably sulfonated bis-azo dyes. Preferred examples of sulphonated bis-azo dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 66, violet Direct 99 and alkoxylated versions of them. Alkoxylated bis-azo dyes are described in WO 2012/054058 and WO 2010/151906.

[0099] An example of an alkoxylated bis-azo dye is:

[0100] Thiophene dyes are available from Milliken under the brand name Liquitint Violet DD and Liquitint Violet ION.

[0101] Azine dye are preferably selected from sulfonated 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 phenazine dye selected from: where: 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.

[0102] The toning dye is present in the composition in the range of 0.0001 to 0.5% by weight, preferably 0.001 to 0.1% by weight. Depending on the nature of the toning dye, there are preferred ranges depending on the effectiveness of the toning dye which is class-dependent and particularly effective within any particular class. As mentioned above, the tinting dye is a blue or violet tinting dye.

[0103] A mixture of toning dyes can be used.

[0104] The tinting dye is even more preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine. Alkoxylation is preferably selected from ethoxylation and propoxylation, more preferably propoxylation. Preferably 80 to 95 mol% of the N-H groups in the polyethyleneimine are substituted as isopropyl alcohol groups by propoxylation. Preferably polyethylene imine prior to reaction with the dye and propoxylation has a molecular weight of 600 to 1800.

[0105] An example of the structure of a covalently reactive anthraquinone linked to a propoxylated polyethyleneimine is:

(Structure I) Perfumes

[0106] The composition may comprise from 0.001 to 3% by weight of a perfume, preferably from 0.1 to 2% by weight of perfume. This can suitably be present as an oil-free perfume or as an encapsulated perfume.

Others

[0107] When alkyl groups are long enough to form branched or cyclic chains, alkyl groups encompass branched, cyclic and linear alkyl chains. The alkyl groups are preferably linear or branched, even more preferably linear.

[0108] The indefinite article “one” or “one” and its corresponding defined articles “o”, “a”, “os” or “as” as used here mean at least one, or one or more, unless specified otherwise.

Experimental

[0109] The examples below are intended to illustrate the invention in detail without, however, limiting them. Examples indicated by a letter are comparative, examples indicated by a number are in accordance with the invention.

Example 1 This example shows the detrimental effect of adding alkoxylated polyamine and polyester-based dirt release polymer to a fluid cleaning composition (laundry liquid), and the need to include a HASE polymer to overcome the damaging effect on viscosity .

Table 1: liquid laundry washing formulation

ABCD Ingredient% in% in% in% by weight weight weight weight Demineralized 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 (Polymer thickener 0.55-0.85 0.55-0.85 0.55-0.85 0.55-0.85 HASE) 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 (polymer - - 2.17 2.17 alkoxylated polyethyleneimine) 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 (Dirt release polymer - 0.70 - 0.70 polyester)

[0110] Formulation A has no polyester dirt-releasing polymer (Texcare UL50), nor alkoxylated polyamine (HP20); formulations B and C have one or the other; formulation D has both polymers. Viscosity was measured using the Anton Paar ASC rheometer - using a pendulum configuration and reporting viscosity measured at a shear rate of 23s-1 based on inclusion levels of HASE thickener polymer (Acusol WR) from 0, 55 to 0.85.

Table 2: Polymer HASE Polymer HASE Polymer HASE Polymer HASE 0.55% by 0.65% by 0.75% by 0.85% by weight weight weight weight A 350 420 515 605 B 255 308 385 460 C 200 230 300 330 D 175 205 260 298

[0111] These data show the drop in viscosity due to the inclusion of polyester dirt release polymer (Texcare UL50), and alkoxylated polyamine (HP20). It shows that the HASE polymer is used to improve viscosity.

Example 2

[0112] This example shows the enhanced viscosity built using low pH ramnolipid.

Table 3: liquid laundry formulation Ingredient E (% by weight) 1 (% by weight) Demineralized water for 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 - Ramnolipid - 1.27 HP20 - 1.00 (Polyoxyethyleneimine alkoxylated polymer) Texcare UL50 - 0.13 (Polyester dirt release polymer) BIT 0.02 0.02 MIT 0.10 0.10 Salt 1.00 1.00 Perfume 0.45 0 , 45

[0113] Formulation E has no polyester dirt release polymer (Texcare UL50), nor alkoxylated polyamine (HP20), nor ramnolipid; formulation 1 has both polymers and ramnolipid (ramnolipid R2) at an inclusion level of 10% of the total surfactant. Viscosity was measured using an Anton Paar ASC rheometer - using a pendulum configuration and reporting the viscosity measured at a shear rate of 23s -1 at different pHs ~ 3 to ~ 6 by the addition of citric acid.

Table 4 - Formulation E (control) - Viscosity of E in Cps at a shear rate of 23s-1 Formulation E (0% Ramnolipid) 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% substitution by ramnolipid) pH Viscosity (Cps) 6.94 56.5 6.04 188 5.53 377 4.92 606 4.50 633 4.01 604

[0114] These data show the improvement in viscosity (a higher viscosity) as seen by the addition of biotransactive ramnolipid to the surfactant system at low pH (pH 3 to 6).

Claims (15)

Claims 1. Fluid cleaning composition characterized by comprising: a) from 5% to 70% by weight of a surfactant system comprising: i) at least one anionic and / or non-ionic surfactant; and ii) a ramnolipid biotensoactive that is present at a level in the range of 1% to 95% by weight, preferably from 1% to 50% by weight, more preferably from 2.5% to 50% by weight, even more preferably from 5% to 25% by weight of the total surfactant in said surfactant system; and iii) from 0.5% to 10% by weight of a zwitterionic surfactant; and b) water; and c) from 0.1% to 15% by weight of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester dirt release polymer and mixtures thereof; wherein the composition has a pH of from 3 to 6. Fluid cleaning composition according to claim 1, characterized in that the composition comprises 0.75% to 5% by weight, more preferably from 1% to 4% by weight of zwitterionic surfactant, preferably the zwitterionic surfactant is a betaine, more preferably betaine cocoamidopropyl, said surfactant being counted as part of the surfactant system. Fluid cleaning composition according to claim 1 or 2, characterized in that it comprises an anionic surfactant, in which the anionic surfactant is selected from: linear alkyl benzene sulfonate; alkyl sulfates; alkyl ether sulfates; alkyl ether carboxylates, and mixtures thereof. Fluid cleaning composition according to any one of claims 1 to 3, characterized in that the anionic surfactant comprises linear alkyl benzene sulfonate and / or alkyl ether sulfates. Fluid cleaning composition according to any one of claims 1 to 4, characterized in that it comprises a non-ionic surfactant, wherein the nonionic surfactant is an alcohol ethoxylate, preferably 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. Fluid cleaning composition according to any one of claims 1 to 5, characterized in that the fluid cleaning composition comprises from 5% to 60% by weight, preferably from 5% to 50% by weight, more preferably from 7.5% to 30% by weight, even more preferably from 7.5% to 25% by weight, more preferably from 8% to 25% by weight, for example from 8% to 20% by weight of a surfactant system. Fluid cleaning composition according to any one of claims 1 to 6, characterized in that the composition has a pH of 3.5 to 6, more preferably 4 to 6, even more preferably 4 to 5.75, more preferably 4, 5 to 5.5. Fluid cleaning composition according to any one of claims 1 to 7, characterized in that the ramnolipid comprises at least 50% by weight of di-ramnolipid, preferably at least 60% by weight of di-ramnolipid, more preferably at least 70% in weight of di-amnolipid, even more preferably at least 80% by weight of di-amnolipid. Fluid cleaning composition according to claim 8 characterized in that the ramnolipid comprises di-ramnolipid of the formula: Rha2C8-12C8-12, where the alkyl chains can be saturated or unsaturated. Fluid cleaning composition according to any one of claims 1 to 9, characterized in that the composition comprises a sodium chloride salt or magnesium sulfate. A liquid laundry detergent composition as defined in any one of claims 1 to 10, characterized in that it comprises: a) from 5% to 50% by weight of a surfactant system comprising: i) at least one anionic and / or non-ionic surfactant; and ii) a ramnolipid biotensoactive that is present at a level in the range of 1% to 95% by weight, preferably from 1% to 50% by weight, more preferably from 2.5% to 50% by weight, even more preferably from 5% to 25% by weight of the total surfactant in said surfactant system; and iii) from 0.5% to 10% by weight of a betaine surfactant; b) water; c) from 0.1% to 15% by weight, preferably from 0.1% to 10% by weight of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester dirt release polymer and mixtures thereof; d) from 0.1% to 2% by weight of a perfume; wherein the composition has a pH of from 3 to 6, preferably from 4 to 5.5; wherein the ramnolipid biotensoactive comprises at least 70% by weight of di-ramnolipid, preferably at least 80% by weight of di-ramnolipid, preferably of the formula: Rha2C8-12C8-12, where the alkyl chains can be saturated or unsaturated. Fluid cleaning composition according to any one of claims 1 to 11, characterized in that the polyester-based dirt-releasing polymer is a polyester of the following formula (I) OOOO 1 2 ROCCO C3H6 OCCOR (I) a in which R1 and R2 independently of one another are X- (OC2H4) n- (OC3H6) m where X is C1-4 alkyl and preferably methyl, the groups - (OC2H4) and the groups - (OC3H6) are arranged in blocks and the block consisting of groups - (OC3H6) is linked to a COO group or are HO- (OC3H6), and preferably are independently of each other X- (OC2H4) n- (OC3H6 ) m, n is based on a molar average number from from 12 to 120 and preferably from 40 to 50, m is based on a molar average number from from 1 to 10 and preferably from 1 to 7, and a is based on an average molar number from 4 to 9. Fluid cleaning composition according to any one of claims 1 to 12, characterized in that the alkoxylated polyamine comprises an alkoxylated polyethyleneimine and / or alkoxylated polypropyleneimine, preferably the alkoxylation is ethoxylation or propoxylation or a mixture thereof. Fluid cleaning composition according to any one of claims 1 to 13, characterized in that the fluid cleaning composition is a liquid laundry detergent composition. 15. Use of a combination of surfactants characterized by comprising a ramnolipid biotensoative and a zwitterionic surfactant to increase the viscosity of a fluid cleaning composition at a pH of 3 to 6, preferably from 3.5 to 6, more preferably from 4 to 6 , even more preferably from 4 to 5.75, even more preferably from 4.5 to 5.5.