Cleansing composition comprising gelled polysaccharide

Abstract

A structured cleansing composition comprising a) from 0.1 to 40 wt % of a non-sulphate containing anionic surfactant comprising i) an amino acid head group; ii) an alkyl tail with a carbon-carbon chain length of from C6 to C22, b) from 0.15 to 4 wt % of a polysaccharide selected from the group consisting of agar, agarose, agaropectin and mixtures thereof; and c) an oil; wherein the polysaccharide is in the form of gel particles; wherein the composition has viscosity in the range of from 1,000 to 50,000 mPa.s, preferably from 1,000 to 25,000, more preferably from 2,000 to 25,000 mPa.s, even more preferably from 2,100 to 15,000 mPa.s, when measured at 25 degrees C and 4s-1, using sandblasted 40mm parallel plates, on a Wingspan rheometer (TA instruments); and wherein the composition comprises no added salt.

Description

[0001] CLEANSING COMPOSITION

[0002] Field of the Invention

[0003] The present invention relates to cleansing compositions, comprising a fluid gel phase and nonsulphate containing surfactants. The compositions have particular application in personal care cleansing.

[0004] Background of the Invention

[0005] Consumers desire home and personal cleaning formulations that have an acceptable, and stable, viscosity so that the product can, for example, be applied in a controlled manner and readily spread in use. Such compositions are sometimes referred to as “structured”.

[0006] Microstructure and rheology are important factors in consumer acceptance as well as product performance. Microstructure can impact rheological properties such as composition viscosity and viscosity-building characteristics and may also contribute to composition stability.

[0007] When sulfate surfactants are eliminated, developing a microstructure that results in desirable rheological properties can be challenging, particularly in the case of compositions which employ low surfactant concentrations; additionally, building the viscosity of such compositions by the addition of a simple salt can be problematic. Glutamate based formulations are particularly known to be very poor at building viscosity. High salt levels have been found to be inadequate in building viscosity in such formulations. A combination of salt with other surfactants to has been found necessary to build viscosity.

[0008] Alternatives to traditional sulphate-based surfactants are increasingly in demand for use in home and personal cleansing formulations. “Sulphate free” cleaning surfactants have provided one such alternative and can be used with traditional co-surfactants. However, such surfactant systems have either proven difficulty to thicken and have limited solubility or limited pH window for use. Use of higher levels of salt and of polymeric thickeners result in cost and processing issues and do not always overcome the issues faced. It has thus been necessary to employ narrow ratios of anionic surfactant to co-surfactant, with higher proportions of the co-surfactant in order to boost viscosity. Such restrictions on formulation space are clearly limiting to product development and choice. There is much interest in alternatives to traditional silicone conditioning agents. Oils such as triglycerides or hydrocarbon oil droplets are natural alternatives. However, worm micelle structured isotropic liquids are prone to catastrophic viscosity failure on incorporation of oils.

[0009] There is a need for sulphate free cleansing compositions, suitable for hair, skin and scalp, having desirable rheological properties, that are able to incorporate oil even at relatively low surfactant concentrations.

[0010] W002 / 36086 (Unilever) describes a composition which has a thickened fluid form comprising: (i) a first (shear gel) phase comprising at least one polymer which is capable of forming a gel, which polymer is present in the composition as a shear gel (i.e. , a multiplicity of separate gel particles which have been formed by subjecting the polymer to shear while gel formation takes place); and (ii) a second (entrapped) phase which is in the form of particles or droplets comprising a hair benefit agent, wherein at least some of the particles or droplets are entrapped in at least a proportion of the gel particles of the first (shear gel) phase.

[0011] WO99 / 51193 (Unilever) describes a hair treatment composition which has a thickened fluid form comprising: (i) a first (shear gel) phase comprising at least one naturally derived polymer which is capable of forming a reversible gel, which polymer is present in the composition as a shear gel (i. e., a multiplicity of separate gel particles which have been formed by subjecting the polymer to shear while gel formation takes place), and (ii) a second (suspended) phase suspended therein.

[0012] US2021 / 0401716 discloses shampoo compositions comprising thickeners such as guar based thickeners, in combination with sulphate-free surfactants including acyl taurates, acyl glutamates, acyl isethionates, salts thereof, and mixtures thereof and squalane.

[0013] We have now found that a composition, comprising a sheared gel particle phase and nonsulphate containing amino acid based surfactants, can be used with or without a co-surfactant, it can contain oil very successfully, whilst maintaining excellent viscosity and stability characteristics.

[0014] Definition of the Invention

[0015] Accordingly, and in a first aspect there is provided a structured cleansing composition comprising: a) from 0.1 to 40 wt % of a non-sulphate containing anionic surfactant comprising i) an amino acid head group derived from an amino acid; ii) an alkyl tail with a carbon-carbon chain length of from C6 to C22; b) from 0.15 to 4, preferably from 0.4 to 4 wt %, most preferably 0.5 to 3 wt %, of a polysaccharide selected from the group consisting of agar, agarose, agaropectin and mixtures thereof; c) an oil; wherein the polysaccharide is in the form of gel particles; wherein the composition has viscosity in the range of from 1 ,000 to 50,000 mPa.s, preferably from 1 ,000 to 25,000, more preferably from 2,000 to 25,000 mPa.s, even more preferably from 2,100 to 15,000 mPa.s, when measured at 25 degrees C and 4s-7, using sandblasted 40mm parallel plates, on a Wingspan rheometer (TA instruments).

[0016] Detailed Description of the Invention

[0017] The anionic surfactant (a)

[0018] The anionic surfactant is a non-sulphate containing surfactant selected from amino acid based anionic surfactants, which comprise: i) an anionic head group derived from an amino acid; and ii) a hydrocarbon tail having from 6 to 22, preferably 8 to 18, more preferably 10 to 16 carbon atoms and mixtures thereof.

[0019] The hydrocarbon tail may be saturated or unsaturated

[0020] The anionic surfactant may include n-acyl amino acids, n-alkyl amino acid surfactants and mixtures thereof.

[0021] The most common cation associated with the acyl amino acid can be sodium or potassium. Alternatively, the cation can be an organic salt such as triethanolamine (TEA) or a metal salt.

[0022] Non-limiting examples of useful amino acids include those of the general formula (I): Formula I wherein Ri R2, or R3 is individually selected from either any C12-C24 saturated or unsaturated tailed surfactant or a methyl group (CH3) or a hydrogen atom (H), and X is COO' or SOs'.

[0023] The first anionic surfactant is preferably selected from alaninates, argininates, aspartates, glycinates, isoleucinates, leucinates, lysinates, phenylalaninates, serinates, tyrosinates, valinates, sarcosinates, threoninates, prolinates, glutamates, and taurates.

[0024] In a preferred embodiment the first anionic surfactant is selected from a taurate, a glutamate, a sarcosinate and mixtures thereof. The taurates may be defined by Formula II; the glutamate by Formula III; the sarcosinate by Formula IV:

[0025] Formula II where R1 is a C12-C24, saturated or unsaturated, linear or branched hydrocarbon chain; where R is a C12-C24, saturated or unsaturated, linear or branched hydrocarbon chain; Formula IV where R is a C12-C24, saturated or unsaturated, linear or branched hydrocarbon chain.

[0026] The amount of the anionic surfactant in formulations according to the invention can be between 0.1 and 40 wt% of the total composition more preferably between 0.5 and 30 wt %, still more preferably between 0.5 and 20 wt % most preferably between 2 and 20 wt %.

[0027] The

[0028] The compositions of the invention comprise from 0.15 to 4 wt %, preferably from 0.4 to 4 wt %, most preferably 0.5 to 3 wt %, of a polysaccharide, which is capable of being formed into gel particles, selected from the group consisting of agar, agarose, agaropectin and mixtures thereof.

[0029] One polysaccharide which may be used is agar. The term agar covers a family of polymers containing agarose and / or agaropectin, i. e., polymers with backbone structure containing alternating 1,3-D-galactose and 1,4-L-galactose residues.

[0030] Agarose is a linear polysaccharide, basically made up from P-1,3 galactose residues alternating with oc-1,4 galactose residues. The latter are present as the 3,6 anhydride and are the L- enantiomer.

[0031] Agaropectin likewise has -1,3 galactose residues alternating with oc-1,4 galactose residues, but includes sulphate, pyruvate and / or glucuronic acid residues.

[0032] Agar is extracted from certain species of red seaweed, principally in Japan. A description of agar is given by Tetsujiro Matsuhashi as Chapter 1 in "Food Gels", edited by Peter Harris, Elsevier, 1990.

[0033] The polysaccharide is present in an amount of from 0.15 to 4 wt %, preferably from 0.4 to 4 wt %, most preferably 0.5 to 3 wt %, by weight of the total composition. In general, the viscosity of a shear gel composition in accordance with this invention will increase with the concentration of polymer contained in it.

[0034] Viscosity will also be affected by the size and shape of the gel particles, which in turn is affected by the conditions used to apply shear during cooling. In general, combinations of variable cooling rates and different rotor speeds during shearing permits the optimisation of particle dispersion smoothness, suspending properties and viscosity, possibly because gel particle shapes can vary between spherical and filamentous forms.

[0035] Preferably the composition comprises no additional salt other than that present as carry over in the raw materials. The salt level of any raw material is typically less than 5 wt % by weight of the raw material.

[0036] The Oil (c)

[0037] It is advantageous to include insoluble hydrophobic oils, in the cleansing composition of the invention. These may be deposited onto the skin or hair to provide a conditioning effect. The oil is not suspended within, or not entrapped within the gel phase, that is to say the oil is not added during the molten agar phase so is no way it can be entrapped.

[0038] Suitable examples include, hydrocarbon oils and waxes, mono-, di- and tri-fatty acid esters of glycerol such as natural oils, fatty acid esters, fatty acid polymers, fatty acids, fatty alcohols and blends thereof.

[0039] Hydrocarbon oils suitable for use in the present invention may be mineral oils, petroleum jelly and paraffin waxes are petrochemically-derived substances usually comprising alkanes and cycloalkanes of varying molecular weights, typically from 15 to 40 carbons. Other suitable examples include squalene, sourced for instance from olive or from bio-fermentation of cane sugar, and its hydrogenated equivalent squalane. The polyolefins may be chosen from hydrogenated and nonhydrogenated polybutene, such as hydrogenated and nonhydrogenated polyisobutene. An additional example of poly-alpha-olefins include hydrogenated and nonhydrogenated polydecene poly-alpha-olefins.

[0040] Suitable triglyceride oils are those mainly composed of triglycerides comprising fatty acid ester groups from 8 to 24 carbons preferably 10 to 22 carbons. The fatty acids may be saturated or unsaturated. The fatty acids may be linear or branched in nature. Triglyceride oils may preferably be selected from sunflower oil (for example sunflower seed oil), maize, castor, soyabean, palm stearin, avocado, jojoba, gourd, grapeseed, sesame, hazelnut, coconut, shea tree nut, cocoa bean, cocoa butter, olive, amla fruit, algae oil and other oils obtained by bio-fermentation. Most preferably, triglyceride oils are selected from cocoa butter, palm stearin, sunflower oil, soyabean oil and coconut oil.

[0041] Fatty acid esters, fatty acids and fatty alcohols may be typically synthesized from the abovementioned triglyceride oils. Other examples may include polyestolide esters of hydroxy fatty acids, such as ricinoleic acid or hydroxystearic acid. A preferred plant based ester is a BioEstolide™ available from numerous suppliers including Biosynthetic Technologies. For example, Acetyl Ethylhexyl Polyhydroxystearate Emulsion(<500nm)" or "Acetyl IsoOctyl Polyricinoleate Emulsion (<500nm)".

[0042] Preferred oils are selected from silicone, triester oils, mineral oil, coconut oil, sunflower oil, emulsified silicone, non-emulsified silicone, squalane, shea butter and a plant-based ester of a hydroxy fatty acid, more preferably silicone, triester oils, mineral oil, coconut oil, sunflower oil, emulsified silicone, non-emulsified silicone, shea butter and a plant-based ester of a hydroxy fatty acid.

[0043] The oils may be incorporated into the formulation in neat form (as a free oil) or as a pre-formed emulsion, or a combination thereof.

[0044] Optional amphoteric and / or zwitterionic co-surfactant

[0045] The surfactant composition of the invention may include a co-surfactant, which is an amphoteric or zwitterionic surfactant. Preferably, the amphoteric and / or zwitterionic surfactant is selected from an alkyl betaine, an alkyl amphoacetate, an alkyl sultaine, a glucotaine, and mixtures thereof.

[0046] The level of co-surfactant is generally from 0.5 to 20 wt %, preferably from 1 to 15 wt %, more preferably most preferably from 1 .5 to 10 % by weight based on the total weight of surfactant present in the composition and based on 100 % active level.

[0047] Preferably the co-surfactant is an amphoteric surfactant. Suitable amphoteric surfactants are betaines, such as those having the general formula R(CH3)2N+CH2COO', where R is an alkyl or alkylamidoalkyl group, the alkyl group preferably having from 6 to 22 carbon atoms, more preferably from 8 to 22 carbon atoms, even more preferably form 8 to 18 carbon atoms, still more preferably from 10 to 18 carbon atoms, most preferably from 12 to 18 carbon atoms, and mixtures thereof.

[0048] Betaine Surfactant

[0049] Betaines that are suitable for use in the present invention can be represented by the general formula:

[0050] R10[C(O)NH-(CH2)y]z -N+(R11)(R12) CH2CO2’ (A) where R10is C6 to C30, more particularly C6 to C24 alkyl, z is 0 or 1 , R11and R12are independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms, and y is 2 or 3; and salts thereof. In one embodiment, at half of the groups R10are C8 to C18 alkyl. In another embodiment, at least half of the groups R10are C 10 to C14 alkyl. R10may be saturated or unsaturated. In one embodiment, R10is derived from coconut oil or palm kernel oil. In one embodiment R11and R12are methyl.

[0051] The formula (IV) betaines include the simple betaines:

[0052] R10-N+(R11)(R12) CH2CO2- (Aa) where R10, R11, and R12are as described above, and the amidobetaines:

[0053] R10C(O)NH-(CH2)y-N+(R11)(R12) CH2CO3- (Ab) where R10, R11, R12, and y are as described above.

[0054] Particularly suitable betaines are oleyl betaine, caprylamidopropyl betaine, lauramidopropyl betaine, isostearylamidopropyl betaine, and cocoamidopropyl betaine and mixtures thereof.

[0055] Zwitterionic surfactants

[0056] Zwitterionic surfactants that are suitable for use in the present invention, include at least one acid group. Such an acid group may be a carboxylic or a sulphonic acid group. They may include quaternary nitrogen, and therefore, can be quaternary amino acids. They should generally include an alkyl or alkenyl group with from 6 to 22 carbon atoms, more preferably from 8 to 22 carbon atoms, even more preferably from 8 to 18 carbon atoms, still more preferably from 10 to 18 carbon atoms, most preferably from 12 to 18 carbon atoms, and mixtures thereof. These surfactants will generally comply with an overall structural formula:

[0057] R6-[-C(O)-NH(CH2)q-]r-N+-(R7-)(R8)A— B, where R7is alkyl or alkenyl of from 6 to 22, preferably 8 to 22, more preferably 8 to 18 carbon atoms, still more preferably from 10 to 18 carbon atoms , even more preferably 12 to 18 carbon atoms; R7and R8are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms; q is 2 to 4; r is 0 to 1 ; A is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl, and B is --CO2-- or --SO3--.

[0058] Amphoacetates

[0059] Zwitterionic surfactants suitable for use in the invention include sodium acyl amphoacetates, sodium acyl amphopropionates, disodium acyl amphodiacetates and disodium acyl amphodipropionates where the acyl (i.e. , alkanoyl group) can comprise a alkyl portion with from 6 to 22 carbon atoms, more preferably from 8 to 22 carbon atoms, even more preferably form 8 to 18 carbon atoms, still more preferably from 10 to 18 carbon atoms, most preferably from 12 to 18 carbon atoms, and mixtures thereof. Illustrative examples of the amphoteric surfactants suitable for use include sodium lauroamphoacetate, sodium cocoamphoacetate, sodium lauroamphoacetate, sodium cocoamphoacetate and mixtures thereof.

[0060] Sultaines

[0061] Non-limiting examples of sultaine surfactants are alkyl hydroxysultaines conforming to the general formula (B) (Formula B)

[0062] Where R is a saturated or unsaturated alkyl chain having 8 to 18 carbon atoms.

[0063] Such surfactants are made commercially available from suppliers like Verdant Specialty Chemicals, and it is within the scope of the invention to employ mixtures of the aforementioned surfactants.

[0064] Optional cationic polymer

[0065] The use of cationic polymers to deliver conditioning benefits either alone or as a means of delivery for other benefit agents (for example silicones, fragrance encaps, oils and scalp actives) is well known in the art. Several review articles are available in the scientific literature including G.Luengo et al, Advances in Colloid and Interface Science, volume 222, pages 461- 487 and M.Gradzielski, Langmuir, volume 38, pages 13330-13343.

[0066] Cationic polymers are often defined by their molecular weight and charge density. Molecular weight used herein refers to the weight average molecular weight. Molecular weight is measured using an industry standard method, gel permeation chromatography (GPC). Charge density can be measured using the Kjeldahl method.

[0067] Preferred cationic polymers are selected from cationically modified polysaccharides, cationic polymers designated by the CTFA as Polyquaternium -X where X is an integer, homopolymers or copolymers comprising an acrylamidopropyltrimonium moiety, and mixtures thereof.

[0068] Examples of cationic polymers suitable for use in the present invention include but are not limited to:

[0069] (a) Cationically modified polysaccharides including those obtained from guar gum, tara gum, inulin, locust bean gum, fenugreek gum, hydroxyethyl cellulose, dextran, konjac root, starch, cassia gum and chitosan. They can include cationically modified polygalactomannans, polyglucomannans, polygalactoglucomannans and mixtures thereof.

[0070] (b) Cationic polymers designated by the CTFA as Polyquaternium -X where X is an integer examples of which include, but are not limited to Polyquaternium-6, Polyquaternium 7, Polyquaternium-10, Polyquaternium-11 and Polyquaternium-67 and mixtures thereof

[0071] (c) Cationic polymers that are homopolymers or copolymers comprising an acrylamidopropyltrimonium moiety

[0072] (d) In some instances, the cleansing compositions include one or more cationic conditioning polymers selected from a,b or c. In one embodiment, the cationic conditioning polymer(s) are selected from a and b OR a and c or mixtures thereof. In another preferred embodiment, the mixture of cationic conditioning polymers are selected from either a) and or b) for example cationic guar and Polyquaternium-10

[0073] The cationic guar polymer may be a guar hydroxypropyltrimonium chloride. Specific examples of guar hydroxypropyltrimonium chlorides include the Jaguar series commercially available from Syensqo (for example Jaguar ® C13S) or Ashland Specialty Ingredients (for example n- hance™ cationic polymers)

[0074] The cationic cellulose polymer may be a cationic hydroxyethyl cellulose such as polyquaternium-10 commercially available from Dow (for example the JR, LR and KG series of polymers). The cationic cellulose polymer may also be a polyquaternium-67 commercially available from Dow (for example softCAT polymers or the SL and SK series) or a mixture thereof.

[0075] Cationic starch polymers may be a starch hydroxypropyltrimonium chloride derived from corn, potato or tapioca starch.

[0076] The cationic dextran polymer may be a dextran hydroxypropyltrimonium chloride such as DEXCARETMCD-1 commercially available from Dow

[0077] Cationic homo- or co-polymers consisting of an acrylamidopropyl trimonium moiety may be exemplified by N-DurHance™ AA2000 or N-Hance SP100 both available commercially from Ashland Specialty Ingredients. Other examples include Salcare ® SC-60 and Salcare® SC-30 (a polyquaternium-6) available commercially from BASF.

[0078] The nature of cationic conditioning polymers means that they have specific charge density and molecular weight values and these are often associated with particular grades of a polymer class for example polyquaternium-10 is available as Polymer J R30M (a high molecular weight, high charge density form) and LR30M (of lower molecular weight than JR30M but identical charge density).

[0079] Whilst not being limited by example preferred molecular weights for the cationic conditioning polymers in some embodiments of the invention are preferably between 1000 and 2,000,000 Daltons or from about 100,000 to around 1,500,000 Daltons.

[0080] The charge density of cationic conditioning polymers also varies and in some embodiments of the invention is preferably between 0.2 and 7meq / g

[0081] As efficacy of delivery from cationic polymers differs based upon polymer-surfactant interactions this list of cationic polymers includes some polymers which will have lower, or zero efficacy in particular embodiments of this invention whilst others on the list will work well in many embodiments of the invention. The choice of cationic polymer to pair with any particular embodiment of the invention will be within the remit of one skilled in the art. The cationic polymer is preferably selected from cationically modified polysaccharides, cationic polymers designated by the CTFA as Polyquaternium -X where X is an integer, homopolymers or copolymers comprising an acrylamidopropyltrimonium moiety, and mixtures thereof.

[0082] Optional benefit agent

[0083] A benefit agent may be used, that is preferably selected from a scalp agent, a silicone and a fibre benefit material.

[0084] Scalp agent

[0085] The hair care composition may comprise a scalp health agent to provide scalp benefits. This group of materials is varied and provides a wide range of benefits including moisturization, barrier improvement, anti-fungal, anti-microbial and anti-oxidant, anti-itch, sensates, and antidandruff.

[0086] The anti-dandruff agents can be selected from pyridinethione salts, zinc carbonate, hydroxy pyridines such as piroctone olamine, azoles such as ketoconazole or climbazole, selenium sulfide, particulate sulfur, hinokitiol, salicylic acid, and mixtures thereof.

[0087] The anti-microbial active can be selected from a group consisting of zinc pyrithione, copper pyrithione, coal tar, sulfur, charcoal, whitfield's ointment, castellani's paint, aluminium chloride, gentian violet, hydroxyl pyridine and wherein the hydroxyl pyridine may be piroctone olamine, octopirox (piroctone olamine), ciclopirox olamine, rilopirox, MEA-Hydroxyoctyloxypyridinone, strobilurins such as azoxystrobin and metal chelators such as 1 ,10-phenanthroline, undecylenic acid and its metal salts, potassium permanganate, selenium sulfide, sodium thiosulfate, propylene glycol, oil of bitter orange, urea preparations, griseofulvin, 8-hydroxyquinoline ciloquinol, thiobendazole, thiocarbamates, haloprogin, polyenes, hydroxypyridone, morpholine, benzylamine, allylamines (such as terbinafine), tea tree oil, clove leaf oil, coriander, palmarosa, berberine, thyme red, cinnamon oil, cinnamic aldehyde, citronellic acid, hinokitol, ichthyol pale, Sensiva SC-50, Elestab HP-100, azelaic acid, lyticase, iodopropynyl butylcarbamate (IPBC), isothiazalinones such as octyl isothiazalinone, and azoles, and mixtures thereof.

[0088] Other scalp health agents may include but are not limited to: niacinamide, glycerin, hydroxamic acid such as caprylhydroxamic acid and benzohydroxamic acid, glycine, alanine, vitamin E and F, caffeine, panthenol, glycols, glycolic acid, PCA, PEGs, erythritol, triclosan, lactates, hyaluronates, allantoin and other ureas, betaines, sorbitol, glutamates, xylitols, menthol, menthyl lactate, iso cyclomone, benzyl alcohol, natural extracts / oils including peppermint, spearmint, argan, jojoba and aloe.

[0089] Fibre benefit material

[0090] The compositions of the invention preferably comprise at least one fibre benefit material, to confer an increase in the Tg of the internal protein of the hair. The fibre benefit material may be selected from lactones, disaccharides, inorganic salt selected from sodium sulphate and ammonium carbonate, diacids and mixtures thereof, preferably selected from lactones, disaccharides, inorganic salts and mixtures thereof.

[0091] Preferably, the lactone is a delta lactone. More preferably the lactone is selected from gluconolactone±galactonolactone, glucuronolactone, galacturonolactone, gulonolactone, ribonolactone, saccharic acid lactone, pantoyllactone, glucoheptonolactone, mannonolactone, galactoheptonolactone and mixtures thereof. Most preferably, the lactone is gluconolactone. The total amount of lactone in compositions of the invention generally ranges from 0.01 to 20%, preferably from 0.01% to 2%, more preferably from 0.05 to 0.8% by total weight lactone based on the total weight of the composition.

[0092] Suitable disaccharides preferably comprise of pentose or hexose sugars, more preferably the disaccharide comprises of two hexose units. Particularly preferred are trehalose and cellobiose or mixtures thereof. Trehalose is the most preferred disaccharide. The level of disaccharides present in the total formulation from 0.001 to 8 wt% of the total composition, preferably from 0.005 wt% to 5 wt%, more preferably from 0.01 to 3 wt%, most preferably from 0.05 wt% to 2 wt%.

[0093] Preferred di-acids having the formula: HOOC-(CH2)n-COOH, where n is an integer from 2 to 8, more preferably where n equal to 2 or 4 (succinic acid and adipic acid respectively). Di-acids are best used at levels in the total formulation from 0.01 wt% to 5wt% of the total composition, more preferably at levels from 0.01wt% to 2wt%.

[0094] Where present, the weight ratio of di-acid to disaccharide is 1:10 to 20:1, more preferably 1 :5 to 5:1. In addition, acids are best used at di-acid:disaccharide molar ratios of between 0.1:1 and 10: 1 , preferably between 0.1:1 and 2: 1. A further preferred fibre benefit material is sodium gluconate. Preferably, sodium gluconate is used in combination with citric acid, for example as described in WO2021 / 069533A1.

[0095] Further preferred benefit agents include amino acids.

[0096] Silicones

[0097] The compositions of the invention may comprise emulsified droplets of a silicone conditioning agent, for enhancing conditioning performance.

[0098] The emulsified silicone is preferably selected from the group consisting of polydiorganosiloxanes, silicone gums, amino functional silicones and mixtures thereof.

[0099] Suitable silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes which have the CTFA designation dimethicone. Also suitable for use compositions of the invention (particularly shampoos and conditioners) are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. Also suitable for use in compositions of the invention are silicone gums having a slight degree of cross-linking, as are described for example in WO 96 / 31188.

[0100] The viscosity of the emulsified silicone itself (not the emulsion or the final hair conditioning composition) is typically at least 10,000 cst at 25 °C the viscosity of the silicone itself is preferably at least 60,000 cst, most preferably at least 500,000 cst, ideally at least 1 ,000,000 cst. Preferably the viscosity does not exceed 109cst for ease of formulation.

[0101] Emulsified silicones for use in the shampoo compositions of the invention will typically have a D90 silicone droplet size in the composition of less than 30, preferably less than 20, more preferably less than 10 micron, ideally from 0.01 to 1 micron. Silicone emulsions having an average silicone droplet size (D50) of 0.15 micron are generally termed microemulsions.

[0102] Silicone particle size may be measured by means of a laser light scattering technique, for example using a 2600D Particle Sizer from Malvern Instruments.

[0103] Examples of suitable pre-formed emulsions include Xiameter MEM 1785 and microemulsion DC2-1865 available from Dow Corning. These are emulsions / microemulsions of dimethiconol. Cross-linked silicone gums are also available in a pre-emulsified form, which is advantageous for ease of formulation.

[0104] A further preferred class of silicones for inclusion in shampoos and conditioners of the invention are amino functional silicones. By "amino functional silicone" is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. Examples of suitable amino functional silicones include: polysiloxanes having the CTFA designation "amodimethicone".

[0105] Specific examples of amino functional silicones suitable for use in the invention are the aminosilicone oils DC2-8220, DC2-8166 and DC2-8566 (all ex Dow Corning).

[0106] Suitable quaternary silicone polymers are described in EP-A-0 530 974. A preferred quaternary silicone polymer is K3474, ex Goldschmidt.

[0107] Also suitable are emulsions of amino functional silicone oils with non ionic and / or cationic surfactant.

[0108] Pre-formed emulsions of amino functional silicone are also available from suppliers of silicone oils such as Dow Corning and General Electric. Specific examples include DC939 Cationic Emulsion and the non-ionic emulsions DC2-7224, DC2-8467, DC2-8177 and DC2-8154 (all ex Dow Corning).

[0109] The total amount of silicone is preferably from 0.01 wt% to 10 %wt of the total composition more preferably from 0.1 wt% to 5 wt%, most preferably 0.5 wt% to 3 wt% is a suitable level.

[0110] £H

[0111] Amino acids are a well known class of surfactants however building viscosity via worm like micelles very difficult. The present invention enables a wide range of pH to be used with these sensitive surfactants, for the first time.

[0112] The composition may have a pH of from 3 to 9, preferably from 4 to 8. It is an advantage of the compositions of the present invention that they are effective across an unusually wide pH range. Other Ingredients

[0113] A composition of the invention may contain further optional ingredients to enhance performance and / or consumer acceptability. Examples of such ingredients include, for example, fragrance, dyes and pigments, pH adjusting agents (for examples organic acids, sodium hydroxide), pearlescers, opacifiers, preservatives, antimicrobials, structurants, solvents, feel modifying polymers. 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% (by weight based on the total weight of the composition).

[0114] The compositions for use in the invention preferably comprise a preservative. Preferred preservatives include sodium benzoate and caprylyl glycol. Another preferred preservative is methylchloroisothiazolinone I methylisothiazolinone (Kathon CG). A preservative may advantageously be used in combination with and EDTA salt such as disodium EDTA. Other suitable preservatives can be found in Annex V-preservatives list for cosmetic products Ell.

[0115] Where present, the preservative is preferably present in an amount of from 0.01 to 2 wt %, more preferably 0.01 to 1 wt %, most preferably 0.1 to 1 wt %, by total weight of the composition.

[0116] Preferably the composition further comprises appearance modifier preferably selected from mica, dyes, pigments, fluorescent agent and pearlescer.

[0117] Preferably the composition comprises a fragrance, which may be added as a free oil or encapsulate.

[0118] A multiplicity of separate gel particles are formed by subjecting the polymer to shear while gel formation takes place. Suitable routes for the preparation of the gel particles required for this invention are given in WO9951193.

[0119] Viscosity of the inventive compositions are affected by the size and shape of the gel particles, which in turn is affected by the conditions used to apply shear during cooling. In general, combinations of variable cooling rates and different rotor speeds during shearing permits the optimisation of particle dispersion smoothness, suspending properties and viscosity, possibly because gel particle shapes can vary between spherical and filamentous forms. Unless otherwise indicated, ratios, percentages, parts, and the like, referred to herein, are by weight.

[0120] Except where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and / or use are to be understood as modified by the word “about.”

[0121] It should be noted that in specifying any range of concentration or amount, any particular upper concentration can be associated with any particular lower concentration or amount as well as any subranges consumed therein. In that regard, it is noted that all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. examples were the method:

[0122] 1. Using a beaker on a hotplate (set to 95°C) with a magnetic stirrer (stirring at 300 rpm), water was heated to 95°C followed by the pre-dissolved preservatives (if used). Agar was then added and mixed until dissolved. The molten liquid was then transferred to a preheated ESCO-Labor process mixing unit (e.g. EL1pm ex ESCO-Labor AG) (90°C) and mixed for a few minutes using a wall scraper at 200rpm.

[0123] 2. The wall scraper speed was then lowered to 100rpm and cooling set to 35°C and was allowed to cool slowly (~1 degree / min) with stirring until the temp had plateaued.

[0124] 3. The cooling unit was switched back and the temperature set to below 25°C to make sure the agar / agarose had completely gone through the gelling point and stirred for 20mins

[0125] 4. Once gelled, the agar was heated to 40°C, at which point the surfactant(s) were added - vacuum switched on and the wall scraper lowered to 50rpm, mixing until homogeneous, followed by addition of any remaining ingredients

[0126] 5. After pH adjustment, the homogeniser was run for 3 mins at 1 ,500rpm

[0127] In the examples below, inventive compositions are denoted by the letter “A” and comparative compositions by the letter “B”. compositions 1A-4A in accordance with the invention and com com 1 B - 4B P0000789WC

[0128] 18

[0129] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions are given in Table 1.

[0130] Compositions 1A - 4A are in accordance with the invention, whilst 1 B - 4B are corresponding comparative examples.

[0131] Table 1 : Ingredients (wt %) of Compositions 1A - 4A in accordance with the invention and comparative compositions 1B - 4B

[0132] 10

[0133] Table 2: Viscosity Data of Compositions 1 A— 4A in accordance with the invention and comparative compositions 1 B - 4B. P0000789WQ

[0134] 19

[0135] Viscosity of the compositions in these examples was measured at 30 degrees C and 4s- 1, using sandblasted 40mm parallel plates, on a Wingspan rheometer (TA instruments).

[0136] The comparative examples, with and without oil, have very low viscosities.

[0137] 5 The agar in the inventive example is structuring the composition by forming a shear gel. For the first time, we also show this for compositions comprising oil.

[0138] Sodium cocoyl glutamate, used without added salt, does not thicken. In a traditional system, the addition of salt would enable the formation of worm-like micelles to create viscosity.

[0139] 10

[0140] Example 2: 10% active level 1 :1 (Glutamate: CAPB) ratio shampoo compositions 5A-8A in accordance with the invention and comparative compositions 5B - 8B

[0141] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions are given in Table 3.

[0142] P0000789WQ

[0143] 20

[0144] Table 3: Ingredients (wt %) of Compositions 5A - 8A in accordance with the invention and comparative compositions 5B - 8B.

[0145] 5 Formulations were made as follows: All ingredients were mixed to make a shampoo base, in the presence or absence of the agar shear gel component in accordance with the invention. Finally, the pH was adjusted with citric acid to adjust to 6.8 and the viscosity measured.

[0146] Table 4: Viscosity Data of Compositions 5A - 8A in accordance with the invention and

[0147] 10 comparative compositions 5B - SB- P0000789WQ

[0148] 21

[0149] Even with the addition of the co-surfactant, glutamate cannot thicken the composition.

[0150] Again, excellent thickening is achieved with oil in the inventive compositions.

[0151] Example 3: 10% active level 9:1 (Glutamate: CAPB) shampoo compositions 9A-12A in 5 accordance with the invention and comparative compositions 9B - 12B

[0152] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions are given in Table 5.

[0153] Table 5: Ingredients (wt %) of Compositions 9A - 12A in accordance with the invention 10 and comparative compositions 9B - 12B . P0000789WQ

[0154] 22

[0155] Table 6: Viscosity Data of Compositions 9A - 12A in accordance with the invention and comparative compositions 9B - 12B.

[0156] 5 An anionic rich ratio does not improve viscosity of the comparative compositions. Again the compositions in accordance with the invention provide excellent viscosity.

[0157] Example 4: 10% active level 1 :9 (Glutamate: CAPB) shampoo compositions 13A-16A in accordance with the invention and comparative compositions 13B - 16B

[0158] 10

[0159] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions are given in Table 7.

[0160] P0000789WQ

[0161] 23

[0162] Table 7: Ingredients (wt %) of Compositions 13A - 16A in accordance with the invention and comparative compositions 13B - 16B ■

[0163] P0000789WQ

[0164] 24

[0165] Table 8: Viscosity Data of Compositions 13A - 16A in accordance with the invention and comparative compositions 13B - 16B.

[0166] 5 Altering the ratio of surfactants to favour an amphoteric rich system is normally a good way to increase viscosity. The comparative examples fail to thicken, whilst the inventive examples provide excellent viscosity.

[0167] Example 5: 10% active level 1 :1 (Glutamate: LHS) ratio shampoo compositions 17A-20A in 10 accordance with the invention and comparative compositions 17B - 20B

[0168] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions are given in Table 9.

[0169] P0000789WQ

[0170] 25

[0171] Table 9: Ingredients (wt %) of Compositions 17A - 20A in accordance with the invention and comparative compositions 17B - 20B .

[0172] Table 10: Viscosity Data of Compositions 17A - 20A in accordance with the invention and comparative compositions 17B - 20B.

[0173] 10 The addition of hydroxysultaine as an alternative co-surfactant does not enable the comparative examples to thicken. P0000789WQ

[0174] 26

[0175] Example 6: 10% active level 9:1 (Glutamate: LHS) shampoo compositions 21A-24A in accordance with the invention and comparative compositions 21 B - 24B

[0176] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions are given in Table 11.

[0177] Table 11 : Ingredients (wt %) of Compositions 21 A - 24A in accordance with the invention and comparative compositions 21 B - 24B .

[0178] P0000789WQ

[0179] 27

[0180] Table 12: Viscosity Data of Compositions 21 A - 24A in accordance with the invention and comparative compositions 21 B - 24B .

[0181] 5 The addition of hydroxysultaine and an anionic rich system does not enable the comparative examples to thicken. The compositions of the invention thicken well.

[0182] Example 7: 10% active level 1 :9 (Glutamate: LHS) shampoo compositions 25A-28A in accordance with the invention and comparative compositions 25B - 28B

[0183] 10 Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions are given in Table 13 below.

[0184] P0000789WQ

[0185] 28

[0186] Table 13: Ingredients (wt %) of Compositions 25A - 28A in accordance with the invention and comparative compositions 25B - 28B.

[0187] Table 14: Viscosity Data of Compositions 25A - 28A in accordance with the invention and comparative compositions 25B - 28B The addition of hydroxysultaine and an amphoteric rich system does not enable the comparative examples to thicken. The compositions of the invention thicken well.

[0188] Example 8: Shampoo formulations S1 - S4, in accordance with the invention, comprising varying amounts of sodium cocoyl glutamate

[0189] The following Table illustrates further shampoo formulations in accordance with the invention, based on different amounts of sodium cocoyl glutamate surfactant, that were prepared as above and characterised for viscosity.

[0190] Table 15: Viscosities of compositons S1 - S4

[0191] It will be seen that viscous formulations can be prepared at a wide range of concentrations.

[0192] Example 9: Storage stability of a shampoo formulation S5 according to the invention

[0193] A formulation of the invention was made according to the details below and a sample placed on storage at 5°C, 25°C and 45°C with viscosity measurements taken over 12 weeks.

[0194] P0000789WQ

[0195] 30

[0196] Table 16: Composition of inventive shampoo S5

[0197] Table 17: Viscosity of S5 after storage at 5, 25 and 45 degrees C after 0 — 12 weeks

[0198] This formulation is stable for 12 weeks at all temperatures, in the presence of oil and the mica remained suspended throughout the test.

[0199] 10 Example 10: Shampoo compositions T1A-T4A in accordance with the invention and comparative compositions T1B -T4B

[0200] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions are given in Table 18. P0000789WQ

[0201] 31

[0202] Table 18: Ingredients (wt %) of Compositions T1A-T4A in accordance with the invention and comparative compositions T1 B -T4B

[0203] Table 19: Viscosity Data of Compositions T1A-T4A in accordance with the invention and comparative compositions T1 B -T4B Example 11 : Shampoo formulations, S6 - S15 in accordance with the invention, comprising varying amounts of Sodium Methyl Lauryl Taurate, co-surfactant and oil

[0204] The following Table illustrates further shampoo formulations in accordance with the invention, based on different amounts of sodium cocoyl glutamate surfactant, that were prepared as above and characterised for viscosity as given in the table below.

[0205] Table 20: Composition and viscosity of compositions S6 - S15 in accordance with the invention comprising sodium cocoyl glutamate

[0206] Example 12: Shampoo formulation, S16, in accordance with the invention, comprising Piroctone olamine and coconut oil Other benefit agents can also be included in compositions of the invention, for example a scalp benefit agent such as piroctone olamine as shown in the table below: P0000789WQ

[0207] 33

[0208] Table 21 : Composition of S16 in accordance with the invention

[0209] Table 22: Viscosity of composition S16 at fresh and after 1 week storage at 50 degrees C

[0210] Example 13: 6% active level shampoo compositions S1A- S4A in accordance with the invention and comparative compositions S1 B - S4B

[0211] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions 10 are given in Table 23.

[0212] P0000789WQ

[0213] 34

[0214] Table 23: Ingredients (wt %) of Compositions S1A - A4A in accordance with the invention and comparative compositions S1B - S4B

[0215] Table 24: Viscosity Data of Compositions S1A - A4A in accordance with the invention and comparative compositions S1 B - S4B P0000789WQ

[0216] 35

[0217] Example 14: Shampoo formulations, S17 - S20 in accordance with the invention, comprising varying amounts of Sodium Myristyl sarcosinate, co-surfactant and oil

[0218] The following Table illustrates further shampoo formulations in accordance with the invention, 5 based on different amounts of sarcosinate surfactant, that were prepared as above and characterised for viscosity as given in the table below.

[0219] Table 25: Composition and viscosity of compositions S17 - S20 in accordance with the invention comprising Sodium Myristyl sarcosinate

[0220] 10

[0221] Example 15: Shampoo compositions G1A-G4A in accordance with the invention and comparative compositions G1B - G4B

[0222] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions 15 are given in Table 26.

[0223] P0000789WQ

[0224] 36

[0225] Table 26: Ingredients (wt %) of Compositions G1A-G4A in accordance with the invention and comparative compositions G1B - G4B

[0226] 5 Table 27: Viscosity Data of Compositions G1A-G4A in accordance with the invention and comparative compositions G1 B - G4B P0000789WQ

[0227] 37

[0228] Example 16: Shampoo formulations, S21 - S32 in accordance with the invention, comprising varying amounts of sodium lauryl glycinate, co-surfactant and oil

[0229] The following Table illustrates further shampoo formulations in accordance with the invention, 5 based on different amounts of sodium lauryl glycinate, that were prepared as above and characterised for viscosity as given in the table below.

[0230] Table 28: Composition and viscosity of compositions S17 - S20 in accordance with the invention comprising sodium lauryl glycinate

[0231] 10

[0232] Various oils and co- surfactants provide good viscosity formulations P0000789WQ

[0233] 38

[0234] Example 17: Shampoo compositions L1A- L4A in accordance with the invention and comparative compositions L1B - L4B

[0235] Eight hair shampoo formulations were prepared and characterised for viscosity. The compositions are given in Table 29.

[0236] Table 29: Ingredients (wt %) of Compositions L1A- L4A in accordance with the invention and comparative compositions L1B - L4B

[0237] 10 Table 30: Viscosity Data of Compositions L1A- L4A in accordance with the invention and comparative compositions L1 B - L4B P0000789WC

[0238] 39

[0239] Example 18: Shampoo formulations, S33 - S43 in accordance with the invention, comprising varying amounts of Sodium Cocoyl Alaninate, co-surfactant and oil

[0240] The following Table illustrates further shampoo formulations in accordance with the invention, 5 based on Sodium Cocoyl Alaninate, that were prepared as above and characterised for viscosity as given in the table below.

[0241] Table 31 : Composition and viscosity of compositions S33 - S43 in accordance with the invention comprising Sodium Cocoyl Alaninate

[0242] 10 P0000789WQ

[0243] 40

[0244] Example 19: Reworking of example representative of the prior art

[0245] Example 1 of WO99 / 51193 was reworked and oil added.

[0246] Table 32: Composition of Example 1 of WO99 / 51193 rework P0000789WG

[0247] 41

[0248] Table 33: Viscosity of reworked examples before and after storagage

[0249] It will be seen that the resulting compositions suffer catastrophic viscosity loss after storage.

[0250] 5

[0251] Example 20: Comparative examples X1 - X3

[0252] Comparative Shampoo Compositions, X1 - X3, based on formulations given in

[0253] US2021 / 0401716 are shown in the Table below:

[0254] 10

[0255] X1 : comprises 0.3% Squalane with 0.3% Guar (no agar)

[0256] X2: comprises 0.3% Squalane with 0.3% Agar (not as gel particles) (no Guar)

[0257] X3: comprises 1% Squalane with 0.3% Guar (no agar)

[0258] 15 The polysaccharides were added in dry powder form (not in the form of gel particles).

[0259] P0000789WQ

[0260] 42

[0261] Table 34: Compositions of Comparative examples X1 - X3

[0262] The formulations were tested for their ability to form a viscous product, as shown in Table 35 below:

[0263] Table 35: Viscosities of Comparative examples X1 - X3

[0264] It will be seen that the viscosities of the comparative examples X1-X3 are low. P0000789WC

[0265] 43

[0266] Example 21 : Comparative example X4

[0267] Comparative Shampoo Composition, X4, is shown in the Table below:

[0268] X4: comprises 1 % coconut oil with 1.7 % Guar and 1.5 % agar (not as gel particles).

[0269] Table 36: Composition of Comparative example X4

[0270] The viscosity of the resulting composition is shown in the following table.

[0271] 10 Table 37: Viscosities of Comparative example X4

[0272] It will be seen that the product was found to be extremely stringy / snotty and not typical of a consumer desirable shampoo product. Agar (not as gel particles) in combination with a high 15 level of guar results in extreme thickening.

Claims

Claims1. A structured cleansing composition comprising a) from 0.1 to 40 wt % of a non-sulphate containing anionic surfactant comprising i) an amino acid head group; ii) an alkyl tail with a carbon-carbon chain length of from C6 to C22 b) from 0.15 to 4 wt % of a polysaccharide selected from the group consisting of agar, agarose, agaropectin and mixtures thereof; and c) an oil; wherein the polysaccharide is in the form of gel particles; wherein the composition has viscosity in the range of from 1 ,000 to 50,000 mPa.s, preferably from 1,000 to 25,000, more preferably from 2,000 to 25,000 mPa.s, even more preferably from 2,100 to 15,000 mPa.s, when measured at 25 degrees C and 4s-7, using sandblasted 40mm parallel plates, on a Wingspan rheometer (TA instruments); and wherein the composition comprises no added salt.

2. A cleansing composition as claimed in claim 1, wherein the amino acid anionic surfactant is selected from a glutamate, a taurate, a sarcosinate, a glycinate, an alalinate, a serinate, an argininate, an aspartate, an isoleucinate, a leucinate, a lysinate, a phenylalaninate, a tyrosinate, a valinate, a threoninate, a prolinate and mixtures thereof.

3. A cleansing composition as claimed in claim 1 or claim 2, which further comprises a cosurfactant.

4. A cleansing composition as claimed in claim 3, selected from amphoteric, zwitterionic, nonionic, betaine, hydroxysultaine, amphoacetate, glucotaine, amine oxide or combinations thereof.

5. A cleansing composition as claimed in any previous claim that further comprises an oil, added as a neat component at end of processing or as an emulsion, or combination of the two.

6. A cleansing composition as claimed in any preceding claim, wherein the oil is oil is not in an entrapped phase.

7. A cleansing composition as claimed in any preceding claim, wherein the oil is selected from silicone, triester oils, mineral oil, coconut oil, sunflower oil, emulsified silicone, nonemulsified silicone, squalane, shea butter and a plant-based ester of a hydroxy fatty acid8.. A cleansing composition as claimed in any preceding claim, wherein the amount of oil is 0.1 - 10 wt %, preferably 0.25 to 8 and most preferably 0. 5 to 6 wt %.

9. A cleansing composition, wherein the sulphate-free anionic surfactant is present at a level of from 0.5 and 30 wt %, preferably between 0.5 and 20 wt % most preferably between 2 and 20 wt % by total weight of the composition.

10. A cleansing composition as claimed in any preceding claim, which further comprises a cationic polymer wherein the cationic polymer is preferably selected from cationically modified polysaccharides, cationic polymers designated by the CTFA as Polyquaternium -X where X is an integer, homopolymers or copolymers comprising an acrylamidopropyltrimonium moiety, and mixtures thereof.

11. A cleansing composition as claimed in any preceding claim, which further comprises appearance modifier preferably selected from mica, dyes, pigments, fluorescent agent and pearlescer.

12. A cleansing composition as claimed in any preceding claim, which further comprises a fragrance, which may be added as a free oil or encapsulate.

13. A cleansing composition as claimed in any preceding claim, which has a pH of from 3 to 9, preferably from 4 to 8.

14. A cleansing composition as claimed in any preceding claim which further comprises an anti-dandruff active.

15. A method of cleansing a surface, comprising the step of applying a composition as defined by any one of claims 1 to 14.

Images