Composition

Abstract

A liquid composition is disclosed comprising (a) from 0.0001 to 5% by weight of a bacterial cellulose; and (b) from 0.01 to 10% by weight of a copolymer polymerized from monomers comprising: (i) at least one ethylenically unsaturated carboxylic acid; and (ii) at least one C1-C5 alkyl ester and / or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid; wherein the bacterial cellulose and the copolymer are present in a weight ratio of from 1:20 to 10:1.

Description

[0001] COMPOSITION

[0002] Field of the Invention

[0003] The present invention relates to a liquid composition, particularly a liquid detergent composition comprising structurants.

[0004] Background of the Invention

[0005] Nowadays there are various detergent products on the market such as laundry detergent compositions, detergent boosters, dishwash detergent composition and the like. In addition to seeking to improve laundering effectiveness of the detergent compositions, various active materials have been incorporated into the detergent compositions to provide more secondary effects such as smoothness, sterilization, color protection, and long-lasting fragrance retention as functional detergent products are highly favored by consumers.

[0006] However, benefit agents in the form of particulates, for example encapsulated materials such as perfume microcapsules, are often incompatible with liquid detergents. It is difficult to incorporate these materials in a liquid detergent composition as they can lead to phase separation or sediment.

[0007] In order to suspend droplets and particles, structurants have been added to the detergent compositions to provide a structural network. Structurants include both internal and external structurants. Examples of known internal structurants include surfactants and electrolytes. Examples of known external structurants include polymers or gums such as gellan gum, pectine, alginate, carrageenan, xanthan gum, guar gum, and cellulose. It has been reported that certain micro-fibrous cellulose derived from bacteria can be used as external structurants, these may provide efficient suspending properties even at a low polymer level. The bacterial cellulose is believed to form fibrous networks which efficiently trap the particles inside the network and thereby impart good suspending properties.

[0008] W02009 / 101545A1 discloses a structured liquid detergent composition in the form of a liquid matrix made up of an external structuring system of a bacterial cellulose network; water; and surfactant system including an anionic surfactant; a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a zwitterionic surfactant; or mixtures thereof, wherein said liquid matrix has a yield stress of from about 0.003 Pa to about 5.0 Pa at about 25°C and provides suitable particle suspension capabilities and shear thinning characteristics. CN115710539A discloses a microcapsule laundry detergent prepared from the following components in percentage by mass: 0.6 to 3 percent of a suspending agent, 0.5 to 2 percent of a cationic polymer, 15 to 60 percent of a surfactant, 0.05 to 2 percent of microcapsule essence, 0.1 to 15 percent of an auxiliary agent and the balance of water, wherein the suspending agent is bacterial fermentation cellulose; the cationic polymer is chlorinated 2-hydroxy-3- (trimethylamino) propyl polyethylene oxide cellulose ether; and the cationic polymer is a cationic polymer. The surface active agent is selected from at least two of an anionic surface active agent, a nonionic surface active agent and a zwitterionic surface active agent; the molecular weight of the cationic polymer is 1000 to 5000.

[0009] WO2021 / 108335A1 discloses a structured liquid detergent composition including a bacterial- derived cellulose network, a plurality of surfactants including an anionic surfactant and a nonionic surfactant with a weight ratio of the linear alkylbenzene sulfonate to the nonionic surfactant being from about 0.5 to about 5.0, a non-aqueous solvent, and water.

[0010] US2022 / 0387955A1 discloses an aqueous dispersion of microcapsules, said microcapsules comprising a hydrophobic core and a polymeric shell wherein said polymerica shell is formed of the reaction product of (i) at least one monofunctional or multifunctional a,p-unsaturated carbonyl compound, and (ii) at least one nanocellulose or microcrystalline cellulose.

[0011] US2017 / 0211018A1 discloses treatment compositions containing one or more polymers, cationic scavenging agent and an optional structurant as well as methods of making and using the same.

[0012] However, bacterial cellulose alone fails to provide sufficient suspending properties for certain compositions such as those with low levels of internal structurants like surfactants, or where high levels of particles are desired. Another challenge is to achieve a balance between viscosity and suspending ability of a liquid composition that comprises structurants. If the viscosity is too high, the liquid composition may not be easily pourable or spreadable. If the viscosity is too low, the particles may settle or separate from the liquid phase. There remains a need to improve such external structurants.

[0013] Summary of the Invention

[0014] In a first aspect, the present invention is directed to a liquid composition comprising:

[0015] (a) from 0.0001 to 5% by weight of a bacterial cellulose; and

[0016] (b) from 0.01 to 10% by weight of a copolymer polymerized from monomers comprising: (i) at least one ethylenically unsaturated carboxylic acid; and

[0017] (ii) at least one C1-C5 alkyl ester and / or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid; wherein the bacterial cellulose and the copolymer are present in a weight ratio of from 1:20 to 10:1.

[0018] In a second aspect, the present invention is directed to a method for forming a liquid detergent composition or a wash liquor by dispersing a dose of the composition according to any embodiment of the first aspect.

[0019] All other aspects of the present invention will more readily become apparent upon considering the detailed description and examples which follow.

[0020] Detailed Description of the Invention

[0021] Except in the examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and / or use may optionally be understood as modified by the word “about”.

[0022] All amounts are by weight of the final composition, unless otherwise specified. It should be noted that in specifying any ranges of values, any particular upper value can be associated with any particular lower value.

[0023] For the avoidance of doubt, the word “comprising” is intended to mean “including” but not necessarily “consisting of” or “composed of”. In other words, the listed steps or options need not be exhaustive.

[0024] The disclosure of the invention as found herein is to be considered to cover all embodiments as found in the claims as being multiply dependent upon each other irrespective of the fact that claims may be found without multiple dependency or redundancy.

[0025] Where a feature is disclosed with respect to a particular aspect of the invention (for example a composition of the invention), such disclosure is also to be considered to apply to any other aspect of the invention (for example a method of the invention) mutatis mutandis.

[0026] Unless specified otherwise, amounts as used herein are expressed in percentage by weight based on the total weight of the composition and is abbreviated as “wt%” or “weight %”. The liquid composition may find use in a variety of cleaning applications. Preferably the composition is a detergent composition. The term “liquid” in the context of this invention denotes that a continuous phase or predominant part of the composition is liquid and that the composition is flowable at 15°C and above. Accordingly, the term “liquid” may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, known as gels or pastes.

[0027] The liquid composition of the present invention generally has a viscosity of from 550 to 1500 mPa*s, measured at room temperature (25 °C) at a shear rate of 21 s-1by a HAAKE Viscometer. Too low viscosity is not beneficial for suspending particles and the viscosity should not be too high to ensure that the composition is still flowable / pourable.

[0028] In some embodiments the composition is a laundry detergent composition. The term “laundry detergent” in the context of this invention denotes formulated compositions intended for and capable of wetting and cleaning domestic laundry such as clothing, linens and other household textiles. Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid colour care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines. In some embodiments the composition is handwash detergents which involve the consumer using their hands to wash substrates. Fields of use principally involve laundry use (i.e. the hand washing of clothes) and hand dishwash (i.e. the hand washing of dishes and the like). Handwash detergents involve intimate contact of the detergent liquor with the hands during the washing process, whether in laundry or hand dishwash. Laundry detergent composition is particularly preferred.

[0029] The composition may be concentrated or dilute. A “concentrated” composition refers to a composition comprising up to 50% by weight of water, for example up to 40%, up to 30% or up to 20%, based on total weight of the composition. Preferably the composition of the present invention is a “dilute” composition. A “dilute” composition refers to a composition comprising greater than 50% by weight of water, for example greater than 60%, greater than 70% or greater than 80%.

[0030] The term “structural” in the context of this invention refers to any material which is added to the composition to provide rheological and structuring benefits, for example as measured by yield stress. The term “external structural” in the context of this invention refers to a material added to the liquid composition primarily for providing rheological modification purpose and not for an active benefit such as cleaning, conditioning and fragrance. An external structurant is distinct from an internal structurant which may also alter rheology of a composition but which has been incorporated for some additional or alternative primary purpose.

[0031] Amounts of wt.% of bacterial cellulose in the liquid composition refer to wt.% of active bacterial cellulose levels, unless otherwise indicated.

[0032] Amounts of wt.% of copolymer in the liquid composition refer to wt.% of active copolymer levels, unless otherwise indicated.

[0033] Bacterial Cellulose

[0034] The external structurant for use in the present invention comprises a bacterial cellulose. The liquid composition of the present invention comprises from 0.0001 to 5% by weight of a bacterial cellulose, preferably from 0.001 to 3%, more preferably from 0.005 to 2%, most preferably from 0.01 to 1%, based on total weight of the liquid composition and including all ranges subsumed therein. The term “bacterial cellulose” as used in the context of this invention, is intended to encompass any type of cellulose produced via fermentation of a bacteria of the genus Acetobacter and includes materials referred popularly as microfibrillated cellulose, reticulated bacterial cellulose, the like, or a combination thereof.

[0035] The bacterial cellulose is present in the liquid composition of the present invention in the form of a bacterial cellulose network. The bacterial cellulose network may be formed by processing of a mixture of the bacterial cellulose in a hydrophilic solvent, such as water, polyols (e.g., ethylene glycol, glycerin, polyethylene glycol, etc.), or mixtures thereof. This processing is called "activation" and comprises, generally, high pressure homogenization and / or high shear mixing. It has importantly been found that activating the bacterial cellulose under sufficiently intense processing conditions provides for increased yield stress at given levels of bacterial cellulose network. Yield stress is a measure of the force required to initiate flow in a gel-like system. It is believed that yield stress is indicative of the suspension ability of the liquid composition, as well as the ability to remain in situ after application to a vertical surface.

[0036] Activation is a process in which the 3-dimensional structure of the bacterial cellulose is modified such that the cellulose imparts functionality to the base solvent or solvent mixture in which the activation occurs, or to a composition to which the activated cellulose is added. Functionality includes providing such properties as shear-thickening, imparting yield stress - suspension properties, freeze-thaw and heat stability, and the like. The processing that is followed during the activation process does significantly more than to just disperse the cellulose in base solvent. Such intense processing "teases apart" the cellulose fibers to expand the cellulose fibers. The activation of the bacterial cellulose expands the cellulose portion to create a bacterial cellulose network, which is a reticulated network of highly intermeshed fibers with a very high surface area. The activated reticulated bacterial cellulose possesses an extremely high surface area that is thought to be at least 200-fold higher than conventional microcrystalline cellulose (i.e. , cellulose provided by plant sources). It should be noted that conventional microcrystalline cellulose may still be used.

[0037] The bacterial cellulose utilized herein may be of any type associated with the fermentation product of Acetobacter genus microorganisms, and was previously available, for example, from CP Kelco U.S. is CELLULON®. An example of bacterial cellulose suitable for use in the present invention is CELLULON™ R-25. Such aerobic cultured products are characterized by a highly reticulated, branching interconnected network of fibers that are insoluble in water. The preparation of such bacterial cellulose products is well known and typically involve a method for producing reticulated bacterial cellulose aerobically, under agitated culture conditions, using a bacterial strain of Acetobacter aceti var. xylinum. Use of agitated culture conditions results in sustained production, over an average of 70 hours, of at least 0.1 g / liter per hour of the desired cellulose. Wet cake reticulated cellulose, containing approximately 80-85% water, can be produced using the methods and conditions disclosed in the above-mentioned patents. Dry reticulated bacterial cellulose can be produced using drying techniques, such as spray-drying or freeze-drying, that are well known. See U.S. Patent Nos. 5,079,162 and 5,144,021.

[0038] Acetobacter is characteristically a gram-negative, rod shaped bacterium 0.6-0.8 microns by 1.0- 4 microns. It is a strictly aerobic organism; that is, metabolism is respiratory, not fermentative. This bacterium is further distinguished by the ability to produce multiple poly - 1 ,4-glucan chains, chemically identical to cellulose. The microcellulose chains, or microfibers, of reticulated bacterial cellulose are synthesized at the bacterial surface, at sites external to the cell membrane. These microfibers have a cross sectional dimensions of about 1.6 nanometers (nm) to about 3.2 nm by about 5.8 nm to about 133 nm. In one embodiment, the bacterial cellulose network has a widest cross sectional microfiber width of from about 1.6 nm to about 200 nm, alternatively less than about 133 nm, alternatively less than about 100 nm, alternatively less than about 5.8 nm. Additionally, the bacterial cellulose network has an average microfiber length of at least 100 nm, alternatively from about 100 to about 1500 nm. In one embodiment, the bacterial cellulose network has a microfiber aspect ratio, meaning the average microfiber length divided by the widest cross sectional microfiber width, of from about 10:1 to about 1000:1 , alternatively from about 100:1 to about 400:1 , alternatively from about 200:1 to about 300:1.

[0039] The presence of the bacterial cellulose network can be detected by a STEM micrograph imaging. A liquid detergent composition sample is obtained. A 1500 mesh copper TEM grid is placed on filter paper and 15 drops of the sample are applied to the TEM grid. The TEM grid is transferred to fresh filter paper and rinsed with 15 drops of deionized water. The TEM grid is then imaged in a S-5200 STEM micrograph instrument to observe for a fibrous network. Those of skill in the art will understand that if a fibrous network is detected, the cross dimensional of the fibers as well as the aspect ratio can be determined. Those of skill in the art will also recognize that alternative analytic techniques can be used to detect the presence of the bacterial cellulose network such as Atomic Force Microscopy using the same TEM grid and deposition and rinsing steps as disclosed above. An Atomic Force Microscopy 3D representation can be obtained showing the fiber dimensions as well as degree of networking.

[0040] The small cross sectional size of these Acetobacter-produced fibers, together with the large length and the inherent hydrophilicity of cellulose, provides a cellulose product having an unusually high capacity for absorbing aqueous solutions. Additives have often been used in combination with the bacterial cellulose to aid in the formation of stable, viscous dispersions.

[0041] Non-limiting examples of additional suitable bacterial celluloses are disclosed in and U.S. Patent Nos. 6,967,027 to Heux et al ; 5,207,826 to Westland et al ; 4,487,634 to Turbak et al ; 4,373,702 to Turbak et al and 4,863,565 to Johnson et al, U.S. Pat. Publication No. 2007 / 0027108 to Yang et al.

[0042] The bacterial cellulose may be partially coated with a polymeric thickener. This at least partially coated bacterial cellulose can be prepared in accordance with the methods disclosed in U.S. Pat. Publication No. 2007 / 0027108 to Yang et al. at paragraphs 8 - 19. In one suitable process, the bacterial cellulose is subjected to mixing with a polymeric thickener to at least partially coat the bacterial cellulose fibers and bundles. It is believed that the commingling of the bacterial cellulose and the polymeric thickener allows for the desired generation of a polymeric thickener coating on at least a portion of the bacterial cellulose fibers and / or bundles.

[0043] In one embodiment the method of producing said at least partially coated bacterial cellulose comprises a proportion of bacterial cellulose to polymeric thickener comprises from about 0.1% to about 5% of the bacterial cellulose, alternatively from about 0.5% to about 3.0%, by weight of the added polymeric thickener, and from about 10% to about 900% of the polymeric thickener by weight of the bacterial cellulose.

[0044] In one embodiment the polymeric thickener comprises a hydrocolloid, at least on charged cellulose ether, at least one polymeric gum, and mixtures thereof. One suitable hydrocolloid includes carboxymethylcellulose (“CMC”). Suitable polymeric gums comprise xanthan products, pectin, alginates, gellan gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum Arabic, gum ghatti, karay gum, gum tragacanth, tamarind gum, locust bean gum, and the like and mixtures thereof: see U.S. Pat. Publication No. 2007 / 0027108 at paragraphs 6 and 16.

[0045] In another embodiment, the bacterial cellulose undergoes no further modified either chemically or physically aside from the activation and / or the polymeric thickener coating. In one embodiment, the bacterial cellulose is free of a chemical modification comprising esterification or etherification by the addition of hydrophobic groups onto the fibers, meaning that the bacterial cellulose fibers are not modified to be surface active, wherein surface active means the ingredient lowers the surface tension of the medium in which it is dissolved. In another embodiment, the bacterial cellulose is free of any physical modification including coating the fibers with hydrophobic materials.

[0046] The liquid composition of the present invention comprises a copolymer obtainable by polymerizing monomers comprising (i) at least one ethylenically unsaturated carboxylic acid; and (ii) at least one C1-C5 alkyl ester and / or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid. The composition comprises from 0.01 to 10% by weight of the copolymer, preferably from 0.1 to 7%, more preferably from 0.5 to 6% and most preferably from 1 to 3%, based on total weight of the liquid composition and including all ranges subsumed therein. The term “alkyl” as used in the context of this invention, refers to a monovalent moiety derived from alkanes by removing one hydrogen atom.

[0047] Examples of suitable ethylenically unsaturated carboxylic acid includes acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid (anhydride), fumaric acid, crotonic acid, aconitic acid, citraconic acid or mixtures thereof, preferably acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid (anhydride), or mixtures thereof. Acrylic acid and / or methacrylic acid are particularly preferred. Examples of suitable C1-C5 alkyl ester and / or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid includes methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, iso-amyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth) acrylate or mixtures thereof, preferably methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isopropyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or mixtures thereof. Methyl (meth)acrylate and / or ethyl (meth)acrylate are particularly preferred. “(Meth)acrylate” refers to both acrylate and methacrylate.

[0048] The amount of the ethylenically unsaturated carboxylic acid is preferably present in an amount from 20 to 99%, more preferably from 40 to 90%, even more preferably from 60 to 80% by weight of the total monomer contenct of the copolymer. The amount of the C1-C5 alkyl ester and / or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid is preferably present in an amount from 1 to 80%, more preferably from 10 to 60%, even more preferably from 20 to 40% by weight of the total monomer content of the copolymer.

[0049] The copolymer is crosslinked with crosslinking monomers. A crosslinking monomer(s) is utilized to generate a polymer having either a partially or substantially crosslinked three-dimensional network. Preferably the crosslinking monomer is a polyunsaturated compound. Examples of suitable crosslinking monomers include di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di (meth) acrylate, 1 ,3- butylene glycol di(meth)acrylate, 1 ,6-butylene glycol di(meth)acrylate, 1 ,6- hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, 2,2'-bis(4- (acryloxy-propyloxyphenyl)propane, 2,2'-bis(4- (acryloxydiethoxy-phenyl)propane, and zinc acrylate (i.e. , 2(C3HaO2)Zn++); tri(meth)acrylate compounds such as, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and tetramethylolmethane tri(meth)acrylate; tetra(meth)acrylate compounds such as ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate; hexa(meth) acrylate compounds such as dipentaerythritol hexa(meth)acrylate; allyl compounds such as allyl (meth)acrylate, diallylphthalate, diallyl itaconate, diallyl fumarate, and diallyl maleate; polyallyl ethers of sucrose having from 2 to 8 allyl groups per molecule, polyallyl ethers of pentaerythritol such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether; polyallyl ethers of trimethylolpropane such as trimethylolpropane diallyl ether and trimethylolpropane triallyl ether, or mixtures thereof. Other suitable crosslinking monomers include divinyl glycol, divinyl benzene, methylenebisacrylamide, or mixtures thereof.

[0050] The copolymer is preferably functionalized by grafting a graft modification monomer onto the copolymer backbones. Examples of suitable graft modification monomer includes acrylic acid, methacrylic acid, acrylamide, methacrylamide, N,N’-methylenebisacrylamide, or mixtures thereof. When included, the graft modification monomer is in addition to the ethylenically unsaturated carboxylic acid included in the copolymer. The amount of the graft modification monomer is preferably present in an amount from 0.01 to 20%, preferably from 0.1 to 15% by weight of the total monomer content of the copolymer.

[0051] Suitable physiologically acceptable salts of the copolymer include its sodium, magnesium, potassium, ammonium and mono-, di-, and triethanolamine salts. It should be noted that where the copolymer is mentioned in the present disclosure, this also includes the corresponding physiologically acceptable salts thereof, also where not explicitly stated.

[0052] It is preferred that the copolymer is a copolymer of (meth)acrylic acid and C1-C2 alkyl (meth)acrylate, more preferably a copolyme of methacrylic acid and ethyl acrylate. An example is from Guangzhou DX Chemical Co., Ltd under the trade name DX-SF-2.

[0053] The copolymer of the present invention preferably has a weight average molecular weigth of from 500,000 g / mol to 20,000,000 g / mol, more preferably from 1,000,000 g / mol to 18,000,000 g / mol, more preferably still from 5,000,000 g / mol to 15,000,000 g / mol, and most preferably from 8,000,000 g / mol to 12,000,000 g / mol. The term “Weight avearage molecular weight” in the context of this invention, refers to the weight average mass of a given polymer, which is determined by SEC (Size Exclusion Chromatography) analysis using absolute carlibration (universal calibration). Polymethyl methacrylate is used for calibration.

[0054] The copolymer of the present invention may be produced by polymerizing monomers by a method of emulsion polymerization, followed by cross-linking polymerization, and the optionally final step is grafting modification. Suitable copolymers can be prepared by known methods, such as the method disclosed in CN112225846B.

[0055] The bacterial cellulose and the copolymer are present in the liquid composition at a weight ratio of from 1 :20 to 10:1, preferably from 1:15 to 8:1, more preferably from 1:12 to 5:1, most preferably from 1 : 10 to 5: 1. The liquid composition of the present invention may comprise additional external structurants such as non-polymeric crystalline hydroxyl-functional materials, polymeric structurants and mixtures thereof, in addition to the bacterial cellulose and the coplymer included in the composition.

[0056] One suitable additional structurant comprises a non-polymeric (except for conventional alkyoxlation), crystalline hydroxyl-functional materials. Suitable materials can be generally characterized as crystalline, hydroxyl-containing fatty acids, fatty esters or fatty waxes. See e.g. U.S. Patent No. 7,169, 741 at col. 9, line 61 to col.11, line 4, and U.S. Patent No. 6,080, 708 and in WO Publication No. 2002 / 0040627. Preferably, the additional structurant comprises hydrogenated castor oil.

[0057] Suitable polymeric structurants include polysaccharide or polysaccharide derivative type. Polysaccharide derivatives typically used as structurants comprise hydroxypropyl methylcellulose and / or polymeric gum materials. Such gums include pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xuanthan gum and guar gum. Gellan gum is a heteropolysaccharide prepared by fermentation of Pseudomonaselodea ATCC 31461 and is commercially marketed by CP Kelco U.S., Inc. under the KELCOGEL tradename. Processes for preparing gellan gum are described in U.S. Patent Nos. 4,326,052; 4,326,053; 4,377,636 and 4,385,123.

[0058] Preferably, the liquid composition is substantially free of any additional external structurants known in the art such as those listed herein in addition to the bacterial cellulose and the coplymer included in the composition. “Substantially free of’, as used herein, means less than 1.5%, preferably less than 1.0%, more preferably less than 0.75%, more preferably still less than 0.5% and even more preferably less than 0.1% and most preferably from 0 to 0.01% by weight, based on total weight of the composition, including all ranges subsumed therein. It is preferred that the composition does not comprise any additional external structurants.

[0059] Surfactant

[0060] The liquid composition preferably comprises from 0.01 to 60%, more preferably from 1 to 50%, more preferably still from 5 to 30% and most preferably from 8 to 20% by weight of total surfactants, based on total weight of the composition and including all ranges subsumed therein. Suitable surfactants comprise anionic surfactants, non-ionic surfactants, cationic surfactants, amphoteric surfactant or mixtures thereof, preferably the surfactants comprise anionic surfactants, non-ionic surfactants or mixtures thereof. A preferred class of anionic surfactant may be used in the invention includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the “para" position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1 -phenyl isomer. LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ. Examples of alkylbenzene sulfonates include sodium salt of linear alkylbenzene sulphonate, alkyl toluene sulphonate, alkyl xylene sulphonate, alkyl phenol sulphonate, alkyl naphthalene-sulphonate, ammonium diamylnaphthalene-sulphonate and sodium dinonylnaphthalene-sulphonate and mixtures with olefin sulphonates.

[0061] Some alkyl sulfate surfactant (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulphates with an alkyl chain length of from 10 to 18.

[0062] Another anionic surfactant commonly used in compositions are alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 2EO units per molecule.

[0063] The liquid composition of the present invention preferably comprises from 0.01 to 30%, more preferably from 0.1 to 20%, more preferably still from 1 to 15% and most preferably from 5 to 12% by weight of anionic surfactants, based on total weight of the composition and including all ranges subsumed therein.

[0064] The liquid composition may also comprise non-ionic surfactants. Non-ionic surfactants for use in the invention include, for example, a) polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkyl phenols. Where the starter molecule is an alcohol, the reaction product is known as an alcohol alkoxylate. The polyoxyalkylene compounds can have a variety of block and heteric (random) structures. For example, they can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates. Within the block structures, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides. Examples of such materials include Cs to C22 alkyl phenol ethoxylates with an average of from 5 to 25 moles of ethylene oxide per mole of alkyl phenol; and alkyl alcohol ethoxylates such as Cs to Cis primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol; b) fatty acid amides; c) alkoxylated glycerol esters; d) alkyl poly glycosides; e) rhamnolipids; f) methyl ester ethoxylates or a mixture thereof.

[0065] A preferred class of non-ionic surfactant for use in the present invention includes Cs to Cis alkyl alcohol ethoxylates, more preferably C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 3 to 10 moles of ethylene oxide per mole of alcohol. Particularly preferred are lauryl alcohol condensed with 3, 5, 7 and 9 moles of EO (AEO-3, AEO-5, AEO-7 and AEO-9).

[0066] Another preferred class of non-ionic surfactant for use in the invention includes fatty acid amides. Preferably, the fatty acid amide contains at least 6 carbon atoms. Suitable fatty acid preferably contains from 8 to 24 carbon atoms, preferably from 12 to 20 carbon atoms, and most preferably from 12 to 18 carbon atoms. In the most preferred embodiment of the invention, amides of essential fatty acids are employed. Amides suitable for use in the present invention may be simple amides (i.e. , those containing a -CONH2 group), N-alkyl amides, N, N-dialkyl amides, mono-alkanol amides, and di-alkanol amides. Suitable alkyl or alkanol groups contain from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms, and most preferably from 1 to 8 carbon atoms. The preferred amides included in the present invention are mono- and dialkanol amides, particularly of essential fatty acids. Alkanol amides are more commonly available than alkyl amides.

[0067] Preferably, the fatty acid amide is fatty alkanolamides (fatty acid alkanolamides), more preferably Cs to C20 fatty acid Ci to Cs alkanolamide. The preferred fatty acid amides are selected from mono- and diethanolamides of linoleic acid, palmitic acid, and coconut oil. More preferably the fatty acid amide comprises cocamide MEA, cocamide DEA, lauramide DEA, palm kernelamide DEA, stearamide MEA, myristamide DEA, stearamide DEA, oleylamide DEA, tallowamide DEA, tallowamide MEA, isostearamide DEA, isostearamide MEA, cocamide MIPA, or a mixture thereof. Palm kernelamide DEA is particularly preferred.

[0068] Another preferred class of non-ionic surfactant is alkoxylated glycerol esters. The alkoxylated glycerol ester is represented by the formula (V):

[0069] Wherein each of Ri to Re is independently a hydrogen or a methyl group; each of R? to Rg is independently a linear or branched, alkyl or alkenyl group having 5 to 30 carbon atoms, preferably from 8 to 22 carbon atomsTmore preferably from 10 to 18 carbon atoms; m, n, p, x, y, or z is independently a number of from 1 to 30, preferably from 5 to 25 and more preferably from 12 to 21. The sum of m, n, p, x, y, z being in the range of 3 to 90.

[0070] Preferably, the alkoxylated glycerol ester comprises coconut fatty acid esters. Coconut or coco fatty acids include around 82%wt. saturated fatty acids and of the total fatty acid content lauric acid is the most common at around 48% wt. of the fatty acid content. Myristic acid (16%wt.) and palmitic acid (9.5%wt.) are the next most common. Oleic acid is the most common unsaturated acid present at around 6.5% wt. of the fatty acid content.

[0071] Preferably, the alkoxylated glycerol ester comprises palm oil fatty acid esters. Palm oil has a balanced fatty acid composition in which the level of saturated fatty acids is almost equal to that of the unsaturated fatty acids. Palmitic acid (44%-45%) and oleic acid (39%-40%) are the major component acids, with linoleic acid (10%-11 %) and only a trace amount of linolenic acid. Palm kernel oil contains more saturated fatty acids compared to palm oil. The major fatty acids in palm kernel oil are about 48% lauric acid, 16% myristic acid and 15% oleic acid. The most preferred alkoxylated glycerol ester is palm kernel oil ethoxylates. An example is commercially available under the trade name SOE-N-60 from Sinolight Surfactant Technology Co., Ltd.

[0072] Other suitable alkoxylated glyceryl esters are commercially available from Kao under the Levenol brand name. Variants such as Levenol F-200 which has an average EO of 6 and a molar ratio between glycerol and coco fatty acid of 0.55, Levenol V501 / 2 which has an average EO of 17 and a molar ratio between glycerol and coco fatty acid of 1.5 and Levenol C201 which is also known as glycereth-17 cocoate. Another preferred class of non-ionic surfactants which can be used in accordance with this invention are glycoside surfactants. Alkyl poly glycoside surfactants suitable for use in accordance with the present invention include those of the formula:

[0073] RO-(R2O)y-(Z)x wherein R is a monovalent organic radical containing from about 6 to about 30 (preferably from about 8 to about 18) carbon atoms; R2is a divalent hydrocarbon radical containing from about 2 to 4 carbons atoms; O is an oxygen atom; y is a number which can have an average value of from 0 to about 12 but which is most preferably zero; Z is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; and x is a number having an average value of from 1 to about 10 (preferably from about 1 1 / 2 to about 10).

[0074] A particularly preferred group of glycoside surfactants for use in the practice of this invention includes those of the formula above in which R is a monovalent organic radical (linear or branched) containing from about 6 to about 18 (especially from about 8 to about 18) carbon atoms; y is zero; z is glucose or a moiety derived therefrom; x is a number having an average value of from 1 to about 4 (preferably from about 1 1 / 2 to 4).

[0075] Another preferred class of non-ionic surfactants which can be used in accordance with this invention are methyl ester ethoxylates (MEE). Methyl ester ethoxylate surfactant is of the form:

[0076] R3(-C=O)-O-(CH2CH2-O)n-CH3

[0077] Where R3COO is a fatty acid moiety, such as oleic, stearic, palmitic. Fatty acid nomenclature is to describe the fatty acid by 2 numbers A:B where A is the number of carbons in the fatty acid and B is the number of double bonds it contains. For example oleic is 18:1, stearic is 18:0 and palmitic 16:0. The position of the double bond on the chain may be given in brackets, 18:1(9) for oleic, 18:2 (9,12) for linoleic where 9 if the number of carbons from the COOH end.

[0078] The integer n is the mole average number of ethoxylates.

[0079] Methyl ester ethoxylates (MEE) are described in chapter 8 of Biobased Surfactants (Second Edition) Synthesis, Properties, and Applications Pages 287-301 (AOCS press 2019) by G.A. Smith; J. Am. Oil. Chem.Soc. vol 74 (1997) page 847-859 by Cox M.E. and Weerasooriva II;

[0080] Tenside Surf.Det. vol 28 (2001) page by 72-80 by Hreczuch et al; by C. Kolano. Household and Personal Care Today (2012) page 52-55; J. Am. Oil. Chem.Soc. vol 72 (1995) page 781-784 by A. Hama et al. MEE may be produced the reaction of methyl ester with ethylene oxide, using catalysts based on calcium or magnesium. The catalyst may be removed or left in the MEE.

[0081] The methyl ester ethoxylate preferably has a mole average of from 8 to 13 ethoxylate groups (EO). The most preferred ethoxylate has a mol average of from 9 to 11 EO, even more preferably 10EO. When the MEE has a mole average of 10EO then at least 10 wt.% of the MEE should consist of ethoxylate with 9, 10 and 11 ethoxylate groups.

[0082] In the context of the wider MEE contribution, it is preferred that at least 40wt% of the total MEE in the composition is C18:1.

[0083] In addition, it is preferred that the MEE component also comprises some C16 MEE.

[0084] Accordingly, it is preferred that the total MEE component comprises from 5 to 50% wt. total MEE, C16 MEE. Preferably the C16 MEE is greater than 90wt%, more preferably greater than 95wt% C16:0.

[0085] Further, it is preferred that the total MEE component comprises less than 15% wt, more preferably less than 10wt%, most preferably less than 5wt% total MEE of polyunsaturated C18, i.e. C18:2 and C18:3. Preferably C18:3 is present at less than 1 wt%, more preferably less than 0.5wt%, most preferably essentially absent. The levels of polyunsaturation may be controlled by distillation, fractionation or partial hydrogenation of the raw materials (triglyceride or methyl ester) or of the MEE.

[0086] Further, it is preferred that the C18:0 component is less than 10wt% by weight of the total MEE present.

[0087] Further, it is preferred that the components with carbon chains of 15 or shorter comprise less than 4wt% by weight of the total MEE present.

[0088] A particularly preferred MEE has 2 to 26 wt.% of the MEE C16:0 chains, 1 to 10 wt.% C18:0 chains, 50 to 85 wt.% C18:1 chains and 1 to 12 wt.% C18:2 chains.

[0089] Preferred sources for the alkyl groups for the MEE include methyl ester derived from distilled palm oil and distilled high oleic methyl ester derived from palm kernel oil, partially hydrogenated methyl ester of low euric rapeseed oil, methyl ester of high oleic sunflower oil, methyl ester of high oleic safflower oil and methyl ester of high oleic soybean oil.

[0090] High Oleic oils are available from DuPont (Plenish high oleice soybean oil), Monsanto (Visitive Gold Soybean oil), Dow (Omega-9 Canola oil, Omega-9 sunflower oil), the National Sunflower Association and Oilseeds International.

[0091] Preferably the double bonds in the MEE are greater than 80wt% in the cis configuration.

[0092] Preferably the 18:1 component is oleic. Preferably the 18:2 component is linoleic.

[0093] The methyl group of the methyl ester may be replaced by an ethyl or propyl group. Methyl is most preferred.

[0094] Preferably, the non-ionic surfactant comprises alkyl alcohol ethoxylates. Mixtures of two or more of the non-ionic surfactants can be used. When the composition comprises non-ionic surfactants, the non-ionic surfactant is typically present at a level from 0.01 to 30%, more preferably from 0.1 to 20% and most preferably from 1 to 10%, based on total weight of the composition and including all ranges subsumed therein.

[0095] The composition may also comprise one or more types of cationic surfactant. Many cationic surfactants are known in the art, and almost any cationic surfactant having at least one long chain alkyl group of about 10 to 24 carbon atoms may be present as an auxiliary component of the surfactant system. Such compounds are described in "Cationic Surfactants", Jungermann, 1970, incorporated by reference.

[0096] Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof. More cationic surfactants which can be used as surfactants are described in detail in U.S. Patent No. 4,497,718, hereby incorporated by reference. As with the non-ionic and anionic surfactants, the compositions of the invention may use cationic surfactants alone or in combination with any of the other surfactants known in the art. Cationic surfactant, when included, may be present in an amount ranging from 0 to 5% based on total weight of the composition. It is preferred that the composition does not comprise any cationic surfactants. The composition may also comprise one or more types of amphoteric surfactant. Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from 0 to 5% based on total weight of the composition. It is preferred that the composition does not comprise any amphoteric surfactants.

[0097] Source of alkyl chains

[0098] The alkyl chains of the surfactant are 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.

[0099] 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 Kernel and Coconut oils are the source. The required ratio of C12:C14 may be obtained by fractionation / distillation and mixing of components.

[0100] 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.

[0101] 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), Stil lingia, 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.

[0102] The C12 C14 linear alcohols which are suitable as an intermediate step in the manufacture of C12 C14 ether sulphate ca be obtained from many different sustainable sources. These include:

[0103] Primary sugars

[0104] Primary sugars are obtained from cane sugar or sugar beet, etc., and may be fermented to form bioethanol. The bioethanol is then dehydrated to form bio-ethylene which then undergoes olefin methathesis to form alkenes. These alkenes are then processed into linear alcohols either by hydroformylation or oxidation.

[0105] An alternative process also using primary sugars to form linear alcohols can be used and where the primary sugar undergoes microbial conversion by algae to form triglycerides. These triglycerides are then hydrolysed to linear fatty acids and which are then reduced to form the linear alcohols.

[0106] Biomass

[0107] Biomass, for example forestry products, rice husks and straw to name a few may be processed into syngas by gasification. Through a Fischer Tropsch reaction these are processed into alkanes, which in turn are dehydrogenated to form olefins. These olefins may be processed in the same manner as the alkenes described above [primary sugars].

[0108] An alternative process turns the same biomass into polysaccharides by steam explosion which may be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol which in turn is dehydrated to form bio-ethylene. This bio-ethylene is then processed into linear alcohols as described above [primary sugars], l / l / aste Plastics

[0109] Waste plastic is pyrolyzed to form pyrolysed oils. This is then fractioned to form linear alkanes which are dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars]. Alternatively, the pyrolyzed oils are cracked to form ethylene which is then processed to form the required alkenes by olefin metathesis. These are then processed into linear alcohols as described above [primary sugars].

[0110] Municipal Solid Waste

[0111] MSW is turned into syngas by gasification. From syngas it may be processed as described above [primary sugars] or it may be turned into ethanol by enzymatic processes before being dehydrogenated into ethylene. The ethylene may then be turned into linear alcohols by the Ziegler Process.

[0112] The MSW may also be turned into pyrolysis oil by gasification and then fractioned to form alkanes. These alkanes are then dehydrogenated to form olefins and then linear alcohols.

[0113] Marine Carbon

[0114] There are various carbon sources from marine flora such as seaweed and kelp. From such marine flora the triglycerides can be separated from the source and which is then hydrolysed to form the fatty acids which are reduced to linear alcohols in the usual manner.

[0115] Alternatively, the raw material can be separated into polysaccharides which are enzymatically degraded to form secondary sugars. These may be fermented to form bio-ethanol and then processed as described above [Primary Sugars],

[0116] Waste Oils

[0117] Waste oils such as used cooking oil can be physically separated into the triglycerides which are split to form linear fatty acids and then linear alcohols as described above.

[0118] Alternatively, the used cooking oil may be subjected to the Neste Process whereby the oil is catalytically cracked to form bio-ethylene. This is then processed as described above.

[0119] Methane Capture

[0120] Methane capture methods capture methane from landfill sites or from fossil fuel production. The methane may be formed into syngas by gasification. The syngas may be processed as described above whereby the syngas is turned into methanol (Fischer Tropsch reaction) and then olefins before being turned into linear alcohols by hydroformylation oxidation. Alternatively, the syngas may be turned into alkanes and then olefins by Fischer Tropsch and then dehydrogenation.

[0121] Carbon Capture

[0122] Carbon dioxide may be captured by any of a variety of processes which are all well known. The carbon dioxide may be turned into carbon monoxide by a reverse water gas shift reaction and which in turn may be turned into syngas using hydrogen gas in an electrolytic reaction. The syngas is then processed as described above and is either turned into methanol and / or alkanes before being reacted to form olefins.

[0123] Alternatively, the captured carbon dioxide is mixed with hydrogen gas before being enzymatically processed to form ethanol. This is a process which has been developed by Lanzatech. From here the ethanol is turned into ethylene and then processed into olefins and then linear alcohols as described above.

[0124] The above processes may also be used to obtain the C12 / 14 chains of the C 12 / 14 ether sulfates.

[0125] Perfume

[0126] Preferably, the liquid compositon of the present invention comprises perfume materials. The terms “perfume” and “fragrance” as used herein are used interchangeable to refer to the same material.

[0127] Preferably the perfume materials are present at a level from 0.01 to 5%, more preferably from 0.05 to 3%, even more preferably 0.1 to 1% by weight of the composition. Preferably the composition comprises a combination of both free perfume and perfume microcapsules.

[0128] Free perfume

[0129] The liquid composition of the present invention preferably comprises from 0.01 to 5%, more preferably from 0.05 to 3%, even more preferably 0.1 to 1% by weight of free perfume.

[0130] Useful perfume components may include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and / or aromatizing consumer products.

[0131] Particularly preferred perfume components are blooming perfume components and substantive perfume components. Blooming perfume components are defined by a boiling point less than 250°C and a LogP greater than 2.5. Substantive perfume components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Preferably a perfume composition will comprise a mixture of blooming and substantive perfume components. The perfume composition may comprise other perfume components.

[0132] It is commonplace for a plurality of perfume components to be present in a perfume composition. In the compositions for use in the present invention it is envisaged that there will be three or more, preferably four or more, more preferably five or more, most preferably six or more different perfume components. An upper limit of 300 perfume ingredients may be applied. Preferably, the perfume comprises a component selected from the group consisting of ethyl-2- methyl valerate (manzanate), limonene, (4Z)-cyclopentadec-4-en-1-one, dihyro myrcenol, dimethyl benzyl carbonate acetate, benzyl acetate, spiro[1 ,3-dioxolane-2,5'-(4',4',8',8'- tetramethyl-hexahydro-3',9'-methanonaphthalene)], benzyl acetate, Rose Oxide, geraniol, methyl nonyl acetaldehyde, decanal, octanal, undecanal, verdyl acetate, tert-butylcyclohexyl acetate, cyclamal, beta ionone, hexyl salicylate, tonalid, phenafleur, octahydrotetramethyl acetophenone (OTNE), the benzene, toluene, xylene (BTX) feedstock class such as 2-phenyl ethanol, phenoxanol and mixtures thereof, the cyclododecanone feedstock class, such as habolonolide, the phenolics feedstock class such as hexyl salicylate, the C5 blocks or oxygen containing heterocycle moiety feedstock class such as gamma decalactone, methyl dihydrojasmonate and mixtures thereof, the terpenes feedstock class such as dihydromycernol, linalool, terpinolene, camphor, citronellol and mixtures thereof, the alkyl alcohols feedstock class such as ethyl-2-methylbutyrate, the diacids feedstock class such as ethylene brassylate, and mixtures of these components.

[0133] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the perfume component ethyl-2-methyl valerate (manzanate).

[0134] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to

[0135] 15 wt.% and especially preferably from 6 to 10% wt. of the perfume component limonene. Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component (4Z)-cyclopentadec-4-en-1-one.

[0136] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component dimethyl benzyl carbonate acetate.

[0137] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component dihyromyrcenol.

[0138] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component rose oxide.

[0139] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component tert-butylcyclohexyl acetate.

[0140] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component verdyl acetate.

[0141] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component benzyl acetate.

[0142] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component spiro[1 ,3-dioxolane-2,5'- (4',4',8',8'-tetramethyl-hexahydro-3',9'-methanonaphthalene)].

[0143] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component geraniol.

[0144] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component methyl nonyl acetaldehyde.

[0145] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the perfume component cyclamal. Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the perfume component beta ionone.

[0146] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the perfume component hexyl salicylate.

[0147] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the perfume component tonalid.

[0148] Preferably, the perfume comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the perfume component phenafleur.

[0149] Preferably, the perfume comprises a component selected from the benzene, toluene, xylene (BTX) feedstock class. More preferably, the perfume component is selected from 2-phenyl ethanol, phenoxanol and mixtures thereof.

[0150] Preferably, the perfume comprises a component selected from the cyclododecanone feedstock class. More preferably, the perfume component is habolonolide.

[0151] Preferably, the perfume comprises a component selected from the phenolics feedstock class. More preferably, the perfume component is hexyl salicylate.

[0152] Preferably, the perfume comprises a component selected from the C5 blocks or oxygen containing heterocycle moiety feedstock class. More preferably, the perfume component is selected from gamma decalactone, methyl dihydrojasmonate and mixtures thereof.

[0153] Preferably, the perfume comprises a component selected from the terpenes feedstock class. More preferably, the perfume component is selected from, linalool, terpinolene, camphor, citronellol and mixtures thereof.

[0154] Preferably, the perfume comprises a component selected from the alkyl alcohols feedstock class. More preferably, the perfume component is ethyl-2-methylbutyrate.

[0155] Preferably, the perfume comprises a component selected from the diacids feedstock class.

[0156] More preferably, the perfume component is ethylene brassylate. Preferably, the perfume component listed above is present in the final composition at from 0.0001 to 1% by wt. of the composition.

[0157] The liquid composition of the present invention preferably comprises microcapsules. The microcapsules may be provided simply as microcapsules but preferably are provided in a microcapsule composition.

[0158] By microcapsule composition it is herein understood to mean the composition comprising microcapsules which is added to a liquid composition. The microcapsule composition may comprise only microcapsules or may be in the form of a slurry comprising microcapsules.

[0159] By microcapsule it is herein understood to mean the microcapsule (shell and core) i.e., without a solvent or slurry.

[0160] The liquid composition of the present invention preferably comprises 0.01 to 5%, more preferably from 0.05 to 3%, even more preferably from 0.1 to 1% by weight of microcapsules. The weight of the microcapsules is of the material as supplied, which may be in the form of a slurry comprising microcapsules.

[0161] Microencapsulation may be defined as the process of surrounding or enveloping one substance within another substance on a very small scale, yielding capsules ranging from less than one micron to several hundred microns in size. The material that is encapsulated may be called the core, the active ingredient or agent, fill, payload, nucleus, or internal phase. The material encapsulating the core may be referred to as the coating, membrane, shell, or wall material. Microcapsules typically have at least one generally spherical continuous shell surrounding the core. The shell may contain pores, vacancies or interstitial openings depending on the materials and encapsulation techniques employed. Multiple shells may be made of the same or different encapsulating materials, and may be arranged in strata of varying thicknesses around the core. Alternatively, the microcapsules may be asymmetrically and variably shaped with a quantity of smaller droplets of core material embedded throughout the microcapsule.

[0162] Microcapsule shell materials

[0163] The shell may have a barrier function protecting the core material from the environment external to the microcapsule, but it may also act as a means of modulating the release of core materials such as fragrance. Thus, a shell may be water soluble or water swellable and core materials release may be actuated in response to exposure of the microcapsules to a moist environment. Similarly, if a shell is temperature sensitive, a microcapsule might release core materials in response to elevated temperatures. Microcapsules may also release core materials in response to shear forces applied to the surface of the microcapsules.

[0164] The shell material typically makes up from 0.1 to 30%, more preferably from 0.5 to 25%, even more preferably from 1 to 20% and most preferably from 2 to 15% by weight of the microcapsule. Suitable shell materials include, but not limited to, aminoplasts, protein, polysaccharides, polyurethanes, polyacrylates, polymethacrylates, polyamides, polyolefins, gums, silicones, lipids, modified cellulose, polyphosphate, polystyrene, polyesters or combinations thereof.

[0165] A preferred shell material comprises aminoplast, such as polycondensation product of melamine (2,4,6-triamino-1,3,5-triazine) with formaldehyde or urea with formaldehyde. Another preferred shell material comprises protein and / or polysaccharides. The protein and / or polysaccharide may be treated by various processes to provide derivatives, including but not limited to hydrolysis, condensation, functionalising such as ethoxylating, crosslinking, etc. The microcapsule shell materials are preferably in an aqueous solution. The microcapsule shell preferably comprises 20 wt.% to 100 wt.% protein, polysaccharide, or combinations thereof, more preferably 30 wt.% to 98 wt.%, more preferably 35 wt.% to 95 wt.%, and most preferably 65 wt.% to 90 wt.% by weight of the microcapsule shell.

[0166] As is conventional in the art, a “polypeptide” or “protein” is a linear organic polymer composed of amino acid residues bonded together in a chain, forming part of (or the whole of) a protein molecule. “Polypeptide” or “protein” as used herein means a natural polypeptide, polypeptide derivative, and / or modified polypeptide. The polypeptide may exhibit an average molecular weight of from 1,000 Da to 40,000,000 Da, preferably greater than 10,000 Da, more preferably, 100,000 Da, most preferably greater than 1,000,000 Da and preferably less than 3,000,000 Da.

[0167] Suitable proteins for use in this invention include whey proteins, plant proteins and gelatine. Preferably the plant proteins are used. Suitable preferred proteins include proteins selected from: pea, potato proteins, brown rice, white rice, wheat, egg, barley, pumpkin seed, oat, almond, whey, casein, silk, gelatin, algae, rye, spelt, gluten, rapeseed, sunflower, corn, soybean, bean, chickpea, lentil, lupin, peanut, alfalfa, hemp, proteins resulting from fermentation, proteins from food waste and combinations thereof. Particularly preferred proteins include proteins selected from chickpea, pea proteins, potato proteins, brown rice proteins, white rice proteins, wheat proteins, barley proteins, pumpkin seed proteins, oat proteins, almond proteins, and combinations thereof. This includes derivatives of the aforementioned proteins.

[0168] As used herein, whey protein refers to the protein contained in whey, a dairy liquid obtained as a supernatant of curds when milk or a dairy liquid containing milk components, is processed into cheese curd to obtain a cheese-making curd as a semisolid. Whey protein is generally understood in principle to include the globular proteins b-lactoglobulin and a-lactalbumin at various ratios such as 1: 1 to 5: 1 (e.g., 2: 1). It may also include lower amounts of serum albumin, immunoglobulin and other globulins. The term whey protein is also intended to include partially or completely modified or denatured whey proteins. Purified b-lactoglobulin and / or a- lactalbumin polypeptides may also be used in preparation of microcapsules of this invention.

[0169] Gelatin refers to a mixture of proteins produced by partial hydrolysis of collagen extracted from the skin, bones, and connective tissues of animals. Gelatin can be derived from any type of collagen, such as collagen type I, II, III, or IV. Such proteins are characterized by including Gly- Xaa-Yaa triplets wherein Gly is the amino acid glycine and Xaa and Yaa can be the same or different and can be any known amino acid. At least 40% of the amino acids are preferably present in the form of consecutive Gly-Xaa-Yaa triplets.

[0170] A preferred class of proteins are plant proteins. Plant proteins are proteins that accumulate in various plant tissues. Preferred plant proteins can be classified into two classes: seed or grain proteins and vegetable proteins. Seed / grain proteins are a set of proteins that accumulate to high levels in seeds / grains during the late stages of seed / grain development, whereas vegetable proteins are proteins that accumulate in vegetative tissues such as leaves, stems and, depending on plant species, tubers.

[0171] Preferred examples of seed / grain / legumes storage proteins are proteins from: soya, lupine, pea, chickpea, alfalfa, horse bean, lentil, and haricot bean; from oilseed plants such as colza, cottonseed and sunflower; from cereals like wheat, maize, barley, malt, oats, rye and rice (e.g., brown rice protein), or a combination thereof.

[0172] Preferred examples of vegetable protein are proteins form: potato or sweet potato tubers.

[0173] The term plant protein is intended to include a plant protein isolate, plant protein concentrate, or a combination thereof. Plant protein isolates and concentrates are generally understood to be composed of several proteins. For example, pea protein isolates and concentrates may include legumin, vicilin and convicilin proteins. Similarly, brown rice protein isolates may include albumin, globulin and glutelin proteins. The term “plant protein” is also intended to include a partially or completely modified or denatured plant storage protein. Individual polypeptides (e.g., legumin, vicilin, convicilin, albumin, globulin or glutelin) may also be used in preparation of microcapsules of this invention.

[0174] A native protein maybe preferred. However, the process may include a step of denaturing the protein by pH adjustment, heat, or adding a chaotropic agent to the oil-in-water emulsion or to the protein before adding to the oil-in-water emulsion.

[0175] Denaturation is a process in which proteins (polypeptides) lose the quaternary structure, tertiary structure, and secondary structure present in their native state, by application of a denaturation condition. During denaturation, proteins change their conformational structure by unfolding, thereby making amine and hydroxyl groups available for crosslinking (such as crosslinking with polyisocyanate) to form a microcapsule wall. Exemplary conditions for protein denaturation include, but are not limited to, radiation, exposure to heat or cold, changes in pH with an acid or base, exposure to denaturing agents such as detergents, inorganic salt, organic solvent (e.g., alcohol, ethyl acetate, and chloroform), urea, or other chaotropic agents, or mechanical stress including shear. Exemplary chaotropic agents are guanidine salts (e.g., guanidine hydrochloride and guanidine carbonate), urea, polysorbate, sodium benzoate, vanillin, o-cresol, phenol, propanol, formamide, ethanol, fructose, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium phosphate, potassium sulfate, potassium chloride, potassium iodide, potassium nitrate, potassium phosphate, sodium sulfate, sodium chloride, sodium bromide, sodium nitrate, sodium phosphate, guanidine thiocyanate, xylose, glycerol, benzyl alcohol, ethyl acetate, triton X-100, ethyl acetate, cetyltrimethylammonium halide, acetone, sodium dodecyl sulfate (SDS), hydrochloric acid, sulfuric acid, polyethylene glycol, glutaraldehyde, and combinations thereof. Any amount of the chaotropic agent can be used.

[0176] It may be preferred that the protein is denatured with a chaotropic agent so that 20 wt. % to 100 wt.% preferably 40 wt. % to 100 wt. %, more preferably 60 wt.% to 100 wt.%, most preferably 90 wt.% to 100 wt.% of the protein used in the preparation of the microcapsules is denatured.

[0177] The protein used in the microcapsule can also be derivatized or modified (e.g., derivatized or chemically modified). For example, the protein can be modified by covalently attaching sugars, lipids, cofactors, peptides, or other chemical groups including phosphate, acetate, methyl, and other natural or unnatural molecule.

[0178] Polysaccharides are a class of carbohydrates comprising multiple monosaccharide units. “Polysaccharide” as used herein means a natural polysaccharide, polysaccharide derivative, and / or modified polysacharide. Suitable polysaccharides maybe selected from the group consisting of fibres, starch, sugar alcohols, sugars and mixtures thereof.

[0179] Examples of suitable fibres include: particular cellulose, cellulose derivatives such as hydroxyethyl cellulose, in particular quaternized hydroxyethyl cellulose, carboxymethylcellulose (CMC) and microcrystalline cellulose (MCC), hemicelluloses, lichenin, chitin, chitosan, lignin, xanthan, plant fibers, in particular cereal fibers, potato fibers, apple fibers, citrus fibers, bamboo fibers, extracted sugar beet fibers; oat fibers and soluble dietary fibers, in particular inulin, especially native inulin, highly soluble inulin, granulated inulin, high performance inulin, pectins, alginates, agar, carrageenan, gum arabic (Senegal type, Seyal type), konjac gum, gellan gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose, xylose, polydextrose and lactulose and combinations thereof. This includes derivatives of the aforementioned polysaccharides.

[0180] Examples of suitable starches include starch from: wheat, potatoes, corn, rice, tapioca and oats, modified starch, and starch derivatives, e.g., dextrins or maltodextrins, in particular dextrins and maltodextrins from wheat, potatoes, corn, rice, pea, chickpea and oats, oligosaccharides, in particular oligofructose. Preferred starches are selected from: corn starch, potato starch, rye starch, wheat starch, barley starch, oat starch, rice starch, pea starch, chickpea starch, tapioca starch, and mixtures thereof.

[0181] Examples of suitable sugar alcohols include: sorbitol, mannitol, isomalt, maltitol, maltilol syrup, lactitol, xylitol, erythritol.

[0182] An example of suitable sugar includes: glucose.

[0183] Particularly preferred polysaccharides include: gum Arabic, dextrins and maltodextrins are particularly preferred.

[0184] The polysaccharide used in the microcapsule can also be derivatized or modified (e.g., derivatized or chemically modified). For example, the protein can be modified by covalently attaching sugars, lipids, cofactors, peptides, or other chemical groups including phosphate, acetate, methyl, and other natural or unnatural molecule. Examples of suitable polysaccharide derivatives include: starch glycolate, carboxymethyl starch, hydroxyalkyl cellulose and crosslinked modified cellulose.

[0185] Mixtures of any of the above-described shell materials may also be suitable.

[0186] The microcapsule shell materials described herein can be crosslinked. Suitable methods of crosslinking include: isocyanate crosslinking, salt bridge cross linking and internal crosslinking within the microcapsule wall polymer structures (including the formation of a coacervate). Where a cross linking agent is used, such as polyisocyanate crosslinking agents or ionic crosslinking agents the crosslinking agent is preferably present at a level of 0.1 wt.% to 10 wt.% by weight of the microcapsule, preferably 0.5 wt.% to 9 wt.% by weight of the microcapsule, even more preferably 1 to 8 wt.% by weight of the microcapsule.

[0187] The microcapsule may optionally comprise further crosslinking agents. The further crosslinking agent maybe selected from the group consisting of transglutaminase, peroxidase, secondary plant substances selected from the group consisting of polyphenols, in particular tannin, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the aforementioned crosslinking agents.

[0188] The microcapsule may optionally comprise one or more deposition aids attached to the shell of the microcapsule. Deposition aids serve to modify the properties of the exterior of the microcapsule, for example to make the microcapsule more substantive to a desired substrate. Desired substrates include cellulosics (including cotton) and polyesters (including those employed in the manufacture of polyester fabrics).

[0189] If used, then preferably the deposition aid is from the group consisting of trimonium, methacrylamidopropyl trimethyl ammonium, acrylamidopropyl trimethylammonium, acrylamide, acrylic acid, dimethyl ammonium, xlylose, galactose, hydroxypropylated glucose, chitosan, hydroxyethylated glucose, hydroxymethylated glucose, vinylamine, ethylenimine, functionalized branched polyethylenimine, vinylformamide, vinylpyrollidone, caprolactone, catechol, vinylalcohol, chitosan, polyquatemium-4, polyquatemium-5, polyquatemium-6, polyquatemium- 7, polyquatemium-10, polyquatemium-11, polyquatemium-16, polyquatemium-22, polyquatemium-24, polyquatemium-28, polyquatemium-37, polyquatemium-39, polyquatemium- 44, polyquatemium-46, polyquatemium-47, polyquatemium-53, polyquatemium-55, polyquatemium-67, polyquatemium-68, polyquatemium-69, polyquatemium-73, polyquatemium- 74, polyquatemium-77, polyquatemium-78, polyquatemium-79, polyquatemium-80, polyquatemium-81, polyquatemium-82, polyquatemium-86, polyquatemium-88, polyquatemium- 101 , polyquatemium-79 hydrolyzed keratin, polyvinylamine, polyethyleneimine, a copolymer of vinylamine and vinylformamide, a copolymer of acrylamide and 3-methacryloylaminopropyl trimethylammonium, a 3-acrylamidopropyl trimethylammonium polymer or its copolymer, a diallyldimethylammonium-chloride polymer and its copolymer, a polysaccharide with saccharide unit functionalized with hydroxypropyl trimmonium, ethyltrimonium chloride methacrylate and hydrolyzed wheat protein copolymer, alkyl-monium hydroxypropyl hydrolyzed protein, and combinations thereof.

[0190] Microcapsule core materials

[0191] The core may also be referred to as the internal phase. The core of the microcapsule comprises active material and optionally further comprises solvents, crosslinking agents as described above or combinations thereof. The core is preferably non-aqueous.

[0192] The internal non-aqueous phase may preferably comprise from 20 to 99 wt.%, preferably from 25 to 98 wt.% and even more preferably from 33 to 95 wt.% active material to be encapsulated and preferably from 0.1 to 5 wt.%, preferably from 0.15 to 3.5 wt.% and even more preferably from 0.5 to 2.5 wt.% crosslinking agent and the remaining composition solvent.

[0193] Preferably the active materials are selected from perfume, fabric care actives, fabric softener actives, hard surface cleaning actives, antimicrobial actives, antiviral actives, emollients, skin moisturizing actives and combinations thereof. Exemplary active materials include: perfume; malodour agents for example: uncomplexed cyclodextrin, odor blockers, reactive aldehydes, flavonoids, zeolites, activated carbon, and mixtures thereof; dye transfer inhibitors; shading dyes; silicone oils, resins, and modifications thereof such as linear and cyclic polydimethylsiloxanes, amino-modified, allcyl, aryl, and alkylaryl silicone oils, which preferably have a viscosity of greater than 50,000 cst; insect repellents; organic sunscreen actives, for example, octylmethoxy cinnamate; antimicrobial agents, for example, 2-hydroxy-4, 2,4- trichlorodiphenylether; ester solvents, for example isopropyl myristate; lipids and lipid like substance, for example, cholesterol; hydrocarbons such as paraffins, petrolatum, and mineral oil; fish and vegetable oils; hydrophobic plant extracts; waxes; pigments including inorganic compounds with hydrophobically- modified surface and / or dispersed in an oil or a hydrophobic liquid; sugar-esters, such as sucrose polyester (SPE); and combinations thereof. The active materials may be dissolved in a solvent. Examples of suitable solvents include vegetable oils, glycerides, esters of fatty acids and branched alcohols, hydrocarbon, etc. specific examples include: diethyl phthalate, isopropyl myristate, Abalyn® (rosin resins, available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes, triacetin or isoparaffins, preferably Abalyn®, benzyl benzoate, limonene or other terpenes, isoparaffins, or combinations thereof. Preferably, if present, the solvent is 0 to 30 wt.% of the active material, more preferably 0 to 20 wt.% and most preferably 0 to 10 wt.% of the active material.

[0194] Most preferably the active material comprises perfume. Perfume components are well known in the art. Useful perfume components may include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and / or aromatizing consumer products.

[0195] Particularly preferred perfume components are blooming perfume components and substantive perfume components. Blooming perfume components are defined by a boiling point less than 250°C and a LogP greater than 2.5. Preferably encapsulated perfume compositions comprise at least 20 wt.% blooming perfume ingredients, more preferably at least 30 wt.% and most preferably at least 40 wt.% blooming perfume ingredients. Substantive perfume components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Preferably encapsulated perfume compositions comprise at least 10 wt.% substantive perfume ingredients, more preferably at least 20 wt.% and most preferably at least 30 wt.% substantive perfume ingredients. Boiling point is measured at standard pressure (760 mm Hg). Preferably a perfume composition will comprise a mixture of blooming and substantive perfume components. The perfume composition may comprise other perfume components.

[0196] It is commonplace for a plurality of perfume components to be present in a microcapsule. In the compositions for use in the present invention it is envisaged that there will be three or more, preferably four or more, more preferably five or more, most preferably six or more different perfume components in a microcapsule. An upper limit of 300 perfume components may be applied.

[0197] It is particularly preferred that the perfume comprises perfume components as described above. Preferably the encapsulated active material (e.g. perfume) is present at a level from 5 to 99 %, preferably 10 to 99%, more preferably 15 to 95%, and most preferably 20 to 93% by weight of the microcapsule.

[0198] One example of a preferred microcapsule suitable for use in the present invention is a microcapsule with an aminoplast shell formed from the polycondensation product of melamine or urea with formaldehyde and a core comprising perfume.

[0199] Another example of a preferred microcapsule suitable for use in the present invention is a microcapsule with a shell formed from protein and / or polysaccharide and a core comprising perfume.

[0200] The microcapsules of the present invention preferably have a D50 particle size from 0.1 to 1000 microns, more preferably 0.5 to 500 microns, even more preferably from 1 to 200 microns, and most preferably from 1 to 100 microns. The particle size can be determined by dynamic light scattering using a Malvern Mastersizer, for example, Mastersizer 3000.

[0201] The microcapsules may be prepared by any suitable process such as coacervation, interfacial polymerization, polycondensation and 3D printing.

[0202] The microcapsule composition may comprise further ingredients. A preferred further ingredient are polyphenols. Particularly preferred are phenols having a 3,4,5-trihydroxyphenyl group or 3,4-dihydroxypheny group such as tannic acid. In additional to polyphenols, other polyols can also be used to prepare the microcapsule compositions of this invention. Examples include pentaerythritol, dipentaerythritol, glycerol, polyglycerol, ethylene glycol, polyethylene glycol, trimethylolpropane, neopentyl glycol, sorbitol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol, polyphenol, and combinations thereof.

[0203] Polyphenols, polyols, and multi-functional aldehydes are preferably present at a level of 0 wt.% to 40 wt.%, preferably 1 wt.% to 35 wt.% more preferably 5 wt.% to 35 wt.% and most preferably 10 wt.% to 30 wt.%.

[0204] A composition of the invention may comprise non-aqueous carriers such as hydrotropes, cosolvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (Mw) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulfonates).

[0205] Mixtures of any of the above described materials may also be used.

[0206] Non-aqueous carriers, when included, may be present in an amount ranging from 0.1 to 3%, preferably from 0.5 to 1%, based on total weight of the composition and including all ranges subsumed therein. The level of hydrotrope used is linked to the level of surfactant and it is desirable to use hydrotrope level to manage the viscosity in such compositions. The preferred hydrotropes are monopropylene glycol, glycerol, triethanolamines or mixtures thereof.

[0207] Builders

[0208] A composition of the invention may contain one or more builders. Builders enhance or maintain the cleaning efficiency of the surfactant, primarily by reducing water hardness. This is done either by sequestration or chelation (holding hardness minerals in solution), by precipitation (forming an insoluble substance), or by ion exchange (trading electrically charged particles).

[0209] Builders for use in the invention can be of the organic or inorganic type, or a mixture thereof.

[0210] Suitable inorganic builders include chlorides, hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, zeolites, and mixtures thereof. Specific examples of such materials include sodium and potassium chloride, sodium and potassium hydroxide, sodium and potassium carbonate, sodium and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof.

[0211] Suitable organic builders include the alkali metal (e.g. sodium and potassium) citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other examples are DEQUEST™, organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates. Examples of phosphate sequestrants include, but not limited to, 1-hydroxyethylidene-1 , 1-diphosphnic acid (HEDP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP), aminotris(methylenephosphonic acid) (ATMP), ethylenediaminetetra(methylenephosphonic acid) (EDTMP), tetramethylenediaminetetra(methylenephosphonic acid) (TDTMP), phosphonobutanetricarboxylic acid (PBTC) or mixtures thereof.

[0212] Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic / polymaleic acid copolymers and their salts, for example those sold by BASF under the name SOKALAN™. If utilized, the organic builder materials may comprise from about 0.5 percent to 20 wt percent, preferably from 1 wt percent to

[0213] 10 wt percent, of the composition. The preferred builder level is less than 10 wt percent and preferably less than 5 wt percent of the composition.

[0214] More preferably the liquid composition is a non-phosphate built formulation, i.e., contains less than 1 wt.% of phosphate. It is preferred that the composition comprises less than 0.5% wt. phosphonate based sequestrant and more preferably less than 0.1% wt. phosphonate based sequestrant. Most preferably, the composition is free from phosphonate based sequestrant.

[0215] The composition of the present invention preferably comprises the builders in an amount of from 0.01 to 10%, more preferably from 0.1 to 5%, even more preferably from 0.25 to 4% and most preferably from 0.5 to 2.5%, based on total weight of the composition and including all ranges subsumed therein.

[0216] Soil Release Polymers

[0217] Soil release polymers (SRP) help to improve the detachment of soils from fabric by modifying the fabric surface during washing. The adsorption of a SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.

[0218] The composition of the invention may comprise SRPs. SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped. The SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity. The weight average molecular weight (Mw) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000. SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol). The copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification / oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and / or PG, or a combination of DMT, EG and / or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0219] Other types of SRP for use in the invention include cellulosic derivatives such as hydroxyether cellulosic polymers, C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; polymers with poly(vinyl ester) hydrophobic segments such as graft copolymers of poly(vinyl ester), for example Ci-Ce vinyl esters (such as poly(vinyl acetate)) grafted onto polyalkylene oxide backbones; poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

[0220] Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (VI): in which R14 and R15 independently of one another are X-(OC2H4)q-(OC3H6)s ;in which X is C1-4 alkyl and preferably methyl; q is a number from 12 to 120, preferably from 40 to 50; s is a number from 1 to 10, preferably from 1 to 7; and i is a number from 4 to 9.

[0221] Because they are averages, q, s and i are not necessarily whole numbers for the polymer in bulk.

[0222] Mixtures of any of the above described materials may also be used.

[0223] The overall level of SRP, when included, may range from 0.1 to 10% by weight of the composition, depending on the level of polymer intended for use in the final composition and which is desirably from 0.3 to 7%, more preferably from 0.5 to 5%, based on total weight of the composition and including all ranges subsumed therein.

[0224] Suitable SRPs are described in greater detail in II. S. Patent Nos. 5,574,179; 4,956,447; 4,861 ,512; 4,702,857, WO 2007 / 079850 and WO2016 / 005271. If employed, SRPs will typically be incorporated into the composition herein in concentrations ranging from 0.01 to 10%, more preferably from 0.1 to 5% by weight of the composition.

[0225] Polymeric Cleaning Boosters

[0226] To further improve the environmental profile of the composition, it may be preferred in some cases to reduce the volume of composition dosed per wash-load and to add various highly weight efficient ingredients to the composition to boost cleaning performance. In addition to the soil release polymers of the invention described above, a composition of the invention will preferably contain one or more additional polymeric cleaning boosters such as anti-redeposition polymers.

[0227] Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil. Suitable anti-redeposition polymers for use in the invention include alkoxylated polyethyleneimines. Polyethyleneimines are materials composed of ethylene imine units - CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. Preferred alkoxylated polyethyleneimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (Mw). The polyethyleneimine backbone 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 alkoxy groups per modification. A preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.

[0228] Mixtures of any of the above described materials may also be used.

[0229] When included, a composition of the invention will preferably comprise from 0.025 to 8% by weight of one or more anti-redeposition polymers such as, for example, the alkoxylated polyethyleneimines which are described above.

[0230] Preservative

[0231] The composition preferably comprises a preservative or a mixture of preservatives. Preferably the preservative is selected from benzoic acid and salts thereof, alkylesters of p-hydroxybenzoic acid and salts thereof, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and salts thereof, most preferably sodium benzoate.

[0232] An alternatively preferred preservative is selected from sodium benzoate, phenoxyethanol, dehydroacetaic acid and mixtures thereof.

[0233] The preservative is present at 0.1 to 3wt%, preferably 0.3wt% to 1.5wt%. Weights are calculated for the protonated form where appropriate.

[0234] Preferably, the composition comprises sodium benzoate at from 0.1 to 3wt%, preferably 0.3wt% to 1.5wt% of the composition.

[0235] Preferably, the composition comprises phenoxyethanol at from 0.1 to 3wt%, preferably 0.3wt% to 1.5wt% of the composition.

[0236] Preferably, the composition comprises dehydroacetic acid at from 0.1 to 3wt%, preferably 0.3wt% to 1.5wt% of the composition.

[0237] Preferably, the composition comprises less than 0.1% wt. isothiazolinone-based preservative, more preferably less than 0.05% wt. Fluorescent Agent

[0238] It may be advantageous to include fluorescent agents (optical brightener) in the compositions. 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 0.005 to 2%, more preferably 0.01 to 0.5% by weight of the composition.

[0239] Preferred classes of fluorescent agents 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, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g.

[0240] Blankophor SN.

[0241] Preferred fluorescent agents 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' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1 , 3, 5-triazin-2- yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl. Most preferably the fluoescer is a di-styryl biphenyl compound, preferably sodium 2,2'-([1 ,1'- biphenyl]-4,4'-diylbis(ethene-2,1-diyl))dibenzenesulfonate (CAS-No 27344-41-8).

[0242] Anti-foam

[0243] The composition may also comprise an anti-foam. Anti-foam materials are well known in the art and include silicones, fatty acids, fatty alcohols and EO-PO block copolymers.

[0244] Preferably, where present, the fatty acid anti-foam is present at from 1.3 to 3.0% by weight of the composition, more preferably from 1.4 to 2.0% and most preferably from 1.6 to 1.65%.

[0245] Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula R12COOH, where R12is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.

[0246] Preferred examples of such materials include saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures may typically be derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow). The fatty acids may be present in the form of their sodium, potassium or ammonium salts and / or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.

[0247] Suitable fatty alcohols in the context of this invention include aliphatic alcohol of formula R13OH, where R13is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms.

[0248] Suitable EO-PO block copolymers in the context of this invention include a polymer with repeating units of ethylene oxide and propylene oxide and with hydrophile lipophile balance (HLB) value equal or smaller than 4.

[0249] Mixtures of any of the above described materials may also be used.

[0250] For formula accounting purposes, in the formulation, fatty acids and / or their salts (as defined above) are not included in the level of surfactant or in the level of builder.

[0251] Shading dyes

[0252] Shading dye may be used to improve the performance of the compositions. Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics. A further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.

[0253] Shading dyes are well known in the art of laundry liquid formulation.

[0254] Suitable and preferred classes of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes and dye conjugates. Preferred examples are Disperse Violet 28, Acid Violet 50, anthraquinone dyes covalently bound to ethoxylate or propoxylated polyethylene imine as described in WO2011 / 047987 and WO 2012 / 119859 alkoxylated mono-azo thiophenes, dye with CAS-No 72749-80-5, acid blue 59, and the phenazine dye selected from: wherein:

[0255] X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and, -OC2H5;

[0256] X4 is selected from: -H; -CH3; -C2H5; -OCH3; and, -OC2H5;

[0257] Y2is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and, C(O)OCH3. Alkoxylated thiophene dyes are discussed in WO2013 / 142495 and W02008 / 087497.

[0258] Shading dye can be used in the absence of fluorescent agents, but it is especially preferred to use a shading dye in combination with a fluorescent agent, for example in order to reduce yellowing due to chemical changes in adsorbed fluorescent agents.

[0259] The shading dye is preferably present is present in the composition in range from 0.0001 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.

[0260] A composition of the invention may comprise an enzyme. Examples of enzymes suitable for use in the composition include protease, lipase, amylase, mannanase, pectate lyase, cellulase, phospholipase, cutinase, peroxidase, oxidase or mixtures thereof. Most preferred are protease, amylase, cellulase or mixtures thereof.

[0261] The composition of the present invention preferably comprises from 0.00001 to 1% by weight of the enzyme, more preferably from 0.0001 to 0.5%, even more preferably from 0.0005 to 0.4%, still even more preferably from 0.001 to 0.3% and most preferably from 0.001 to 0.2%, based on total weight of the composition and including all ranges subsumed therein. Amounts of wt. % enzymes in the composition refer to wt. % of active protein levels.

[0262] Enzymes may be added in liquid, granular or in encapsulated form to the composition, but preferably are not encapsulated. The composition may also comprise enzyme stabilizers 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-formyl phenyl boronic acid, and the composition may be formulated as described in e.g.

[0263] WO 92 / 19709 and WO 92 / 19708. Other ingredients

[0264] The composition may contain further optional ingredients to enhance performance and / or consumer acceptability. Examples of such ingredients include foam boosting agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anticorrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and / or opacifiers. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally, these optional ingredients are included individually at an amount of up to 5% based on total weight of the composition.

[0265] Packaging and dosing

[0266] Preferably the composition is a liguid detergent composition such as a liguid laundry composition or a liguid dishwash composition, more preferably the composition is a liguid laundry composition.

[0267] The composition of the invention may be supplied in multidose plastics packs with a top or bottom closure. A dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.

[0268] Preferably, the composition is stored in a moulded article. Preferably, such moulded article comprises post-consumer recycled material. The moulded article is preferably blow moulded. Blow moulding involves the formation of a parison or preform which is placed and clamped into the mould. Air is passed into the parison / preform to expand the parison / preform such that it expands to fill the space in the mould. Once the plastic has hardened sufficiently, the mould is de-coupled and the moulded article is removed.

[0269] Preferably, the weight ratio between PCR and any non-recycled material content in the moulded article is from 1:9 to 100:0 but this depends on the physical structure of the article. For example, the article may comprise additional features such as a shrink-wrap outer skin, a cap, a pump assembly all of which may not comprise any PCR.

[0270] Preferably, the moulded article comprises additives to improve the performance of the article. Examples include HDPE, LLDPE and LLDP.

[0271] For example, where the article comprises a monolayer it is preferred that the weight ratio between the additive (for example HDPE and / or LLDPE and / or LDPE) and the PCR in the blow moulded article monolayer is from 5:95 to 30:70. However, where a multilayer article is provided and which only one layer comprises additive and PCR it is preferred that the weight ratio between the additive and the PCR in the individual layer is from 1:99 to 30:1 but the total proportion of additive in the article as a whole will depend on the weight ratio between the additive with PCR layer and any other layer used.

[0272] Typical additional layers may include PCR or virgin polyethylene as desired. For example, where an improved aesthetic is required the outer layer may comprise virgin polymer whereas the inner layer may comprise HDPE and / or LLDPE and / or LDPE with the PCR.

[0273] It is also of course possible that other materials are included with the HDPE / PCR such that in one layer the additive / PCR constitutes from 70 to 100% by weight of the layer and more preferably from 95 to 100% of the layer.

[0274] Preferably the outer and / or inner layer comprises a colourant masterbatch. More preferably, the outer layer comprises a colourant masterbatch. By “colourant masterbatch” it is a meant a mixture in which pigments are dispersed at high concentration in a carrier material. The colorant masterbatch is used to impart colour to the article.

[0275] The carrier may be a biobased plastic or a petroleum-based plastic, or a biobased oil or a petroleum-based oil or made of post-consumer resin (PCR).

[0276] Nonlimiting examples of the carrier include bio-derived or oil derived polyethylene (e.g, LLDPE, LDPE, HDPE), bio-derived oil (e.g., olive oil, rapeseed oil, peanut oil), petroleum-derived oil, recycled oil, bio-derived or petroleum derived polyethylene terephthalate, polypropylene, recycled high density polyethylene (rHDPE), recycled low density polyethylene (rLDPE). Preferably the carrier is recycled high density polyethylene (rHDPE) or recycled low density polyethylene (rLDPE).

[0277] When it is desired that all the layers are made of 100% of PCR, the carrier is also preferably selected from PCR. Similarly, when it is desired that a layer has a 100% of a specific PCR, the carrier is preferably selected from the same PCR.

[0278] The pigment, when present, of the masterbatch is a NIR detectable pigment. Carbon black is not preferred in the scope of the present invention. The NIR detectable pigment is preferably black. The pigment is typically made of a combination of known colours. By consumer acceptable black, it may be defined as the colour measured using a reflectometer and expressed as the CIE L*a*b* values and the values of L being less than 25, preferably less than 23, more preferably less than 20, even more preferably less than 15, still more preferably less than 12 or even less than 10, the values of a being in the ranges of -5 to 5, preferably -2 to 3, more preferably 0 to 2 and the values of b being in the ranges of -10 and 10, preferably -8 to 5.

[0279] By NIR detectable pigment is meant detectable by Near Infrared (NIR) spectroscopy.

[0280] The pigment of the carrier may include, for example, an inorganic pigment, an organic pigment, a polymeric resin, or a mixture thereof.

[0281] Optionally, the colourant masterbatch can further include one or more additives. Nonlimiting examples of additives include slip agents, UV absorbers, nucleating agents, UV stabilizers, heat stabilizers, clarifying agents, fillers, brighteners, process aids, perfumes, flavors, and a mixture thereof.

[0282] Such NIR detectable pigments are known in the art and are provided by various suppliers such as Clariant, globally and Colourtone Masterbatch Ltd. in Europe.

[0283] The moulded article according to the invention is preferably a container, e.g. for a bottle; in particular the article according to the invention is a non-food grade container.

[0284] Alternatively, the composition of the invention may be packaged as unit doses in polymeric film soluble in the wash water. The unit dose composition of the invention is contained within a pouch formed by a water dissoluble film. Preferably, the pouch has from one to four compartments. More preferably, the pouch has three compartments. It is preferred that the pouch is a unit dose of product and may be from 10 to 50 g in weight to represent a unit dose.

[0285] Compositions were prepared as shown in table 1. All ingredients are expressed by weight percent of the total composition, and as level of active ingredients.

[0286] Compositions having various ratios of bacterial cellulose to copolymer were freshly prepared and stored at 45°C. After 4 weeks, the appearances of the compositions were assessed qualitatively. A determination of whether the composition is acceptable was conducted.

[0287] “Acceptable” according to the present invention, means an appearance of the composition in which all the phases are mixed homogeneously and there is no phase separation or precipitation.

[0288] Table 1 a. A copolymer of methacrylic acid and methyl acrylate under the trade name DX-SF-2 from Guangzhou

[0289] DX Chemical Co., Ltd b. Bacterial cellulose under the trade name CELLULON™ R-25 from CP Kelco. It can be seen from table 1 that samples 1 to 3 showed improved stability compared to comparative samples A and B.

Claims

CLAIMS1. A liquid composition comprising:(a) from 0.0001 to 5% by weight of a bacterial cellulose; and(b) from 0.01 to 10% by weight of a copolymer polymerized from monomers comprising:(i) at least one ethylenically unsaturated carboxylic acid; and(ii) at least one C1-C5 alkyl ester and / or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid; wherein the bacterial cellulose and the copolymer are present in a weight ratio of from 1:20 to 10:1.

2. The composition according to claim 1 , wherein the ethylenically unsaturated carboxylic acid comprises acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid (anhydride), fumaric acid, crotonic acid, aconitic acid, citraconic acid or mixtures thereof, preferably the ethylenically unsaturated carboxylic acid comprises acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid (anhydride), or mixtures thereof.

3. The composition according to claim 1 or claim 2, wherein the C1-C5 alkyl ester and / or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid comprises methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, iso-amyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth) acrylate or mixtures thereof, preferably, the C1-C5 alkyl ester and / or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid comprises methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isopropyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or mixtures thereof.

4. The composition according to any of the preceding claims, wherein the ethylenically unsaturated carboxylic acid is present in an amount from 20 to 99%, more preferably from 40 to 90% by weight of the total monomer content of the copolymer.

5. The composition according to any of the preceding claims, wherein the C1-C5 alkyl ester and / or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid is present in an amount from 1 to 80%, more preferably from 10 to 60% by weight of the total monomer content of the copolymer.

6. The composition according to any of the preceding claims, wherein the copolymer is a copolymer of (meth)acrylic acid and C1-C2 alkyl (meth) acrylate, preferably a copolymer of methacrylic acid and methyl acrylate.

7. The composition according to any of the preceding claims, wherein the composition comprises from 0.1 to 7% by weight of the copolymer, preferably from 0.5 to 6%.

8. The composition according to any of the preceding claims, wherein the copolymer has a weight average molecular weight of from 500,000 g / mol to 20,000,000 g / mol, preferably from 1000,000 g / mol to 18,000,000 g / mol, the weight average molecular weight is determined by SEC (Size Exclusion Chromatography) analysis using absolute carlibration and polymethyl methacrylate is used for calibration.

9. The composition according to any of the preceding claims, wherein the bacterial cellulose comprises a cellulose produced by fermentation of a bacteria of the genus Acetobacter.

10. The composition according to any of the preceding claims, wherein the composition comprises from 0.001 to 3% by weight of the bacterial cellulose, preferably from 0.005 to 2%.

11. The composition according to any of the preceding claims, wherein the bacterial cellulose and the copolymer are present in a weight ratio of from 1 :15 to 8:1 , preferably from 1:12 to 5:1.

12. The composition according to any of the preceding claims, wherein the composition further comprises perfume microcapsules.

13. The composition according to any of the preceding claims, wherein the composition is a detergent composition, preferably a laundry detergent composition.

14. The composition according to any of the preceding claims, wherein the composition is in a unit dose format.

15. A method for forming a liquid detergent composition or a wash liquor by dispensing a dose of the composition according to any of the preceding claims in water.

Images