Hair care composition

Abstract

The present invention relates to hair care compositions for conditioning hair, in particular hair care compositions providing conditioning to hair without the use of silicones. Despite the apparent effects in making hair look full and shiny, conditioning formulations that contain silicone-based conditioning agents raise concerns among consumers. There remains a need to provide compositions which can provide superior conditioning performance in a sustainable manner. It is therefore an object of the present invention to provide a hair conditioning composition that provides superior conditioning performance. It has been found that the conditioning performance of a hair care composition can be improved when an acrylate polymer with side chains having a specific carbon chain length is added to a hair care composition comprising a dialkyl cationic surfactant and a conditioning oil such as mineral oils, vegetable oils etc.

Description

[0001] HAIR CARE COMPOSITION

[0002] Field of the Invention

[0003] The present invention relates to hair care compositions for conditioning hair, in particular hair care compositions providing conditioning to hair without the use of silicones.

[0004] Background of the Invention

[0005] For years silicones have been widely used as conditioning agents in hair care products. For example, silicone based conditioning agents, such as dimethicone and cyclodimethicone, have been popular in hair care products because they are useful in making hair look full, shiny, feel smooth as well as making it easy to comb.

[0006] Historically, silicone was seen as a reliable, universal and highly efficient hair care ingredient. Recently, however, consumers and formulators are becoming more aware of the bioaccumulation and potential for build-up on hair and scalp that can sometimes result from silicone use. Concerns have also been raised about the energy required to produce silicone polymers. Hair care consumers now expect sustainably formulated, environmentally friendly, silicone-free solutions that maintain excellent performance when compared to products traditionally formulated with silicone.

[0007] Therefore, despite their apparent effects in making hair look full and shiny, conditioning formulations that contain silicone-based conditioning agents raise concerns among consumers.

[0008] The use of non-silicone based conditioning agents such as mineral oil, vegetable oil etc. have been well known for conditioning for decades. However, their conditioning effect does not match that of silicones.

[0009] Therefore, there is still a need to provide compositions which can provide hair care compositions which provide superior conditioning performance in a sustainable manner without the use of silicones. For example, there is still a need to provide hair care compositions which provide excellent reduction of friction of hair fibres. It is an object of the present invention to provide a hair conditioning composition that provides superior conditioning performance.

[0010] It is another object of the present invention to improve the conditioning performance of hair care compositions comprising conditioning oils such as mineral oils, vegetable oils etc.

[0011] It is yet another object of the present invention to provide a hair conditioning composition free of silicones.

[0012] Surprisingly, it has been found that the conditioning performance of a hair care composition can be improved when an acrylate polymer with side chains having a specific carbon chain length is added to a hair care composition comprising a dialkyl cationic surfactant and a conditioning oil such as mineral oils, vegetable oils etc.

[0013] Summary of the Invention

[0014] Accordingly, in a first aspect, the present invention relates to a hair care composition comprising: a a silicone-free conditioning oil selected from a natural oil or a mineral oil; b a quaternary ammonium surfactant of structure 1,

[0015] Structure 1 wherein:

[0016] • Ri and R2 are independently linear alkyl chains, saturated or unsaturated, with a carbon chain length of from C4 to C20;

[0017] • R3 is an alkyl chain having a carbon chain length of from Ci to C4, preferably Ci to C2;

[0018] • R4is selected from hydrogen and an alkyl chain having a carbon chain length of from Ci to C4, preferably Ci to C2; and

[0019] • n has a range of from 0 to 10;

[0020] • m has a range of from 1 to 6, preferably selected from 1 and 2;

[0021] • X® is an organic or inorganic anion; c a polymer comprising monomers of formula I

[0022] Formula I wherein

[0023] A is CO2R5;

[0024] B is selected from hydrogen and methyl;

[0025] Rs is a linear or branched alkyl or alkenyl group with a carbon chain length of from C2 to C22 carbon atoms; d a high melting point (25°C or higher) fatty compound; e an aqueous carrier.

[0026] In a further aspect, the present invention relates to use of a hair care composition according to the invention for silicone-free conditioning of hair.

[0027] These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. 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. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight / weight percentages unless otherwise indicated. Except in the operating and comparative 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 are to be understood as modified by the word “about”. Numerical ranges expressed in the format "from x to y" are understood to include x and y.

[0028] When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated. Detailed Description of the Invention

[0029] Polyacrylate Polymer

[0030] The invention includes a polymer comprising monomers of Formula I

[0031] Formula I wherein

[0032] A is CO2R5;

[0033] B is selected from hydrogen and methyl;

[0034] R5is a linear or branched alkyl or alkenyl group with a carbon chain length of from C2 to C22 carbon atoms;

[0035] The polymer of the invention is a homopolymer or a copolymer, preferably a homopolymer. Preferably, B in Formula I is hydrogen. Most preferably, the polymer is a homopolymer and B is hydrogen.

[0036] Rs is a linear or branched alkyl or alkenyl group. More preferably R5 is an alkyl group. Most preferably, R5 is a linear alkyl group.

[0037] Preferably, R5 comprises up to 20 carbon atoms, more preferably up to 18 carbon atoms, such as 14 carbon atoms, more preferably up to 12 carbon atoms. Typically, R5 comprises at least 4 carbon atoms.

[0038] The polymer may be a copolymer. When the polymer is a copolymer preferably at least 50% of the polymer consists or consists essentially of monomers of Formula I. More preferably at least 70% of the polymer consists of or consists essentially of monomers of Formula I, such as at least 75%, at least 80%, at least 90%, at least 95% or at least 99%.

[0039] In some embodiments, the polymer comprises one or more monomers selected from the group of ethyl acrylate, propyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, propylheptyl acrylate, undecyl acrylate, dodecyl acrylate, tetradecyl acrylate, octadecyl acrylate, dodcosyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, 2-propylheptyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate and hexadecyl methacrylate, octadecyl methacrylate, docosyl methacrylate.

[0040] Preferably the polymer is poly (hexyl acrylate), poly(2-ethylhexyl acrylate), poly(nonyl acrylate), poly (decyl acrylate), poly (undecyl acrylate), poly (octadecyl acrylate), poly (decyl acrylate-co- tetradecyl acrylate) or poly (dodecyl acrylate).

[0041] The weight average molecular weight of the polymer of the present invention is preferably below 8,000,000 Da, such as below 7,500,000 Da, still more preferably less than 7,000,000 Da, even more preferably less than 500,000 Da, even more preferably less than 400,000 Da such as less than 350,000 Da, but typically more than 5,000 Da, preferably more than 6,000 Da, preferably more than 7,000 Da, preferably more than 20,000 Da, preferably more than 30,000 Da, most preferably more than 35,000 Da as measured using gel permeation size exclusion chromatography. For the avoidance of doubt, the unit Dalton (Da) is also known as unified atomic mass unit (u). Preferably, the GPC is calibrated using poly(methyl methacrylate) (PM MA).

[0042] The number average molecular weight of the polymer of the present invention is preferably below 120,000, more preferably below 80,000 Da, such as below 70,000 Da, still more preferably less than 50,000 Da, even more preferably less than 30,000 Da, but typically more than 5,000 Da, preferably more than 6,000 Da, preferably more than 7,000 Da, preferably more than 10,000 Da as measured using gel permeation size exclusion chromatography. For the avoidance of doubt, the unit Dalton (Da) is also known as unified atomic mass unit (u). Preferably, the GPC is calibrated using poly(methyl methacrylate) (PMMA).

[0043] Preferably, the polymer is synthesized by free radical polymerization (FRP) or emulsion polymerization. Most preferably, the polymer is synthesized using free radical polymerization.

[0044] In hair care compositions according to the invention, such as rinse-off conditioner compositions, the polymer can be present in a concentration of 0.001 to 5% by weight of the composition. Preferably, at least 0.01 %, more preferably at least 0.02%, still more preferably at least 0.05%, but typically not more than 3%, preferably not more than 2.5%, more preferably not more than 2%, still more preferably not more than 1 %, even more preferably not more than 0.5% by weight of the composition.

[0045] In the application, a “monomer” can be defined as a molecule which is polymerised to form a polymer e.g. ethyl acrylate. The monomer may also be represented in the application as the repeating structural unit provided by a molecule in a polymeric structure after polymerisation has occurred e.g. Formula I.

[0046] Conditioning oil

[0047] Conditioning oils which can be used in the present invention are chosen from mineral oils, or natural oils or combinations thereof e.g. plant oils such as vegetable oils.

[0048] Preferably, the conditioning oil has a melting point below 35°C, preferably below 30°C, more preferably below 28°C.

[0049] As understood by a person skilled in the art, a natural oil in the context of conditioning oils is a cosmetic oil derived from plants, seeds, nuts and fruits which is suitable for providing lubrication to the hair. Typically, natural oils have a melting point below 35°C, such as below 30°C, more preferably below 28°C.

[0050] Non-limiting examples of natural oils that may be used include sweet almond oil, argan oil, avocado oil, castor oil, olive oil, jojoba oil, moringa oil, sunflower oil, wheat germ oil, sesame oil, ground- nut oil, grape seed oil, soybean oil, rapeseed oil, safflower oil, coconut oil, maize oil, hazelnut oil, palm oil, apricot kernel oil, calophyllum oil and squalane.

[0051] In some embodiments, preferably the conditioning oil is a fatty acid ester oil formed from fatty acid and alcohol. Preferably, the conditioning oil comprises fatty acid esters formed from polyols such as triglycerides. Preferably, the conditioning oil comprises triglycerides comprising fatty acyl chains with a C chain length from 10 to 18 C atoms. The portion of the fatty acyl chains with 10 to 18 C atoms is preferably in the range of 45 to 95%, preferably 55 to 95%, more preferably 65 to 95% by weight, calculated to the total fatty acyl chain content of the triglyceride. Preferably, the conditioning oil comprises triglycerides with a carbon number of 15 to 60 C, preferably 30 to In some embodiments, the conditioning oil is a triglyceride-based vegetable oil such as sunflower oil, sesame oil, rapeseed oil, sweet almond oil, calophyllum oil, palm oil, avocado oil, jojoba oil, olive oil, coconut oil, castor oil or cereal germ oils such as wheat germ oil. Preferably, the conditioning oil is sunflower oil or coconut oil.

[0052] In some embodiments, preferably the conditioning oil is a hydrocarbon oil. Preferably, the hydrocarbon oil comprises a carbon chain number of from 10 to 50 C atoms. Preferably, the hydrocarbon oil comprises substantially saturated carbon chains which may be linear or branched. Preferably, the carbon number of the hydrocarbon oil is from 15 to 40 C atoms, preferably not more than 30 carbon atoms. In some preferred embodiments, the conditioning oil is squalane. Squalane from a variety of sources, whether vegetable or otherwise, is suitable for use in the invention.

[0053] As understood by a person skilled in the art, a mineral oil in the context of conditioning oils is a liquid derived from petroleum which is suitable for providing lubrication to the hair. Typically, mineral oils have a melting point below 25°C, such as below 10°C, more preferably below 0°C.

[0054] Non-limiting examples of mineral oils that may be used include highly refined white mineral oils such as, liquid paraffin, liquid petrolatum, isododecane, isohexadecane, as well as several cosmetic grade oils of varying chain length distribution and viscosity, such as Parol™, or Lytol™ white mineral oils ex Sonneborn, Netherlands.

[0055] In addition to the conditioning oils of the invention, further conditioning oils may be used in the conditioning composition. For example, the conditioning composition may comprise synthetic oils. Among the synthetic oils that can be used, non-limiting examples include those chosen from hydrogenated polydecenes, poly(alpha-olefin)s, transesterified vegetable oils and squalane.

[0056] Further non-limiting examples of synthetic oils that can be used include oil derived emollient esters such as isononyl isononanoate and dioctyldodecyl dodecanedioate, as well as low molecular weight terpene derived liquid polymers such as those commercially available within the Citropol™ series from P2 Science Inc. of Woodbridge, Connecticut, USA, such as Citropol™ 1A, or Citropol™ HA, or Bioestolides™, such as Bioestolide™ 1300 from Biosynthetic® Technologies of Indianapolis, USA.

[0057] The conditioning oil according to the invention is a natural oil or a mineral oil. Preferably, the conditioning oil is selected from a plant oil and / or a hydrocarbon oil with a melting point below 35°C, preferably below 30°C, more preferably below 28°C. More preferably, the conditioning oil is selected from a fatty acid ester oil and / or a saturated hydrocarbon oil comprising a carbon number of 10 to 60 C atoms or combinations thereof. More preferably, the conditioning oil is selected from a hydrocarbon oil with a carbon number of from 15 to 40 C atoms and a triglyceride oil or combinations thereof. More preferably, the conditioning oil is selected from one or more of sunflower seed oil, coconut oil, soya bean oil and squalane. Most preferably, the conditioning oil is sunflower seed oil.

[0058] In certain embodiments, particularly preferred are natural oils, particularly those such as sunflower seed oil, which are soluble with a wide range of example polymers. This providing flexibility to add polymer and oil together as a pre-blend, or separately as two distinct emulsions.

[0059] In hair care compositions according to the invention, such as rinse-off conditioner compositions, the conditioning oil can be present in a concentration of 0.1 to 5% by weight of the composition. Preferably, at least 0.2%, more preferably at least 0.5%, still more preferably at least 1%, most preferably at least 1.2% but typically not more than 3.5%, preferably not more than 3%, more preferably not more than 2.5% by weight of the composition.

[0060] The conditioning oil may be emulsified before inclusion in a hair care composition e.g. emulsified in an aqueous solvent, preferably water.

[0061] The polymer and conditioning oil may be included in a hair care composition in the form of a blend, or the polymer can be added to a composition separately to the conditioning oil, for example as an emulsion polymer.

[0062] In hair care compositions according to the invention, such as rinse-off conditioner compositions, the polymer and conditioning oil can be present in a total concentration of 0.1 to 5% by weight of the composition. Preferably, at least 0.2%, more preferably at least 0.5%, still more preferably at least 1%, most preferably at least 1.2% but typically not more than 3.5%, preferably not more than 3%, more preferably not more than 2.5% by weight of the composition.

[0063] The ratio of polymer to conditioning oil in the hair care composition preferably ranges from 1 :1 to 1 :1000, preferably 1 :1 to 1 :200, more preferably from 1 :3 to 1 :99, still more preferably from 1 :4 to 1 :50, even more preferably from 1 :5 to 1 :35, most preferably from 1 :5 to 1 :15, such as a ratio of 1 :9. Preferably, the polymer and conditioning oil is in the form of a blend. Formation of a blend can be achieved either by mechanical mixing of oil with polymer, or through polymerization from the relevant monomers dissolved within the oil.

[0064] The blend preferably comprises, 50 wt% to 99.9 wt% conditioning oil, preferably at least 70 wt%, more preferably at least 80 wt%, more preferably at least 85 wt% conditioning oil, but preferably not more than 99.5 wt%, such as not more than 99 wt%, preferably not more than 98 wt% conditioning oil. Most preferably the blend comprises 90 wt% conditioning oil and 10 wt% polymer. For example, a 10 wt% blend of a homopolymer in 90 wt% sunflower seed oil.

[0065] Preferably, a blend of the polymer with the conditioning oil is emulsified. Preferably, the hair care composition comprises an aqueous emulsion with an aqueous continuous phase of water and a dispersed phase containing the blend. The emulsification of a blend of the polymer with the oil serves to ensure delivery locally of both components into the contact to be conditioned. This is preferred over formation of separate emulsions of oil and of polymer, for which case, the two components may not always both reside simultaneously in a contact to be lubricated.

[0066] Preferably, the hair care composition of the invention comprises an emulsion of a blend of the inventive polymer with the conditioning oil.

[0067] Particle size of the dispersed oil / blend

[0068] One characteristic of an oil or oil / polymer blend in a composition (either directly dispersed in a composition or emulsified before inclusion in a composition) is particle size. This can be measured for example by laser diffraction particle size analysis methods, which are well documented in the art. There are several parameters which can be used to characterise emulsion particle size. For example the parameter Dv(50) represents an upper limit on a range of particle diameters, in which 50% of the volume of all dispersed material is contained.

[0069] Preferably an emulsion of the invention (such as an emulsion of a blend of the inventive polymer with the conditioning oil) has a particle size characterised by Dv(50) as measured by dynamic light scattering, for example using a Malvern Instruments Mastersizer 2000 particle size analyser with Hydro 2000SM Dispersion Unit (Malvern Instruments UK), of between 0.5 and 20 microns, more preferably between 1.5 and 15 microns, even more preferably between 1.5 and 10 microns and most preferably between 2 and 10 microns. The quaternary ammonium surfactant

[0070] The quaternary ammonium surfactant is a branched cationic conditioning surfactant.

[0071] The branched cationic conditioning surfactant contains an ester group and is selected from structure 1 .

[0072] Structure 1 wherein:

[0073] • Ri and R2comprise linear alkyl chains, saturated or unsaturated, with a carbon chain length of from C4 to C20, preferably from Ce to Cis;

[0074] • R3comprises an alkyl chain having a carbon chain length of from Ci to C4, preferably Ci to C2;

[0075] • R4 comprises hydrogen or an alkyl chain having a carbon chain length of from Ci to C4, preferably Ci to C2; and

[0076] • n has a range of from 0 to 10, preferably selected from 0 and 1 ;

[0077] • m has a range of from 1 to 6, preferably selected from 1 and 2;

[0078] • X® is an organic or inorganic anion;

[0079] In structure 1 , the amine head group is charged within the final formulation. Raw materials include, however, species where the charge is not permanent and can be induced by protonation in the formulation using a strong acid.

[0080] Optionally, at least one of R1 and R2, comprise linkages within the alkyl chain selected from the group consisting of an ester group (-OCO- or -COO-), an amido group (-NOC- or NCO-), and an ether group (-O-).

[0081] X® is an organic or inorganic anion. Preferably, X® comprises an anion selected from the halide ions; sulphates of the general formula RSCh', wherein R is a saturated or unsaturated alkyl radical having 1 to 4 carbon atoms, and anionic radicals of organic acids. Preferred halide ions are selected from fluoride, chloride, bromide and iodide. Preferred anionic radicals of organic acids are selected from maleate, fumarate, oxalate, tartrate, citrate, lactate and acetate. Preferred sulphates are methanesulphonate and ethanesulphonate.

[0082] Most preferably, X® comprises an anion selected from a halide, a methanesulfonate group and an ethanesulphonate group.

[0083] In a preferred embodiment,

[0084] • Ri and R2 comprise linear alkyl chains, saturated or unsaturated, with carbon chain lengths of from C4 to C20, preferably from C6to Cis;

[0085] • R3 comprise either hydrogen or linear or branched alkyl chains, saturated or unsaturated, with carbon chain lengths of from Ci to C3;

[0086] • n has a range of from 0 to 10, preferably selected from 0 and 1 ; and

[0087] • X® is an organic or inorganic anion.

[0088] Methods for preparation of suitable branched cationic surfactants are known in the art and described, for example, in Chemistry, A European Journal, 2008, 14, 382. For example, 2-((2- octyldodecyl)oxy)-2-oxoethan-1-aminium methanesulphonate can be synthesized by the acid- catalysed condensation reaction of glycine with the specific guerbet alcohol, furnishing the desired product in one step.

[0089] Examples of suitable materials conforming to structure 1 are 2-((2-butyloctyl)oxy)-2-oxoethan-1- aminium methanesulphonate, 2-((2-hexyldecyl)oxy)-2-oxoethan-1-aminium methanesulphonate, 2-((2-octyldodecyl)oxy)-2-oxoethan-1-aminium methanesulphonate, 2-((2-decyltetradecyl)oxy)- 2-oxoethan-1-aminium methanesulphonate, 2-((2-dodecylhexadecyl)oxy)-2-oxoethan-1- aminium methanesulphonate and 2-((2-tetradecyloctadecyl)oxy)-2-oxoethan-1-aminium methanesulphonate. Alternatively, a chloride counterion may be substituted for the methanesulphonate in the above examples.

[0090] Preferably, the quaternary ammonium surfactant is present in an amount of from 0.01 to 10 wt %, preferably from 0.01 to 5 wt %, most preferably 0.1 to 2 wt % (at 100 % active and based on weight of total composition). Hiqh meltinq fatty

[0091] By “high melting point” in the context of the fatty compound of the invention it is generally meant a melting point of 25°C or higher. Generally, the melting point ranges from 25°C up to 90°C, preferably from 40°C up to 70° C and more preferably from 50°C up to about 65°C.

[0092] The high melting point fatty compound can be used as a single compound or as a blend or mixture of at least two high melting point fatty compounds. When a blend or mixture of fatty compounds is used, the melting point means the melting point of the blend or mixture.

[0093] Suitable fatty compounds of this type have the general formula R-X, wherein R is an aliphatic carbon chain and X is a functional group (e.g. alcohol or carboxylic acid or a derivative thereof such as ester or amide).

[0094] R is preferably a saturated aliphatic carbon chain comprising from 8 to 30 carbon atoms, preferably from 14 to 30 carbon atoms, more preferably from 16 to 22 carbon atoms.

[0095] R can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. Preferably R is a linear alkyl chain comprising from 8 to 30 carbon atoms, preferably from 14 to 30 carbon atoms, more preferably from 16 to 22 carbon atoms.

[0096] X is preferably an -OH group.

[0097] The high melting point fatty compound is preferably selected from linear fatty alcohol, a linear alkoxylated fatty alcohol, a linear fatty acid and mixtures thereof. Preferably the high melting point fatty compound is selected from a linear fatty alcohol and a linear fatty acid and mixtures thereof, most preferably a linear fatty alcohol.

[0098] Most preferably, the fatty compound is a fatty alcohol of general formula CH3(CH2)n OH, where n is an integer from 7 to 29, preferably from 15 to 21.

[0099] Specific examples of suitable fatty alcohols are cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. Cetyl alcohol, stearyl alcohol and mixtures thereof are particularly preferred. The use of these materials is also advantageous in that they contribute to the overall conditioning properties of compositions for use in the invention. Alkoxylated, (e.g. ethoxylated or propoxylated) fatty alcohols having from about 12 to about 18 carbon atoms in the alkyl chain can be used in place of, or in addition to, the fatty alcohols themselves. Suitable examples include ethylene glycol cetyl ether, polyoxyethylene (2) stearyl ether, polyoxyethylene (4) cetyl ether, and mixtures thereof.

[0100] Mixtures of any of the above-described fatty compounds may also be suitable.

[0101] The level of fatty compound suitably ranges from 0.01 to 10 wt%, preferably from 0.1 to 8 wt%, more preferably from 0.2 to 7 wt% and most preferably from 0.3 to 6 wt% (by total weight of fatty compound based on the total weight of the hair care composition).

[0102] The weight ratio of branched cationic conditioning surfactant to fatty compound is suitably from 1:1 to 1 :20, preferably 1 :1 to 1:10, more preferably from 1:1.5 to 1 :8, optimally from 1:1.5 to 1:5.

[0103] Conditioning gel phase

[0104] In some embodiments of the invention a hair care composition comprises a conditioning gel phase.

[0105] Preferably, the conditioning gel phase is formed from a guaternary ammonium surfactant, a high melting point (25°C or higher) fatty compound and an agueous carrier. The combined use of fatty materials and cationic surfactants in conditioning compositions is believed to be especially advantageous, because this leads to the formation of a structured lamellar or liguid crystal phase, in which the cationic surfactant is dispersed.

[0106] Structurant

[0107] Preferably, the composition of the invention comprises a structurant, such as a non-ionic structurant. The structurant can beneficially stabilize the ingredients of a hair care composition and increase the viscosity of a composition so that further improved conditioning effects can be imparted on the hair by a composition.

[0108] The structurant may be hydrophobically modified.

[0109] Preferably, the structurant has a molecular weight ranging from 500 k Da to 2 M Da. Preferred non-ionic structurants are selected from polysaccharides, hydrophobically modified polysaccharides and mixtures thereof.

[0110] Preferably, the non-ionic structurant is a polysaccharide, preferably derived from cellulose.

[0111] Examples of suitable polysaccharide structurants include Hydroxy Ethyl Cellulose (HEC) (a non-ionic structurant) available, for example, under the tradename Natrosol™, in a range available from Ashland. Another suitable polysaccharide example is Structure XL (a non-ionic starch), available from Nouryon. Another suitable cellulosic structurant is Plantasens Biogum Tara, available from Clariant.

[0112] Suitable hydrophobically modified structurants preferably comprise both hydroxyethyl and long- chain alkyl groups. For example, hydrophobically modified HEC, available as Natrosol Plus 330, or Polysurf™ 67 (ex Ashland).

[0113] The most preferred structurant is Hydroxy Ethyl Cellulose.

[0114] Preferably, the level of the structurant suitably ranges from 0.01 to 10 wt%, preferably from 0.1 to 5 wt%, most preferably from 0.1 to 2 wt% such as 1 wt% (by total weight of structurant compound based on the total weight of the hair care composition).

[0115] Product Form and

[0116] The hair care compositions of the invention are primarily intended for topical application to the hair and / or scalp of a human subject in order to improve hair properties such as hair fibre lubrication and friction reduction, but also smoothness, softness, manageability, alignment, bodification, shaping power and shine.

[0117] Preferably, the treatment composition is selected from a rinse-off hair conditioner, a hair mask, a leave-on conditioner composition, and a pre-treatment composition, more preferably selected from a rinse-off hair conditioner, a hair mask, a leave-on conditioner composition, and a pretreatment composition, for example an oil treatment, and most preferably selected from a rinse- off hair conditioner, a hair mask and a leave-on conditioner composition. The treatment composition is preferably selected from a rinse-off hair conditioner and a leave-on conditioner. The hair care compositions of the invention are typically "rinse-off" compositions to be applied to the hair and then, in part, rinsed away.

[0118] Rinse off conditioners for use in the invention are conditioners that are typically left on wet hair for 1 to 2 minutes before being rinsed off. Typically, from about 1g to about 50g of the composition is applied to the hair or scalp.

[0119] Hair masks for use in the present invention are treatments that are typically left on the hair for 3 to 10 minutes, preferably from 3 to 5 minutes, more preferably 4 to 5 minutes, before being rinsed off.

[0120] Leave-on conditioners for use in the invention are typically applied to the hair and left on the hair for more than 10 minutes, and preferably are applied to the hair after washing and not rinsed out until the next wash.

[0121] A particularly preferred product form is a conditioner for the treatment of hair (typically after shampooing) and subsequent rinsing.

[0122] A particular preferred use of the composition is on damaged hair, such as chemically damaged hair, particularly bleached hair.

[0123] The hair care compositions of the invention will generally comprise from about 20% to about 95% of water, preferably at least 30%, more preferably at least 40%, still more preferably at least 50%, even more preferably at least 60% or even at least 70%, but typically not more than 94%, preferably not more than 93%, more preferably not more than 92%, still more preferably not more than 91%, even more preferably not more than 90% or even not more than 80% by weight based on total weight. Other organic solvents may also be present, such as lower alkyl alcohols and polyhydric alcohols. Examples of lower alkyl alcohols include C1 to C6 monohydric alcohols such as ethanol and isopropanol. Examples of polyhydric alcohols include propylene glycol, hexylene glycol, glycerin, and propanediol. Mixtures of any of the above-described organic solvents may also be used.

[0124] The hair care compositions of the invention may also incorporate other optional ingredients to enhance performance and / or consumer acceptability. Suitable optional ingredients include, but are not limited to preservatives e.g. Disodium EDTA or CIT MIT, colouring agents, chelating agents, antioxidants, fragrances, antimicrobials, antidandruff agents, cationic conditioning polymers, styling ingredients, sunscreens, proteins, hydrolyzed proteins, emulsion stabilizers and fiber actives for improving the health of the hair fibers.

[0125] In some embodiments, the hair care composition comprises a further cationic or non-ionic surfactant or combinations thereof. For example the hair care composition comprises an alkoxylated alcohol such as PEG-7 propylheptyl ether or a quaternary ammonium surfactant such as cetrimonium chloride or behentrimonium chloride. The level of the cationic and / or nonionic surfactant suitably ranges from 0.001 to 5 wt%, preferably from 0.005 to 2 wt%, most preferably from 0.01 to 1 wt% such as 0.02 wt% by total weight of the hair care composition.

[0126] Preferably, the hair care composition is silicone-free.

[0127] The invention will now be further described by reference to the following Examples. In the Examples, all percentages are by weight based on total weight, unless otherwise specified.

[0128] Example 1

[0129] Evaluation

[0130] Bleaching

[0131] Hair switches were bleached by the following method. For every 1.5 pounds of hair, 8400 ml of solution are prepared from the following ingredients: 57% Cold Water, 29% Peroxide (34% Concentrate) and 14% Ammonia (6% Concentrate) was made up. Hair is submerged in solution, with a starting pH of approximately 9.0 and left for 1 hour 45 minutes, before washing in light surfactant (Texapon ES2) and water at 30-35 degrees Celsius. It is then left to dry at room temperature.

[0132] Hair Switch Preparation and Friction Measurement of Dry, Treated Switches.

[0133] 2.5 g, 150 mm (6”) European Dark Brown hair switches (also known as swatches, or tresses) (ex I HIP, New York) were used to test the frictional properties of comparative and example formulations. For treatment with any formulation, switches were handled in bundles of 5 per formulation. Such bundles were first washed with a simple stripping shampoo comprising sodium lauryl ether sulphate and water, before 2.5 g of the test product was applied and massaged into the hair bundles for one minute. Rinsing, following massaging was for a further minute under tap water set at 37° C and a flow rate of 4 litres per minute. Switches were then individually detangled and combed through before drying in an oven at 50° C. For friction measurement, individual 2.5 g, 150 mm switches (5 replicate switches per product in turn) were mounted on a flat, metal block. These were held in place using clamps at either end. After fixing the root end, each hair switch was combed through. The switch was held under tension before fixing the second clamp in place, to ensure that fibres remained immobile when a cylindrical, neoprene rubber friction probe was passed over them.

[0134] Frictional properties of individual switches were measured in the dry state, using a Texture Analyser (Model TA XT2i, ex Stable Microsystems, Godaiming, UK). The apparatus was housed in a controlled environment at 20 °C and at 50% relative humidity. The cylindrical, neoprene friction probe was placed in contact with the hair switch under a load of 500 g and driven for 40 mm forward (from root to tip) and then 40 mm backward at a speed of 10 mm / s to generate a plot of frictional force versus distance. For each test run the resulting hysteresis loop was integrated to yield a data point units of grams multiplied by millimetres. On averaging these data across all five switches per product, the resulting mean value was used to represent the frictional properties of dry hair following treatment with test product.

[0135] Example and comparative example formulation data where formulations contained various surfactants and oils. The result was a mean friction, plotted in tables 1 to 3.

[0136] Emulsion of Squalane

[0137] Squalane was emulsified mechanically as follows. A T-25 Ultra Turrax, Basic S2 high shear homogeniser (IKA®-Werke GmbH & CO. KG of Staufen, Germany) equipped with an S25N- 10G dispersing tool, comprising a 7.5 mm rotor housed within a 10 mm stator, was used. 25 g of squalane, 24.5 g of deionized water and 0.5 g of PEG-7-propylheptyl ether (Lutensol XP-79 ex BASF) were added to a stainless-steel beaker. The contents were mixed at 11,000 rpm for 5 minutes. Table 1 Table 2 Table 3

[0138] * In Formulation Ex. 4 the squalane is emulsified before addition to the formulation.

[0139] Table 1 and 2 show comparative compositions including surfactant systems which do not contain the quaternary ammonium surfactant of structure 1. In these compositions the percentage improvement in friction reduction provided by silicone-free conditioning oil containing compositions is poor compared to compositions containing silicones.

[0140] Table 3 demonstrates that when a quaternary ammonium surfactant of structure 1 is included in compositions with the conditioning oils of the invention, the improvement in friction reduction provided by a silicone-free conditioning oil containing composition is increased significantly. The reduction in friction provided by a composition containing the silicone-free conditioning oil is of a similar or greater magnitude to that which can be achieved with a composition containing silicone oils. The data demonstrates that, when used in a hair care composition comprising the quaternary ammonium surfactant of structure 1, the conditioning oils of the invention can provide an effective and environmentally friendly replacement for silicone containing hair care compositions. Example 2

[0141] The polymers were analyzed by dynamic mechanical analysis (DMA) to quantify their glass transition temperature and by Gel Permeation Size Exclusion Chromatography (GPC). DMA data were recorded on a Perkin Elmer DMA8000 with 1 L liquid nitrogen dispenser. The method used was cooling to -100 °C with liquid nitrogen then heating to 100 °C at 2 °C / minute.

[0142] Samples were run in a stainless-steel envelope using single cantilever mode at a frequency of 1 Hz. Polymer Molecular Weight was characterized using tetrahydrofuran (THF) Gel Permeation Size Exclusion Chromatography. All size exclusion chromatography data were recorded on an Agilent Technologies Infinity II MDS instrument equipped with a differential refractive index (DRi), dual angle light scatter (LS), viscometry (VS) and variable wavelength UV detectors. The system was equipped with 2 x PLgel Mixed C columns (300 x 7.5 mm) and a PLgel 5 pm guard column. The mobile phase was THF stabilised with 2 % triethanolamine (TEA) and 0.01 % butylated hydroxytoluene (BHT) and run at a flow rate of 1 mL / minute at 30 °C. Agilent Technologies poly(methyl methacrylate) (PMMA) Easi-Vials were used to create a third order calibration from DRi data between 1 ,568,000 and 550 g I mol. Glass transition temperatures were calculated based on analysis of the DMA thermogram.

[0143] Polymer Example P1 : Poly (2-ethylhexyl acrylate)

[0144] Poly (2-ethylhexyl acrylate) was produced via free radical polymerisation, using toluene as solvent and V601 (dimethyl 2,2’-azobis(2-methylpropionate)) as initiator. 2-ethylhexyl acrylate monomer 98% (Sigma Aldrich) was filtered through active basic alumina to remove inhibitor before reaction. A 2 to 1 ratio by weight of monomer to (40 ml) toluene was used with 15 mg of initiator. These were added to a 250 ml round bottom flask and degassed with nitrogen for 30 minutes before heating. After 12 hours an extra 15 mg V601 was added to increase conversion. The reaction was stirred at 70 °C for 24 hours. After 24 hours, toluene and remaining monomer were removed by rotary evaporation at 50 °C and ~ 5 bar. The resulting material was then transferred into a jar by freezing the round bottom flask in liquid nitrogen and removing the frozen, solid material. This was then dried in a vacuum oven at 50 °C for 24 hours. The weight average molecular weight was calculated as 79,000 g / mol and the number average molecular weight was calculated as 17,300 g / mol, from the GPC chromatogram. The glass transition temperature was calculated as -65.6 °C.

[0145] Polymer Examples P2: Poly (dodecyl acrylate)

[0146] Poly (dodecyl acrylate) was each produced via free radical polymerisation using the same method as set out in Polymer Example P1. However, dodecyl acrylate was used as the monomer instead of 2-ethylhexyl acrylate.

[0147] For poly (dodecyl acrylate) (P2), the weight average molecular weight was calculated as 59,800 g / mol and the number average molecular weight was calculated as 16,900 g / mol, from the GPC chromatogram. The glass transition temperature was calculated as -4 °C, from the DMA thermogram.

[0148] Polymer Examples P3: Poly (octadecyl acrylate)

[0149] Poly (octadecyl acrylate) was produced via free radical polymerisation using cyclohexane as solvent and Trigonox 21s (tert-butyl peroxy-2-ethylhexanoate) as initiator. Octadecyl acrylate monomer (Sigma Aldrich) was filtered through active basic alumina to remove inhibitor before reaction. Cyclohexane solvent and octadecyl acrylate monomer at a 70 / 30 ratio by weight and initiator (13 mol% referred to monomer) were placed in a round bottom flask with a stirrer bar, sealed with a suba-seal and purged with nitrogen for 1 hour prior to the experiment starting. Then, the temperature was set to 80 °C. The reaction was monitored by regular sampling using a 1 mL degassed syringe. The polymer in solvent was collected after 21 hours. Finally, the solvent was removed by rotary evaporator.

[0150] The weight average molecular weight was calculated as 83,000 g / mol and the number average molecular weight was calculated as 51,000 g / mol, from the GPC chromatogram.

[0151] Emulsion example EA: Emulsion of sunflower seed oil

[0152] Sunflower seed oil from Helianthus Annus (Merck KGaA, Darmstadt, Germany) was emulsified mechanically as follows. A T-25 Ultra Turrax, Basic S2 high shear homogeniser (IKA®-Werke GmbH & CO. KG of Staufen, Germany) equipped with an S25N-10G dispersing tool, comprising a 7.5 mm rotor housed within a 10 mm stator, was used. 25 g of sunflower seed oil, 24.5 g of deionized water and 0.5 g of PEG-7-propylheptyl ether (Lutensol XP-79 ex BASF) were added to a stainless-steel beaker. The contents were mixed at 11 ,000 rpm for 5 minutes. Emulsion examples E1-E3 and EB-EC: Emulsion of polymer and sunflower seed oil blend.

[0153] Sunflower seed oil from Helianthus Annus (Merck KGaA, Darmstadt, Germany), was mechanically blended with the polymer in the amounts specified in Table 1. The blends were then emulsified as set out for Example EA above. It is noted that emulsion E3 was difficult to handle and required maintenance of a temperature above 50° C during emulsification.

[0154] Table 4

[0155] Table 5

[0156] Table 6

[0157] Table 7 Evaluation

[0158] Bleaching

[0159] Hair switches were bleached by the following method. For every 1.5 pounds of hair, 8400 ml of solution are prepared from the following ingredients: 57% Cold Water, 29% Peroxide (34% Concentrate) and 14% Ammonia (6% Concentrate) was made up. Hair is submerged in solution, with a starting pH of approximately 9.0 and left for 1 hour 45 minutes, before washing in light surfactant (Texapon ES2) and water at 30-35 degrees Celsius. It is then left to dry at room temperature.

[0160] Hair Switch Preparation and Friction Measurement of Dry, Treated Switches.

[0161] 2.5 g, 150 mm (6”) European Dark Brown hair switches (also known as swatches, or tresses) (ex I HIP, New York) were used to test the frictional properties of comparative and example formulations. For treatment with any formulation, switches were handled in bundles of 5 per formulation. Such bundles were first washed with a simple stripping shampoo comprising sodium lauryl ether sulphate and water, before 2.5 g of the test product was applied and massaged into the hair bundles for one minute. Rinsing, following massaging was for a further minute under tap water set at 37° C and a flow rate of 4 litres per minute. Switches were then individually detangled and combed through before drying in an oven at 50° C. For friction measurement, individual 2.5 g, 150 mm switches (5 replicate switches per product in turn) were mounted on a flat, metal block. These were held in place using clamps at either end. After fixing the root end, each hair switch was combed through. The switch was held under tension before fixing the second clamp in place, to ensure that fibres remained immobile when a cylindrical, neoprene rubber friction probe was passed over them.

[0162] Frictional properties of individual switches were measured in the dry state, using a Texture Analyser (Model TA XT2i, ex Stable Microsystems, Godaiming, UK). The apparatus was housed in a controlled environment at 20 °C and at 50% relative humidity. The cylindrical, neoprene friction probe was placed in contact with the hair switch under a load of 500 g and driven for 40 mm forward (from root to tip) and then 40 mm backward at a speed of 10 mm / s to generate a plot of frictional force versus distance. For each test run the resulting hysteresis loop was integrated to yield a data point units of grams multiplied by millimetres. On averaging these data across all five switches per product, the resulting mean value was used to represent the frictional properties of dry hair following treatment with test product. Example and comparative test formulation data where formulations contained surfactant systems, surfactant systems / conditioning oils, surfactant systems / conditioning oils / polymers. Examples including conditioning oil and polymers / conditioning oils were then referenced to example test data for formulations containing surfactant systems without additional conditioning oils or polymers. The result was a mean friction reduction versus base formulation only, plotted in tables 5 to 7.

[0163] Results

[0164] Table 9 Table 10 A high value of mean friction reduction is desirable as it indicates that the silicone-free formulations of the examples make hair smooth to touch, well aligned, manageable and easy to comb. The results show that when both a conditioning oil and an acrylate polymer according to the invention are added to a composition containing the quaternary ammonium surfactant of structure 1 an enhanced increase in friction reduction effect is seen compared to compositions using other cationic surfactants such as behentrimonium chloride.

Claims

CLAIMS1. A hair care composition comprising: a a silicone-free conditioning oil selected from a natural oil or a mineral oil; b a quaternary ammonium surfactant selected from structure 1 ,Structure 1 wherein:• Ri and R2 comprise linear alkyl chains, saturated or unsaturated, with carboncarbon chain lengths of from C4 to C20;• R3comprises an alkyl chain having a carbon chain length of from Ci to C4, preferably Ci to C2;• R4 comprises H or an alkyl chain having a carbon chain length of from Ci to C4, preferably Ci to C2; and• n has a range of from 0 to 10;• m has a range of from 1 to 6, preferably selected from 1 and 2;• X® is an organic or inorganic anion; c a polymer comprising monomers of Formula IFormula I whereinA is CO2R5;B is selected from hydrogen and methyl;R5is a linear or branched alkyl or alkenyl group having a carbon chain length of from C2 to C22;d a high melting point (25°C or higher) fatty compound; e an aqueous carrier.

2. The hair care composition according to claim 1 wherein the conditioning oil is a natural oil selected from sweet almond oil, argan oil, avocado oil, castor oil, olive oil, jojoba oil, moringa oil, sunflower oil, wheat germ oil, sesame oil, ground- nut oil, grape seed oil, soybean oil, rapeseed oil, safflower oil, coconut oil, maize oil, hazelnut oil, palm oil, apricot kernel oil and calophyllum oil and squalane.

3. The conditioning system according to claim 1 wherein the conditioning oil is a plant oil and / or a hydrocarbon oil with a melting point below 35°C.

4. The hair care composition according to any of the preceding claims wherein Rs comprises at least 4 carbon atoms.

5. The hair care composition according to any of the preceding claims wherein Rs comprises 20 or less carbon atoms, preferably 18 or less carbon atoms.

6. The hair care composition according to any of the preceding claims wherein the polymer is a homopolymer.

7. The hair care composition according to any of claims 1 to 5 wherein the polymer is a copolymer.

8. The hair care composition according to claim 7 wherein at least 50% of the polymer consists of monomers of Formula I, preferably at least 60%, more preferably at least 75%, most preferably at least 90% of the polymer consists of monomers of Formula I.

9. The hair care composition according to any one of the preceding claims wherein the weight ratio of polymer to conditioning oil is between 1:1 to 1 :1000.

10. The hair care composition according to any one of the preceding claims wherein the polymer and the conditioning oil are in the form of a blend.

11. The hair care composition according to claim 10 comprising an aqueous emulsion with an aqueous continuous phase of water and a dispersed phase containing the blend.

12. The hair care composition according to any one of the preceding claims wherein the molar ratio of the quaternary ammonium surfactant to the high melting point (25°C or higher) fatty compound is in the range of from 1 :20 to 1 : 1 , preferably from 1 : 10 to 1 : 1 , most preferably 1 :5 to 1:2.

13. The hair care composition according to any one of the preceding claims further comprising a structurant, preferably a non-ionic structurant.

14. Use of a hair care composition according to any of claims 1 to 13 for silicone-free conditioning of hair.

Images