Hair conditioning composition comprising granulated starch

Abstract

Superior dry conditioning benefits and rheological properties are provided by a hair conditioner composition comprising: A) a blend of: i) starch particles having a Dv(50) particle size of 1 to 12 microns, in a weight ratio of starch:oil of 5:1 to 1:0.5; and ii) 0.01 to 5 weight percent (by weight of the total composition) of a hydrophobic non-silicone oil; B) 0.01 to 5 weight percent of an emulsified non-silicone oil; [A) and B) are dispersed therein.] C) a conditioning gel phase comprising a cationic surfactant and a fatty material, wherein the conditioner is silicone-free.

Description

[Technical field]

[0001] The present invention is in the field of hair conditioner compositions that provide conditioning benefits to silicone-free hair. [Background technology]

[0002] Consumers desire hair treatments, such as shampoos and conditioners, that provide conditioning benefits to the hair, such as smoothness, manageability and softness.

[0003] Conditioning benefits are desired and perceived by consumers both during and after the washing process. Therefore, conditioning is evaluated both when hair is wet and when it is dry. Therefore, it is desirable for rinse-off hair care products such as conditioners to provide multiple benefits at different stages of use. Wet conditioning and dry conditioning have different benefits and are typically delivered in different ways.

[0004] The impact of the gel phase ingredients of a conditioning product is most evident when evaluating wet or damp hair and upon application and distribution onto the hair.

[0005] Product rheology is an important attribute to consumers: conditioners with good rheology, such as thickness and yield stress, can provide improved conditioning benefits and are preferred by consumers.

[0006] Silicones are primarily used to provide conditioning benefits at the post-drying stage, and in silicone-free conditioner formulations, an alternative approach is needed to provide such benefits.

[0007] Starch has been used in hair conditioning compositions.

[0008] WO2017 / 172117 (L'Oreal) discloses a composition for treating keratin substrates to provide conditioning and styling benefits, the composition comprising: (a) a cationic agent comprising a first quaternary ammonium compound as specified, a second quaternary imidazoline compound as specified, (b) modified starch; (c) a first silane compound as specified, (d) a second silane compound, (e) at least one cationic vinylpyrrolidone polymer, and (f) water. Hydroxypropyl starch phosphate is preferred and exemplified.

[0009] US2006 / 0182702 (L'Oreal) describes a cationic surfactant, preferably a starch which is modified, a non-silicone cationic polymer having a cationic charge density of 5 meq / g or more, and a melting point of 35° C. or more and / or a temperature of 40° C. and a shear rate of 1 s -1 The composition includes a nonionic, nonpolymeric solid compound having a viscosity of 1 Pa·s or more at room temperature, and provides improved conditioning benefits to hair, particularly smoothing the ends of the hair.

[0010] FR2976488 (L'Oreal) discloses a cosmetic composition comprising a combination of pumice particles (i); one or more starches (ii); one or more solid fatty alcohols (iii); and one or more fatty acid esters (iv) for providing durable treatment of superficially damaged keratinous fibers. Use for smoothing hair is disclosed. Pregelatinized hydroxypropyl corn distarch phosphate is exemplified.

[0011] US2005069511 (L'Oreal) discloses cosmetic compositions comprising at least one starch, at least one carboxylic acid ester, water, and up to 20% by weight of a fatty phase relative to the total weight of the composition. The use of these compositions based on specific esters and starches is said to provide hair that is easily detangled, smooth from root to tip, and has improved style retention. In the examples, pregelatinized corn distarch phosphate or potato starch modified with 2-chloro-ethylamidodipropionic acid neutralized with sodium hydroxide is used on wet hair to provide light wet hair and easy styling.

[0012] US2016038397 (Penford Corp) discloses a cosmetic composition comprising water; a component selected from detergents and non-detergent conditioning agents; a) an amylopectin / amylose weight ratio of 60 / 40 or more; b) an apparent cationic molecular weight of 12 million Daltons or more; and c) a cationic degree of substitution of 0.5 meq / g to 2.5 meq / g for providing improved conditioning properties to personal care compositions. The personal care formulation can be used with or without silicone. Shampoos containing the cationic substituted starch are claimed to provide wet stage conditioning benefits.

[0013] EP1927346 discloses an aqueous composition for keratin fibres comprising oil and / or wax, natural starch, an emulsifier and a film-forming polymer. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] WO2017 / 172117 [Patent Document 2] US2006 / 0182702 [Patent Document 3] FR2976488 [Patent Document 4] US2005069511 [Patent Document 5] US2016038397 [Patent Document 6] EP1927346 Summary of the Invention [Problem to be solved by the invention]

[0015] Notwithstanding the prior art, a need remains to provide demonstrable conditioning benefits during the cleaning process at the dry stage without compromising consumer desired viscosity characteristics. [Means for solving the problem]

[0016] We have now discovered that the use of particulate starch blended with oil can provide improved dry conditioning from conditioners, along with surprising rheological benefits reflected in superior yield stress.

[0017] Definition of the invention In a first aspect, the present invention provides a method for producing a composition comprising: A) Starch:oil weight ratio of 0.5:1 to 1:0.5 i) starch granules having a Dv(50) particle size of 1 to 12 microns; and ii) Hydrophobic non-silicone oils 0.01 to 5 wt. % (by weight of the total composition) of a blend comprising: B) 0.01 to 5% by weight of an emulsified non-silicone oil; [A) and B) are dispersed internally.] C) A conditioning gel phase comprising a cationic surfactant and a fatty alcohol A hair conditioner composition comprising: To provide a hair conditioner composition, wherein the conditioner is silicone-free.

[0018] In a second aspect, there is provided a method of treating hair comprising applying to the hair a composition of the first aspect.

[0019] There is also provided the use of a blend of particulate starch particles and a non-silicone oil in the silicone-free composition of the first aspect to provide conditioning benefits to hair.

[0020] In the use of the present invention, the conditioning benefit is preferably a reduced coefficient of friction compared to hair treated with the same composition containing non-particulate starch. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The hair conditioner composition of the present invention comprises A): A blend of 0.01 to 5% by weight (based on the weight of the total composition) of a starch:oil weight ratio of 0.5:1 to 1:0.5, comprising: i) a starch that is a particulate starch having a particle size of 1 to 12 microns; and ii) a hydrophobic non-silicone oil.

[0022] The mixture of starch and oil is present in an amount of 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.5 to 4% by weight, and most preferably 0.5 to 3% by weight.

[0023] The starch:oil weight ratio in the blend is from 0.5:1 to 1:0.5, preferably 1:1.

[0024] Starch The compositions of the present invention include a starch that is a granular starch. The starch remains granular in the composition.

[0025] The starch used in the present invention has a Dv(50) particle size of 1 to 12 microns, preferably 2 to 10 microns, and most preferably 3 to 9 microns.

[0026] Starch particles can be characterized using a suitable particle size analyzer such as a Malvern Mastersizer 3000. The preferred refractive index (RI) of starch is 1.530 (as provided in Holes in Starch Granules: Confocal, SEM and Light Microscopy Studies of Starch Granule Structure, Baldwin, PM, Adler, J., Davies, MC, Melia, CD, Starch / Starke 46 (1994) Nr.9, S. 341-346).

[0027] Laser diffraction techniques may also be used. The sample is dispersed in water (which has a refractive index of 1.330) and directed using a recirculating cell to a sample window where the particles present scatter the light. The refractive index of both the particles and the suspending medium are used to measure the particle size. The following methods may be suitably used:

[0028] Starch powder (0.1 g) is suspended in 10 mL of deionized water and pipetted into a Mastersizer 3000 Hydro Medium Volume cell until the 5% obscuration limit is reached. This process is preferably repeated three times for each starch sample at an agitator speed of 2400 rpm.

[0029] Here, results are reported as "particle size (μm) per volume (%)" for Dv(10), Dv(50) and Dv(90), which indicate that 10%, 50% and 90% of the particles are smaller than the quoted size, respectively.

[0030] The starch used in the composition of the invention is in the form of individual particles. The starch used in the invention remains particulate in the composition of the invention.

[0031] The starch is not a gelatinized or "swelling" starch. Gelatinized or gelatinizable starches do not remain as particles when incorporated into formulations such as hair treatment compositions.

[0032] Gelatinization depends on the hydrophilicity of starch. In one study, Senanayake et al (International Journal of Food Science; Volume 2014, Article ID 148982; Suraji Senanayake, Anil Gunaratne, KKDS Ranaweera and Arthur Bamunuarachchi), starch substituted with hydroxypropyl groups showed significantly higher levels of swelling power and water solubility index compared to unmodified native starch. According to the authors, the presence of hydrophilic hydroxypropyl groups enhances the attraction of water molecules to the granule structure, thereby causing premature swelling in the granules.

[0033] Preferably, the starch is selected from rice starch, quinoa starch, amaranth starch and mixtures thereof, more preferably, the starch is selected from rice starch, quinoa starch and mixtures thereof, most preferably, the starch is rice starch.

[0034] Highly preferred rice starches can be selected from those cationically modified or combined with cetrimonium chloride (e.g., DSA 7 rice starch available from Argana Starch), crosslinked diphosphate starch (e.g., Rice PO4 Natural from Agrana Starch), or native rice starch (e.g., Reisita Natural available from Agrana Starch), and mixtures thereof.

[0035] The starch is blended with a hydrophobic, non-silicone oil, so that the starch particles are within a continuous oil phase.

[0036] Hydrophobic non-silicone oil The oils used in the compositions of the present invention are hydrophobic, non-silicone oils.

[0037] Suitable hydrophobic non-silicone oils are selected from hydrocarbon oils, fatty ester oils, and mixtures thereof.

[0038] The hydrocarbon oil may be a natural oil or a synthetic oil.

[0039] Straight chain hydrocarbon oils preferably contain from about 12 to about 30 carbon atoms. Also suitable are branched chain hydrocarbon oils, preferably containing from about 12 to about 42 carbon atoms. Also suitable are polymeric hydrocarbons of alkenyl monomers, such as C2-C6 alkenyl monomers.

[0040] Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, polyalphaolefins, squalane, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched isomers of these compounds, as well as longer chain hydrocarbons, can also be used. Another suitable material is polyisobutylene.

[0041] A preferred polyalphaolefin is commercially available from Ineos under the trade name Silkflo 366.RTM. (dec-1-ene).

[0042] Suitable fatty acid esters are characterized by having at least 6 carbon atoms and include esters with hydrocarbyl chains derived from fatty acids or alcohols. Monocarboxylic acid esters include esters of alcohols and / or acids of the formula R'COOR, where R' and R independently represent alkyl or alkenyl groups, and the sum of the carbon atoms in R' and R is at least 10, preferably at least 20. Di- and tri-alkyl and alkenyl esters of carboxylic acids can also be used.

[0043] Particularly preferred fatty acid esters are mono-, di-, and triglycerides, more specifically the mono-, di-, and triesters of glycerol and long chain carboxylic acids such as C1-C22 carboxylic acids. Preferred sources include cocoa butter, palm stearin, sunflower oil, soybean oil, and coconut oil.

[0044] The hydrophobic non-silicone oil is preferably selected from hydrocarbon oils selected from paraffin oils, mineral oils, polyalphaolefin oils, esters having hydrocarbyl chains derived from fatty acids or alcohols, and mixtures thereof.

[0045] Emulsified non-silicone oil The compositions of the present invention include an emulsified non-silicone oil, which is preferably as described above for the hydrophobic non-silicone oil used in blending with the starch.

[0046] The oil used to blend with the starch and the emulsifying oil may be the same or different.

[0047] Emulsified non-silicone oil can be produced by any suitable process, and those skilled in the art know how to prepare such emulsified oil.In a preferred process, emulsified non-silicone oil can be produced by strong inversion process using high shear homogenizer (e.g., Ultra Turrax T25Basic S2 with S25N-10G dispersion tool, manufactured by IKA, Germany).The emulsion can be formed by dropping water into the mixture of oil and surfactant under shear, for example, at a rate of 0.5mL per minute, before the inversion point.

[0048] The emulsifying surfactant can be nonionic, cationic, or a mixture of nonionic and cationic, and the total surfactant content level can typically range from 0.1% to 2% by weight of the emulsion. Suitable nonionic surfactants are known to those skilled in the art, and include, for example, Lutensol XP-79 (manufactured by BASF). Suitable cationic surfactants are known to those skilled in the art, and include, for example, cetrimonium chloride.

[0049] Silicone Free The composition of the present invention does not contain silicone. In the context of the present invention, "free from" means that silicone has less than 0.4% by weight of the total composition, more preferably less than 0.1% by weight, even more preferably less than 0.05% by weight, even more preferably less than 0.001% by weight, even more preferably less than 0.0001% by weight, and most preferably 0% by weight.

[0050] Preferably, the compositions of the present invention are also silane-free.

[0051] Conditioning gel base The conditioning base includes a cationic conditioning surfactant and a fatty alcohol.

[0052] Compositions according to the present invention comprise one or more conditioning surfactants which are cosmetically acceptable and suitable for topical application to the hair.

[0053] Suitable conditioning surfactants are selected from cationic surfactants used alone or in admixture, such as quaternary ammonium cationic surfactants corresponding to the general formula: [ka] In the formula, R 1 , R 2 , R 3 and R 4are each independently selected from (a) an aliphatic group of 16 to 22 carbon atoms, or (b) an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl, or alkylaryl group having up to 22 carbon atoms, and X is a salt-forming anion, such as a halide (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate, and alkyl sulfate, such as a methosulphate radical.

[0054] The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages and other groups, such as amino groups. Aliphatic groups, for example those of about 12 carbons or higher, can be saturated or unsaturated.

[0055] Specific examples of such quaternary ammonium cationic surfactants of the above general formula are cetyltrimethylammonium chloride, behenyltrimethylammonium chloride (BTAC), cetylpyridinium chloride, tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, tallowtrimethylammonium chloride, cocotrimethylammonium chloride, dipalmitoylethyldimethylammonium chloride, PEG-2 oleylammonium chloride, and salts thereof, in which the chloride is replaced by another halide (e.g. bromide), acetate, citric acid, lactic acid, glycolic acid, phosphate, nitrate, sulfate, or alkyl sulfate.

[0056] In the preferred class of cationic surfactants of the above general formula, R 1 is C 16 ~C 22 R is a saturated or unsaturated, preferably saturated, alkyl chain; 2 , R 3 and R 4are each independently selected from CH3 and CH2CH2OH, preferably CH3.

[0057] Specific examples of such preferred quaternary ammonium cationic surfactants are cetyltrimethylammonium chloride (CTAC), behenyltrimethylammonium chloride (BTAC), and mixtures thereof.

[0058] Preferably, the quaternary ammonium cationic surfactant has a cation selected from cetyltrimethylammonium and behenyltrimethylammonium.

[0059] Alternatively, a primary, secondary or tertiary fatty amine can be combined with an acid to provide a cationic surfactant suitable for use in the present invention, which protonates the amine in situ in the hair care composition to form an amine salt, and thus the amine is effectively a non-permanent quaternary ammonium or pseudoquaternary ammonium cationic surfactant.

[0060] Suitable fatty amines of this type include amidoamines of the general formula: [ka] In the formula, R 1 is a fatty acid chain containing 12 to 22 carbon atoms, and R 2 is an alkylene group containing 1 to 4 carbon atoms, R 3 and R 4 are each independently an alkyl group having 1 to 4 carbon atoms. Specific examples of suitable materials of the above general formula are stearamidopropyl dimethylamine, stearamidopropyl diethylamine, stearamidoethyl diethylamine, stearamidoethyl dimethylamine, palmitamidopropyl dimethylamine, palmitamidopropyl diethylamine, palmitamidoethyl diethylamine, palmitamidoethyl dimethylamine, behenamidopropyl dimethylamine, behenamidopropyl diethylamine, behenamidoethyl diethylamine, behenamidoethyl dimethylamine, arachidamidopropyl dimethylamine, arachidamidopropyl diethylamine, arachidamidoethyl diethylamine, arachiamidoethyl dimethylamine, and diethylaminoethyl stearamide.

[0061] Also useful are dimethylstearamine, dimethylsoyamine, oyamine, myristylamine, tridecylamine, ethylstearylamine, N-tallowpropanediamine, ethoxylated (containing 5 moles of ethylene oxide) stearylamine, dihydroxyethylstearylamine, and arachidylbehenylamine.

[0062] Particularly preferred is stearamidopropyl dimethylamine.

[0063] The conditioning surfactant is present in the composition at a concentration of from 0.1 to 10% by weight of the composition, preferably at least 0.5%, more preferably at least 1%, even more preferably at least 2%, even more preferably at least 3%, or even at least 4% but typically at a concentration of 9% or less, preferably 8% or less, more preferably 7% or less, even more preferably 6% or less, and even more preferably 5% or less.

[0064] Fatty alcohol The composition of the present invention is 22 The fatty alcohols include those having a carbon-carbon chain length of

[0065] The combination of a fatty alcohol and a cationic surfactant in the conditioning composition is preferred because it results in the formation of a lamellar phase in which the cationic surfactant is dispersed.

[0066] The fatty alcohol contains 8 to 22, preferably 16 to 22 carbon atoms, and most preferably C 16 ~C 18 The fatty alcohols are typically compounds containing a straight chain alkyl group. Preferably, the alkyl group is saturated. Examples of preferred fatty alcohols include cetyl alcohol, stearyl alcohol, and mixtures thereof. The use of these materials is also advantageous in that they contribute to the overall conditioning properties of the compositions used in the present invention.

[0067] The level of fatty alcohol in conditioners used in the invention will generally be in the range 0.01 to 10%, preferably 0.1 to 8%, more preferably 0.2 to 7%, most preferably 0.3 to 6% by weight of the composition.

[0068] The weight ratio of cationic surfactant:fatty alcohol is suitably 1:1 to 1:10, preferably 1:1.5 to 1:8, and most preferably 1:2 to 1:5. If the weight ratio of cationic surfactant:fatty alcohol is too high, the composition may cause eye irritation. If it is too low, the hair may feel squeaky to some consumers.

[0069] Preferred conditioners comprise a conditioning gel phase with little or no vesicle content. Such conditioners and methods for their preparation are described in WO2014 / 016354, WO2014 / 016353, WO2012 / 016352 and WO2014 / 016351.

[0070] Such a conditioning gel phase may comprise, by weight of the total composition: i) 0.4 to 8% by weight of a fatty alcohol having 8 to 22 carbon atoms; ii) 0.1 to 2% by weight of a cationic surfactant Including, The composition imparts drool mass of 1 to 250 g, preferably 2 to 100 g, more preferably 2 to 50 g, even more preferably 5 to 40 g, and most preferably 5 to 25 g to hair treated with the composition.

[0071] Drawstring is the mass required to pull the switch through a comb or brush. Thus, the more tangled the hair, the more mass is required to pull the switch through a comb or brush, and the higher the condition of the hair, the lower the pulling mass.

[0072] Draw mass is the mass required to pull a hair piece, for example weighing 1-20 g, 10-30 cm long and 0.5-5 cm wide, through the comb or brush, measured by first placing the hair piece over a comb or brush so that 5-20 cm of hair is hanging from the adhesive end of the hair piece, and then applying a weight to the hanging end until the hair piece falls off the comb or brush.

[0073] Preferably, the weight of the hair piece is 1 to 20 g, more preferably 2 to 15 g, most preferably 5 to 10 g. Preferably, the length of the hair piece is 10 to 40 cm, more preferably 10 to 30 cm, and the width is 0.5 to 5 cm, more preferably 1.5 to 4 cm.

[0074] Most preferably, draw mass is the mass required to pull a hair switch, for example weighing 10 g, 20 cm long and 3 cm wide, through a comb or brush, measured by first placing the hair switch over a comb or brush so that 20 cm of hair is hanging from the adhesive end of the hair switch, and then applying a weight to the hanging end until the hair switch falls off the comb or brush.

[0075] Unless otherwise stated, ratios, percentages, parts, etc. referred to herein are by weight.

[0076] Aspects of the present invention will now be illustrated by the following examples. EXAMPLES

[0077] Example 1: Preparation of the compositions used in the following examples Preparation of compositions 1 to 3 according to the present invention and comparative composition A The following conditioner compositions were prepared: Compositions 1-3: Conditioners containing blends of oils according to the invention and different granular starches Composition A: Comparative conditioner containing a blend of oil and non-particulate (gelatinized) starch

[0078] In the following table, oil and starch are present in the blend.

[0079] The particle size of the granular starch was measured using the method described herein.

[0080] Table 1: Compositions of hair conditioners 1 to 3 according to the present invention and comparative conditioner A [Table 1]

[0081] -Agenajel 20313 is a pregelatinized corn hydroxypropyl starch phosphate from Agrana Starch. -Rice PO4 Natural from Agrana Starch, with a Dv(50) particle size of 7.66 micrometers -Reisita Natural Starch from Agrana Starch, with a Dv(50) particle size of 8.00 micrometers -DSA7 starch particles from Agrana Starch, having a Dv(50) particle size of 8.39 micrometers -Silkflo 366: Polyalphaolefin oil (dec-1-ene) (Ineos) -Ginol 1618 TA from Godrej -Genamin BTLF from Clariant

[0082] The emulsified oil was produced by a strong inversion process using an Ultra Turrax T25 Basic S2 high shear homogenizer and dispersion tool. Before the inversion point, water was added dropwise at a rate of 0.5 mL / min to the oil and surfactant mixture under shear in a 100 mL stainless steel beaker. The resulting composition is shown in Table 2.

[0083] Table 2: Composition of emulsified oil [Table 2]

[0084] The compositions in Table 1 were prepared as follows. 1. Water was added to a suitable vessel, lactic acid was added and the vessel was heated to 80°C. 2. The surfactant and fatty material were added to a suitable vessel and heated above the melting point of the fatty material to form a melt. 3. The melt was combined with the water phase and the resulting mixture was mixed until opaque and viscous. 4. The heat was then turned off and quenching water was added. 5. The mixture was then cooled to below 40°C and the remaining ingredients including emulsified oil, fragrance were added. 6. The starch and oil were mixed together to form a blend and then added to the composition. 7. Finally, the formulation was blended under high shear conditions on a Silverson mixer at 5000 rpm for 5 minutes.

[0085] Preparation of Examples 4 to 6 and Comparative Examples B to E according to the invention Additional compositions were prepared using different conditioner gel bases for use in the following examples. Compositions 4-6: Conditioners containing blends of different granular starches and oils according to the invention Composition B: Comparative conditioner containing a blend of oil and non-granular (gelatinized) starch Composition C: Comparative composition containing unblended non-granular (gelatinized) starch and oil Compositions D and E: Comparative compositions containing unblended granular starch and oil

[0086] The emulsified oil and oil / starch mixtures were prepared as detailed above.

[0087] For compositions containing unblended starch and oil, the oil and starch were added separately.

[0088] In the following tables, oil and starch are present in the blend unless indicated with an *.

[0089] Table 3: Compositions of hair conditioners 4 to 6 according to the present invention and comparative conditioners B to E [Table 3]

[0090] -Agenajel 20313 is a pregelatinized corn hydroxypropyl starch phosphate from Agrana Starch. -Rice PO4 Natural from Agrana Starch -Reisista Natural from Agrana Starch -DSA7 starch granules from Agrana Starch -Silkflo 366: Polyalphaolefin oil (dec-1-ene) (Ineos) -Ginol 1618 TA from Godrej -Genamin BTLF from Clariant

[0091] The compositions in Table 3 were prepared as follows. 1. Water was added to a suitable container and heated to 80°C. 2. The surfactant and fatty material were added to a suitable vessel and heated above the melting point of the fatty material to form a melt. 3. The melt was combined with the water phase and the resulting mixture was mixed until opaque and viscous. 4. The heat was then turned off and quenching water was added. 5. The mixture was then cooled to below 40°C and the remaining ingredients were added including emulsified oil and fragrance. 6. The starch and oil were mixed together to form a blend and then added to the composition. 7. Finally, the formulation was blended under high shear conditions on a Silverson mixer at 5000 rpm for 5 minutes.

[0092] Example 2: Properties of starch in compositions 1 to 3 according to the invention and in comparative example A Compositions 1-3 and A were analyzed for the presence of particles using the following method: Images of the compositions were obtained using a polarized light optical microscope (Olympus BX51). A small amount of the composition was placed on a microscope slide with a cover slip on top. In transmission mode, images were captured under polarized light using a 20x magnification objective, since starch particles are birefringent. Ten images were taken per composition. The number of particles in each image was counted and the average number of particles / mm 2 was calculated.

[0093] The results are shown in Table 4 below.

[0094] Table 4: Average number of starch particles in compositions 1 to 3 according to the invention and in comparative example A [Table 4]

[0095] It will be appreciated that the starches used in the present invention remain as particles in the conditioner compositions. Composition A, which contains Agenajel 20313 starch, does not contain any particles since the gelatinized starch is dissolved.

[0096] Example 3: Effect of mixing oil and starch on the coefficient of friction of treated hair Compositions 4 and 5 according to the invention and comparative examples B to E were used to treat the hair.

[0097] The hair was treated in the following manner.

[0098] 5 g of a 10 inch dark brown European hair switch was wetted with tap water. A solution of 14% by weight sodium laureth sulfate having 1 unit of ethoxylation was applied to the switch (0.1 g per gram of hair). The switch was massaged for 30 seconds and then rinsed with tap water for 30 seconds. This was repeated. The wet switch was detangled using a comb. A conditioner composition (0.2 g per gram of hair) was then applied to the hair and massaged for 1 minute, then rinsed under a controlled water flow for 1 minute. The switch was allowed to dry at room temperature.

[0099] The friction coefficient of treated hair is then analyzed using a plate-based device attached to multiple force transducers with appropriate signal processing and data acquisition.Examples of suitable devices are described in Guest S. et al, Journal of Cosmetics, Dermatological Sciences and Applications, Vol.3, 2013, pp.66-78 and Guest S. et al, Journal of Texture Studies, Vol.43, 2012,pp.77-93 and references therein.The specific device used here is a Micro Analog 3 signal processing system (Fylde Electronic Laboratories Ltd., UK) with Dasylab data acquisition software (National Instruments, USA) and six SMT1 force transducers with 10 Newton capacity (Interface Inc., USA) attached to a glass-balsa panel (Aerospace Composite Products, USA). The data obtained here was collected by an operator running his finger along the surface of a dried treated hair tuft (described above) laid flat on the device, allowing the friction and load forces to be recorded and the resulting coefficient of friction to be calculated.

[0100] The results are provided in Table 5 below.

[0101] Table 5: Coefficient of friction of hair treated with compositions 4 and 5 and comparative compositions B to E [Table 5]

[0102] The results show that compositions according to the invention containing a mixture of oil and starch (Examples 4 and 5) provide significantly lower coefficients of friction than compositions outside the invention containing the same oil and starch but in an unblended form.

[0103] Example 4: Rheological properties of Examples 4 and 6 according to the invention and Comparative Example B The rheological properties of compositions 4 and 6 according to the invention and comparative composition C were investigated by measuring the yield stress. The following method was used and the results are shown in Table 6.

[0104] The yield stress of the products was measured with an AR-G2 rheometer from TA Instruments. The method for measuring the yield stress uses a sawtooth parallel plate geometry of 40 mm diameter mounted on a suitable rheometer with a constant frequency of 1 Hz oscillation and an amplitude sweep ranging from 0.1% to 2000%. The amplitude sweep range is applied with no more than 10 points / decade of strain range covered with no more than 4 cycles per amplitude. The equipment must be operated in tension control. The temperature of the geometry must be set at 25°C, for example using a Peltier controlled plate or a recirculating bath. The yield stress is determined by plotting the elastic stress against the strain amplitude, taking the maximum value at the peak of the curve as the yield stress.

[0105] Table 6: Yield stress of compositions 4 and 6 according to the invention (granular starch) and comparative composition B (non-granular starch) [Table 6]

[0106] The results surprisingly show that the yield stress of Examples 4 and 6 according to the invention is higher than that of Comparative Composition B.

Claims

1. A) Starch:oil weight ratio of 0.5:1 to 1:0.5 i) starch granules having a Dv(50) particle size of 1 to 12 microns; and ii) Hydrophobic non-silicone oils 0.01 to 5 wt. % (by weight of total composition) of a blend comprising: B) 0.01 to 5% by weight of an emulsified non-silicone oil; [A) and B) are dispersed internally.] C) A conditioning gel phase comprising a cationic surfactant and a fatty material. A hair conditioner composition comprising: A hair conditioner composition, wherein said conditioner is silicone-free.

2. The composition of claim 1 , wherein the starch is selected from rice starch, quinoa starch, amaranth starch, and mixtures thereof.

3. 3. The composition of claim 1 or claim 2, wherein the starch has a Dv(50) particle size of 3 to 9 microns.

4. 2. A composition according to any one of the preceding claims, wherein the hydrophobic non-silicone oil is selected from hydrocarbon oils, fatty ester oils and mixtures thereof.

5. 5. The composition of claim 4, wherein the hydrophobic non-silicone oil is selected from paraffin oil, mineral oil, polyalphaolefins, squalane, esters having hydrocarbyl chains derived from fatty acids or alcohols, and mixtures thereof.

6. 20. The composition of claim 1, wherein the emulsified non-silicone oil is selected from paraffin oil, mineral oil, polyalphaolefins, squalane, esters having hydrocarbyl chains derived from fatty acids or alcohols, and mixtures thereof.

7. 2. A composition according to any one of the preceding claims, wherein the cationic conditioning surfactant is a quaternary ammonium cationic surfactant.

8. 8. The composition of claim 7, wherein the quaternary ammonium cationic surfactant has a cation selected from cetyltrimethylammonium and behenyltrimethylammonium.

9. 2. The composition of any one of the preceding claims, wherein the fatty alcohol has a carbon-carbon chain length of from C8 to C22.

10. A method of treating hair comprising the step of applying to the hair a composition according to any one of the preceding claims.

11. Use of a blend of particulate starch and a non-silicone oil in a silicone-free composition as defined in any one of claims 1 to 9 to provide conditioning benefit to hair.

12. 12. The use of claim 11, wherein the conditioning benefit is a reduced coefficient of friction compared to hair treated with the same composition comprising non-particulate starch.