Hair care composition containing 2(1H)-pyridinone and piroctone olamine

Abstract

A hair care composition is disclosed that includes a compound of formula (1) and the photolabile antidandruff agent, wherein the photolabile antidandruff agent is piroctone olamine. The compound of formula (1), which is a 2(1H)-pyridinone, can be a degradation product of piroctone olamine upon exposure to UV radiation and has been shown to improve the stability of piroctone olamine. [Formula 1] TIFF2022533085000008.tif41145

Description

[Technical field]

[0001] The present invention relates to a hair care composition. In particular, the present invention relates to a hair care composition comprising piroctone olamine. [Background technology]

[0002] Dandruff is a condition experienced by many people worldwide. Dandruff conditions vary from mild symptoms such as peeling of the skin to severe inflammation and itching of the scalp. Malassezia yeasts, such as Malassezia furfur, are believed by some to be the primary cause of dandruff, and although this may not represent a complete scientific picture of the condition, Malassezia yeasts appear to be closely related to dandruff. Thus, the traditionally used strategy for treating dandruff is the topical application of antifungal agents such as zinc pyrithione (ZnPTO), piroctone olamine, climbazole and ketoconazole, usually delivered via shampoo.

[0003] Piroctone olamine (also known as Octopirox®) is a compound that is frequently used to treat fungal infections. Piroctone olamine is the ethanolamine salt of piroctone, a hydroxamic acid derivative. Piroctone olamine has antifungal properties that make it ideal for controlling a commonly occurring fungus called Malassezia globosa, which is the root cause of dandruff. It is frequently used in antidandruff shampoos as a replacement for the commonly used compound zinc pyrithione. Generally, piroctone olamine is dissolved in the base composition of a shampoo, which includes surfactants, water, silicones, polymers, and color and fragrance ingredients. When the user applies the composition to the hair and scalp, some of the compounds in piroctone olamine are deposited on it. Summary of the Invention [Problem to be solved by the invention]

[0004] Generally, the effectiveness of an anti-dandruff shampoo or conditioner is determined by the amount of anti-dandruff actives deposited on the scalp and hair, since the higher the deposition, the higher the bioavailability.However, it is well known that piroctone olamine is photolabile, and that piroctone olamine tends to react with UV light and become unstable, so that the deposited piroctone olamine is not bioavailable.This destabilization can be avoided to some extent by using UV light stabilizers or sunscreens.Efforts have also been made to enhance the antibacterial effect of piroctone olamine by combining it with "booster" technology.

[0005] An introductory description of Piroctone Olamine from Spec-Chem Ind. discloses hair care compositions containing Piroctone Olamine, and the anti-dandruff and anti-bacterial benefits of Piroctone Olamine.

[0006] With the introduction of the anti-dandruff active ingredient Octopirox® from Clariant, it became apparent that Octopirox was unstable in light, and therefore also to compositions containing Octopirox and to the manufacture of Octopirox. [Means for solving the problem]

[0007] The present inventors have identified a new way to improve the photostability problem of photolabile antidandruff agents such as piroctone olamine. The present inventors have identified that the photostability of piroctone olamine can be improved when co-formulated into a composition with a new compound that is one of the degradation products of piroctone olamine. Piroctone olamine has a tendency to decompose when exposed to UV light for an extended period of time. Once piroctone olamine has decomposed, it is no longer effective.

[0008] According to a first aspect, (i) a compound of formula 1 which may exist in amide form A or in enol form B; [ka] (ii) photolabile antidandruff agents; and (iii) A cosmetically acceptable carrier wherein the photolabile antidandruff agent is piroctone olamine.

[0009] According to a second aspect, a method for the non-therapeutic treatment of dandruff is disclosed, comprising applying to the dandruff a composition of the first aspect. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] For the avoidance of doubt, any feature of one aspect of the invention can be utilized 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 should be noted that the examples set out in the following description are intended to clarify the invention and are not intended to limit the invention to those examples themselves. Similarly, unless expressly stated otherwise, all percentages are weight / weight percentages. Except in the working examples and comparative examples, or unless expressly stated otherwise, all numbers in the description and claims expressing amounts of materials or reaction conditions, physical properties of materials, and / or uses should be understood to be modified by the word "about". Numerical ranges expressed in the format "from x to y" are understood to include x and y. When multiple preferred ranges for a particular feature are described in the format "from x to y", it is clear that all ranges combining the different endpoints are also contemplated. As used herein, the indefinite article "a" or "an" and its corresponding definite article "the" mean at least one, or one or more, unless otherwise specified. Various features of the invention referred to in individual sections above apply mutatis mutandis to other sections as appropriate. Consequently, features specified in one section may be combined with features specified in other sections as appropriate. Section headings are added for convenience only and are not intended to limit the disclosure in any way.

[0011] As used herein, "hair care composition" is meant to include compositions for topical application to mammalian, particularly human, hair or scalp. Topical means that the composition is applied to the exterior of the body. In the present invention, this is accomplished by applying the composition to the hair or scalp. Such compositions can generally be classified as leave-on or rinse-off, and include products that are applied to improve the appearance, cleansing, odor control, or general beauty of the scalp and hair. It is contemplated that the hair care composition of the present invention can be in the form of a liquid, lotion, cream, foam, scrub, gel, shampoo, conditioner, shower gel, or bar. The hair care composition of the present invention is preferably a leave-on composition. Alternatively, the hair care composition of the present invention is a wash-off composition. Excluded from the scope of the present invention are compositions for achieving the desired benefit by incorporation into the human body.

[0012] Compound of Formula 1 The compositions according to the invention comprise compounds of formula 1 which may exist in the amide form A or in the enol form B. [ka]

[0013] The pH of the composition can affect the structure of the compound of Formula 1. When the pH is less than 7, the amide form predominates, and when the pH is greater than 7, the enol form predominates.

[0014] The compound of formula 1 is i) preparing a solution of piroctone olamine by dissolving piroctone olamine in an organic solvent or in water containing at least one surfactant; ii) exposing the solution to UV light of 100mW to 2000mW in a UV chamber for 0.5 hours to 8 hours to cause decomposition of piroctone olamine to form decomposition products of the piroctone olamine; iii) separating the decomposition products of piroctone olamine by chromatographic techniques to obtain the compound of formula 1. The composition can be produced by a method comprising the steps of:

[0015] In step ii), the time for which the solution is exposed to UV radiation depends on the intensity of the UV radiation, which must be at least 100 mW. When exposed to 100 mW of UV light, it takes about 8 hours.

[0016] Preferably, the organic solvent in step i) is an alcohol, more preferably, the organic solvent in step i) is methanol or ethanol.

[0017] The aqueous surfactant solution of step i) preferably comprises an anionic surfactant or a nonionic surfactant.

[0018] The chromatographic technique used in step iii) is preferably selected from preparative liquid chromatography (pre-LC), using a preparative LC column, or column chromatography, or thin layer chromatography (TLC).

[0019] It is particularly preferred that the method used to separate the degradation products is preparative liquid chromatography (pre-LC) using a preparative LC column (Shieido, 20 x 250 mm, 5 μm). The preferred method is described below.

[0020] The column is eluted with methanol and water at a flow rate of 15 mL / min (5 mL / min for the second purification). The eluent is collected continuously in a series of sample tubes (15 mL / tube). After separation by preparative chromatography, the eluent from each sample tube is analyzed using HPLC-UV. The eluent tubes confirmed to contain the compound of formula 1 are collected and dried to obtain the compound of formula 1 in powder form.

[0021] Preferably, the hair care composition of the present invention comprises the compound of formula 1 in an amount from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight, even more preferably from 0.5 to 2.5% by weight, based on the weight of the composition.

[0022] Photolabile antidandruff agent Photolabile means that the drug is susceptible to photochemical reactions under the influence of radiant energy and especially ultraviolet light, such as photolysis, discoloration, etc. It is in contrast to photostability, which is unstable in the presence of light.

[0023] The photolabile antidandruff agent according to the present invention is piroctone olamine.

[0024] Some anti-dandruff hair care products contain piroctone olamine. It is recognized that the dissolved unmodified piroctone olamine molecule is the only bioactive form of piroctone olamine. When hair care products containing piroctone olamine are used, piroctone olamine dissociates and undergoes photo-oxidation, thereby affecting the stability of the bioactive substance and thereby reducing its anti-dandruff efficacy.

[0025] The amount of piroctone olamine in the compositions of the present invention will depend on the type of hair care composition and the exact nature of other anti-dandruff agents used. It is preferred that the composition comprises from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, even more preferably from 0.5 to 2% by weight of said photolabile anti-dandruff agent, based on the weight of the composition.

[0026] Without wishing to be bound by theory, the inventors believe that the compound of formula 1, due to its chemical structure, can react with UV radiation to prevent or reduce the destabilization of photolabile antidandruff agents such as piroctone olamine. Thus, it is believed that the more compound of formula 1 present in the composition, the more stable the photolabile antidandruff agent will be. The weight ratio of the photolabile antidandruff agent to the compound of formula 1 is preferably 1:0.1-1:10, more preferably 1:0.5-1:5, and even more preferably 1:1-1:3.

[0027] Hair care composition According to a further aspect of the present invention, there is disclosed a hair care composition according to the first aspect. Preferably, the composition is a shampoo, a hair conditioner, a hair cream, a hair gel, a hair serum, a mousse or a hair oil. More preferably, the composition is a shampoo composition.

[0028] Antidandruff agents are compounds that are active against dandruff and are typically antibacterial, preferably antifungal. Antidandruff agents typically exhibit a minimum inhibitory concentration of about 50 mg / mL or less against Malassezia.

[0029] In addition to the photolabile antidandruff agent, the hair care composition according to the invention may also contain free additional antidandruff agents different from those included. Whenever present, the hair care composition according to the invention preferably contains 0.5 to 5% by weight of additional antidandruff agent.

[0030] The additional anti-dandruff agents are preferably selected from azoles, selenium sulfide, salicylic acid, and combinations thereof. Azoles include ketoconazole and climbazole, preferably climbazole.

[0031] Compositions of the invention, particularly shampoos, are preferably formulated with anionic surfactants, such as alkyl sulfates and / or alkoxylated alkyl sulfate surfactants. These anionic surfactants are preferably present at a level of from 2 to 16%, more preferably from 3 to 16% by weight of the composition. Preferred alkyl sulfates are 8-18 Alkyl sulfate, more preferably C 12-18 Alkyl sulfates, preferably in the form of a salt with a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium. Examples include sodium lauryl sulfate (SLS) or sodium dodecyl sulfate (SDS).

[0032] A preferred alkyl ether sulfate has the formula: RO(CHCHO)n It has SO3M.

[0033] where R is an alkyl or alkenyl having 8 to 18 (preferably 12 to 18) carbon atoms; n is a number at least greater than 0.5, preferably having an average value of 1 to 3, more preferably 2 to 3; and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium. An example is sodium lauryl ether sulfate (SLES).

[0034] A preferred alkoxylated alkyl sulfate anionic surfactant is sodium lauryl ether sulfate (SLES) having an average degree of ethoxylation of 0.5-3, preferably 1-3.

[0035] The composition according to the invention optionally and preferably further comprises a betaine surfactant. In a preferred embodiment, the composition comprises 0.1 to 10% by weight, preferably 0.5 to 8% by weight, more preferably 1 to 5% by weight of a betaine surfactant, preferably an alkylamidopropyl betaine, such as cocamidopropyl betaine.

[0036] Preferably, the hair care composition of the present invention in the form of a shampoo comprises a surfactant which is sodium lauryl sulfate, sodium lauryl ether sulfate, sodium lauryl ether sulfosuccinate, ammonium lauryl sulfate, ammonium lauryl ether sulfate, sodium cocoyl isethionate and lauryl ether carboxylic acid, cocobetaine, cocamidopropyl betaine, sodium cocoamphoacetate or mixtures thereof.

[0037] Preferably, the hair care composition of the present invention comprises from 1 to 50%, preferably from 2 to 40%, more preferably from 4 to 25% total surfactants.

[0038] The hair conditioning composition comprises a conditioning surfactant selected from cationic surfactants, used alone or in admixture. Preferably, the cationic surfactant has the formula N+R1 R 2 R 3 R 4 R 1 , R 2 , R 3 and R 4 are independent (C1~C 30 ) alkyl or benzyl. Preferably, R 1 , R 2 , R 3 and R 4 One, two or three of the following are independent (C4~C 30 ) alkyl, other R 1 , R 2 , R 3 and R 4 The group or groups are (C1-C6) alkyl or benzyl. More preferably, R 1 , R 2 , R 3 and R 4 One or two of the following may be independently selected: 30 ) alkyl, other R 1 , R 2 , R 3 and R 4 The groups are (C1-C6) alkyl or benzyl groups. Optionally, the alkyl groups may contain one or more ester (-OCO- or -COO-) and / or ether (-O-) linkages within the alkyl chain. The alkyl groups may be optionally substituted with one or more hydroxyl groups. The alkyl groups may be linear or branched, and for alkyl groups having 3 or more carbon atoms, cyclic. The alkyl groups may be saturated or contain one or more carbon-carbon double bonds (e.g., oleyl). The alkyl groups may be ethoxylated on the alkyl chain with one or more ethyleneoxy groups.

[0039] Cationic surfactants suitable for use in the conditioner compositions according to the invention include cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride, tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, tallow trimethylammonium chloride, dihydrogenated tallow dimethylammonium chloride (e.g. Arquad 2HT / 75 from Akzo Nobel), cocotrimethylammonium chloride, PEG-2-oleammonium chloride and their corresponding hydroxides. Further suitable cationic surfactants include those materials with the CTFA designation Quaternium-5, Quaternium-31, and Quaternium-18. Mixtures of any of the foregoing materials may also be suitable. A particularly useful cationic surfactant for use in conditioners according to the invention is cetyltrimethylammonium chloride, commercially available, for example, from Hoechst Celanese as GENAMIN CTAC. Another particularly useful cationic surfactant for use in conditioners according to the invention is behenyltrimethylammonium chloride, commercially available, for example, from Clariant as GENAMIN KDMP. Yet another preferred cationic surfactant is stearamidopropyldimethylamine.

[0040] The most preferred cationic surfactants for use in the compositions are stearamidopropyl dimethylamine, behentrimonium chloride, or stearyl trimethyl ammonium chloride. In conditioners of the invention, the level of cationic surfactant will generally be in the range 0.1 to 5%, preferably 0.5 to 2.5% by weight of the composition.

[0041] The hair conditioning composition of the present invention may also preferably further comprise a fatty alcohol. It is believed that the combined use of a fatty alcohol and a cationic surfactant in the conditioning composition is particularly advantageous as it results in the formation of a lamellar phase in which the cationic surfactant is dispersed.

[0042] Representative fatty alcohols contain from 8 to 22 carbon atoms, more preferably from 16 to 22 carbon atoms. Fatty alcohols are typically compounds containing a straight chain alkyl group. Examples of suitable 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 of the present invention.

[0043] The level of fatty alcohol in conditioners of the invention will generally be in the range 0.5 to 10%, preferably 0.1 to 8%, more preferably 0.2 to 7%, most preferably 0.3 to 6% by weight of the composition. The weight ratio of cationic surfactant to fatty alcohol is suitably 1:1 to 1:10, more preferably 1:1.5 to 1:8, optimally 1:2 to 1:5.

[0044] It is further preferred that the hair care composition of the present invention comprises a cosmetic ingredient. Preferably, the cosmetic ingredient is selected from the group consisting of silicones, antimicrobial agents other than antidandruff agents, foam boosters, fragrances, encapsulants (e.g. encapsulated fragrances), dyes, colorants, pigments, preservatives, thickeners, proteins, phosphate esters, buffers, pH adjusters, pearlescent agents (e.g. mica, titanium dioxide, mica coated with titanium dioxide, ethylene glycol distearate (INCI glycol distearate) and / or opacifiers, viscosity modifiers, emollients, sunscreens, emulsifiers, sensory actives (e.g. menthol and menthol derivatives), vitamins, mineral oils, essential oils, lipids, natural actives, glycerin, natural hair nutrients such as plant extracts, fruit extracts, sugar derivatives and amino acids, microcrystalline cellulose and mixtures thereof.

[0045] Preferably, the hair care composition of the present invention comprises from 0.01 to 20% by weight of at least one cosmetic ingredient, more preferably from 0.05 to 10% by weight, even more preferably from 0.075 to 7.5% by weight, and most preferably from 0.1 to 5% by weight, based on the weight of the total composition, of at least one cosmetic ingredient.

[0046] The hair care composition of the present invention may also contain synergistic antimicrobial compounds that provide a synergistic antimicrobial effect when used in combination with an antidandruff active (e.g., piroctone olamine) to enhance its properties and further inhibit the growth of Malassezia furfur. Non-limiting examples of these compounds include compounds with an alcohol group (e.g., honokiol, magnolol, or paeonol), piperazines, and phenolic compounds found in natural plant extracts, such as thymol and terpeniol.

[0047] The composition may further comprise a vitamin B3 compound. A preferred vitamin B3 compound is niacinamide.

[0048] Niacinamide is known to secrete AMPs (antimicrobial proteins) from keratinocytes. The AMPs thus secreted can, for example, boost the scalp's immunity. Thus, the use of niacinamide can enhance the anti-dandruff effect not only through its antifungal activity, but also by strengthening the scalp's own protective shield against bacteria with the use of niacinamide. It is believed that this combination can provide even longer-term protection, for example, protection against bacteria for up to 24 hours.

[0049] When present, hair care compositions of the present invention preferably contain 0.1-5% niacinamide by weight of the composition, more preferably 0.5-5%, even more preferably 0.5-3%, optimally 1.0-3.0%.

[0050] silicone The hair care composition of the present invention preferably comprises a silicone.

[0051] For example, compositions of the present invention may include emulsified droplets of a silicone conditioning agent to enhance conditioning performance.

[0052] Suitable silicones include polydiorganosiloxanes, such as polydimethylsiloxane, which has the CTFA designation dimethicone. Also suitable for use in the compositions of the present invention, particularly shampoos and conditioners, are polydimethylsiloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol.

[0053] Preferably, the viscosity of the emulsified silicone is at least 10,000 cst at 25° C., preferably the viscosity of the silicone is at least 60,000 cst, most preferably at least 500,000 cst, and ideally at least 10,000,000 cst. Preferably, for ease of formulation, the viscosity is less than 10 9 Not to exceed cst.

[0054] Examples of suitable preformed emulsions include Xiameter MEM1785 and microemulsion DC2-1865 available from Dow Corning. These are dimethiconol emulsions / microemulsions. Crosslinked silicone gums are also available in preemulsified form, which is advantageous for ease of formulation. A further preferred type of silicone to include in shampoos and conditioners is aminofunctional silicone. By "aminofunctional silicone" is meant silicone that contains at least one primary, secondary or tertiary amine group, or quaternary ammonium group. Examples of suitable aminofunctional silicones include polysiloxanes with the CTFA designation "amodimethicone".

[0055] Specific examples of amino functional silicones suitable for use in the present invention are the amino silicone oils DC2-8220, DC2-8166 and DC2-8566 (all from Dow Corning).

[0056] The total amount of silicone is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and most preferably 0.5 to 3% by weight.

[0057] shampoo When the hair care compositions of the present invention are shampoos, they are generally aqueous, that is to say they have water or an aqueous solution or a lyotropic liquid crystalline phase as their major component.

[0058] Suitably the shampoo composition comprises from 50 to 98%, preferably from 60 to 92% water.

[0059] Preferably, the shampoo composition includes one or more cationic polymers for conditioning the hair.

[0060] Suitable cationic polymers include homopolymers which may be cationically substituted or formed from two or more types of monomers. The weight average (M w ) molecular weight is generally between 100,000 and 3 million daltons. The polymer will have cationic nitrogen-containing groups such as quaternary ammonium or protonated amino groups, or mixtures thereof. If the molecular weight of the polymer is too low, conditioning efficacy will be reduced. If it is too high, the extensional viscosity will be high, which can cause problems with the composition becoming stringy when poured.

[0061] The cationic nitrogen-containing groups will generally be present as substituents on some of the total monomer units of the cationic polymer. Thus, if the polymer is not a homopolymer, it may contain spacer non-cationic monomer units. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of cationic to non-cationic monomer units is selected to give a polymer with a cationic charge density in the required range, which is generally 0.2-3.0 meq / gm. The cationic charge density of the polymer is suitably measured via the Kjeldahl method described in the United States Pharmacopeia under Chemical Tests for Nitrogen Determination.

[0062] Suitable cationic polymers include copolymers of vinyl monomers having cationic amine or quaternary ammonium functional groups with water-soluble spacer monomers such as (meth)acrylamides, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylates, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C 1-3 Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol. The cationic amines may be primary, secondary, or tertiary amines, depending on the particular species and the pH of the composition. Generally, secondary and tertiary amines, especially tertiary amines, are preferred.

[0063] Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization.

[0064] The cationic polymer may comprise a mixture of monomer units derived from amine and / or quaternary ammonium substituted monomers and / or compatible spacer monomers.

[0065] Suitable (non-limiting) examples of cationic polymers include: - cationic diallyl quaternary ammonium containing polymers, such as dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride (referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively); - mineral acid salts of amino-alkyl esters of homo- and copolymers of unsaturated carboxylic acids having 3 to 5 carbon atoms (described in U.S. Pat. No. 4,009,256); - cationic polyacrylamides (described in WO95 / 2231) etc.

[0066] Other cationic polymers that can be used include cationic polysaccharide polymers such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives.

[0067] A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimethylammonium chloride (commercially available from Rhodia in its JAGUAR trademark series). Examples of such materials are JAGUAR C13S, JAGUAR C14, and JAGUAR C17.

[0068] Mixtures of any of the above cationic polymers can be used.

[0069] The hair care composition of the present invention preferably contains 0.01 to 5%, preferably 0.02 to 1%, and more preferably 0.05 to 0.8% of a cationic polymer.

[0070] The hair care composition of the present invention may further comprise a cationic deposition polymer that is a cationic polygalactomannan having an average molecular weight (Mw) of 1,000,000 to 2,200,000 g / mol and a degree of cationic substitution of 0.13 to 0.3.

[0071] Polygalactomannans are polysaccharides composed primarily of galactose and mannose units and are typically found in the endosperm material of seeds from legumes such as guar, carob, honey locust, bracken, and other members of the Fabaceae family. Polygalactomannans are composed of a backbone of 1→4 linked β-D-mannopyranosyl main chain units (also referred to as mannoside units or residues) with repeating 1→6 linked α-D-galactosyl side groups (also referred to as galactoside units or residues) branching from the sixth carbon atom of the mannopyranose residues in the polymer backbone. Polygalactomannans from different legume species differ from each other in the frequency of occurrence of galactoside side chain units branching from the polymannoside backbone. Mannoside and galactoside units are generally referred to herein as glycoside units or residues. The average ratio of mannoside units to galactoside units in the polygalactomannans contained in guar gum (hereinafter referred to as "guar") is about 2:1.

[0072] Suitable cationic polygalactomannans include guar and hydroxyalkyl guar (eg, hydroxyethyl guar or hydroxypropyl guar) that have been cationically modified by chemical reaction with one or more derivatizing agents.

[0073] In a typical composition, the amount of cationic polygalactomannan will generally range from about 0.05 to 1%, preferably 0.1 to 0.8%, more preferably 0.2 to 0.6% by weight of the composition.

[0074] The hair care compositions of the present invention may further comprise anionic polymeric rheology modifiers, such as carboxylic acid polymers.

[0075] The term "carboxylic acid polymer" in the context of the present invention generally denotes a homopolymer or copolymer resulting from the polymerization of ethylenically unsaturated monomers containing pendant carboxylic acid groups (hereinafter referred to as "carboxylic acid monomers").

[0076] Suitable carboxylic acid monomers generally have one or two carboxylic acid groups, one carbon-carbon double bond, and contain a total of from 3 to about 10 carbon atoms, more preferably from 3 to about 5 carbon atoms.

[0077] Specific examples of suitable carboxylic acid monomers include α,β-unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and α,β-unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, maleic acid, aconitic acid, etc. Salts, esters, or anhydrides of the above α,β-unsaturated mono- or dicarboxylic acids may also be used. Examples include C α,β-unsaturated dicarboxylic acids such as monomethyl fumarate, 1-4 Half esters with alkanols; cyclic anhydrides of α,β-unsaturated dicarboxylic acids such as maleic anhydride, itaconic anhydride, and citraconic anhydride; and C acrylates of acrylic or methacrylic acid such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, hexadecyl acrylate, and octadecyl acrylate. 1-30 Esters with alkanols.

[0078] Optionally, other ethylenically unsaturated monomers can be copolymerized into the carboxylic acid polymer backbone. Examples of such other ethylenically unsaturated monomers include styrene, vinyl acetate, ethylene, butadiene, acrylonitrile, and mixtures thereof. The carboxylic acid polymer preferably has a molecular weight of at least 1 million Daltons.

[0079] Suitable examples include copolymers of one or more comonomers selected from acrylic acid, methacrylic acid and mixtures thereof with C 1-4 and crosslinked copolymers polymerized from alkyl acrylates or methacrylates (e.g., ethyl acrylate). Such materials are sometimes commonly referred to by the INCI name of acrylic acid copolymer. Commercially available examples include Aculyn® 33 from Rohm and Haas.

[0080] Acrylic acid, methacrylic acid and their respective C1-4 C of acrylic acid or methacrylic acid with one or more comonomers selected from alkyl esters 10-30 Crosslinked copolymers polymerized from alkyl esters are also suitable. Such materials are generally acrylate / C 10-30 They can be referred to by the INCI name Alkyl Acrylate Crosspolymer. Commercially available examples include Carbopol® Polymers 1342 and 1382 from Lubrizol Advanced Materials.

[0081] Also suitable are copolymers of acrylic or methacrylic acid with alkyl acrylates and ethoxylated hydrophobically modified alkyl acrylates, optionally crosslinked. Such materials may be generally referred to by the INCI names of Acrylates / Steareth-20 Methacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer, Acrylates / Steareth-20 Methacrylate Crosspolymer and Acrylates / Palmeth-25 Methacrylate Copolymer. Commercially available examples include Aculyn® 22, 28 or 88 from Rohm & Haas and Synthalen® from 3V Sigma.

[0082] Preferably the carboxylic acid is a carbomer such as a homopolymer of acrylic acid crosslinked with an allyl ether of pentaerythritol or an allyl ether of sucrose.

[0083] Mixtures of any of the aforementioned materials may also be used.

[0084] Preferably, the hair care composition of the present invention comprises from 0.1 to 3.0% by weight of the composition, more preferably from 0.4 to 1.5% by weight of the carboxylic acid polymer.

[0085] In formulations containing anionic polymeric rheology modifiers, such as the carboxylic acid polymers described above, it is often necessary to neutralize at least a portion of the free carboxyl groups by adding an inorganic or organic base. Examples of suitable inorganic or organic bases include alkali metal hydroxides (e.g., sodium or potassium hydroxide), sodium carbonate, ammonium hydroxide, methylamine, diethylamine, trimethylamine, monoethanolamine, triethanolamine, and mixtures thereof.

[0086] The hair care compositions of the present invention may also include a nonionic polymeric rheology modifier selected from one or more nonionic cellulose ethers. Suitable nonionic cellulose ethers, or nonionic polymeric rheology modifiers for use in the present invention, include: 1-3 alkyl)cellulose ethers, such as methylcellulose and ethylcellulose; hydroxy(C 1-3 alkyl)cellulose ethers, such as hydroxyethyl cellulose and hydroxypropyl cellulose; mixed hydroxy (C 1-3 (alkyl)cellulose ethers, such as hydroxyethyl hydroxypropyl cellulose; and (C 1-3 Alkyl)hydroxy(C 1-3 alkyl)cellulose ethers, such as hydroxyethyl methylcellulose and hydroxypropyl methylcellulose.

[0087] The preferred nonionic cellulose ethers for use as nonionic polymeric rheology modifiers in the present invention are water-soluble nonionic cellulose ethers such as methylcellulose and hydroxypropylmethylcellulose.The term "water-soluble" in this context refers to a solubility in water of at least 1 gram, more preferably at least 3 grams, and most preferably at least 5 grams in 100 grams of distilled water at 25°C and 1 atm.This level refers to the formation of a macroscopically isotropic or transparent, colored or colorless solution.

[0088] Methylcellulose and hydroxypropyl methylcellulose are commercially available in many viscosity grades from Dow Chemical under the METHOCEL® trademark series.

[0089] Mixtures of nonionic cellulose ethers may also be suitable. In representative compositions according to the invention, the level of nonionic cellulose ether will generally be in the range of about 0.01 to about 2.0 wt.%, preferably 0.1 to 0.5 wt.%, more preferably 0.1 to 0.3 wt.%, based on the total weight of the composition.

[0090] Preferably, the hair care composition of the present invention contains 0.1 to 0.3% by weight of the nonionic cellulose ether.

[0091] The hair care composition of the present invention may contain additional optional ingredients to enhance performance and / or consumer acceptance. Examples of such ingredients include fragrances, dyes and pigments, and preservatives. Each of these ingredients is present in an amount effective to achieve its purpose. Generally, these optional ingredients are included individually at a level of up to 5% by weight based on the total weight of the composition.

[0092] Methods and Uses The present invention also provides a non-therapeutic method of treating dandruff comprising applying thereto a composition of the first aspect, preferably for cosmetic purposes.

[0093] The present invention also provides the use of the composition of the first aspect for treating dandruff. In one aspect, the use is non-therapeutic in nature, preferably cosmetic in nature.

[0094] Mode of Use The hair care compositions of the present invention are primarily intended for topical application to the hair and scalp.

[0095] If the composition is a shampoo, it is applied topically to the hair and then massaged into the hair and scalp.The hair is then rinsed with water and then dried.The leave-on hair care composition, hair oil or hair serum, is left on for 1 to 10 hours after application and then rinsed off.

[0096] The invention is further illustrated by the following non-limiting examples in which all percentages quoted are by weight based on total weight unless otherwise specified.

[0097] These examples are intended to illustrate the invention and are not intended to limit the invention to those exact examples. EXAMPLES

[0098] Example 1 Preparation of Compounds of Formula 1 The compounds of formula 1 used in the experiments were prepared using the materials, methods and procedures set forth below.

[0099] UV Treatment: Octopirox® 0.05 g was dissolved in 10 mL of methanol in a clear glass vial. UV irradiation was performed in an X-Rite® (Macbeth) Spectra Light III chamber. The UV mode was selected for UV irradiation, which provides both UVA and UVB light. UV light was tested by a UVX radiometer (UVX-36, E24195, UVP) and the intensity was 250 μw / cm for UVA. 2 , 110μw / cm for UVB 2 The chamber temperature was the same as room temperature (20±2°C). The samples were placed in a row near the center of the chamber. After 6 hours, the samples were concentrated in a rotary evaporator.

[0100] Separation: The mixture of UV decomposition products thus formed upon exposure of the compound of formula 1 to UV light was first concentrated by rotary evaporator. Separation was performed using a silica gel column (2 x 48 cm, V = 150 mL) packed with 60 g of silica gel (200-300 mesh size). The silica gel column was activated and balanced with petroleum ether / ethyl acetate (2 / 1, by volume). After loading onto the silica gel column, the concentrated mixture of UV decomposition products was separated by gradient elution at a rate of 6 mL / min. The compound of the present invention was then recovered by distilling off the solvent on a rotary evaporator.

[0101] Elemental analysis, IR, MS, and NMR analyses were used to confirm the chemical structure of the compound, which was as follows: [ka]

[0102] At pH below 7, the amide form predominates, and at pH above 7, the enol form predominates.

[0103] Preparation of Hair Care Compositions The following compositions were prepared having specific combinations of Octopirox® and compounds within the invention as shown in Table 1. The pH of the compositions was adjusted by adding either formic acid or ammonia, respectively.

[0104] Table 1 [Table 1]

[0105] For the compositions / ingredients shown in Table 1 above, studies were conducted to provide an estimate of the amount of Octopirox® remaining in hair care compositions after extended exposure to UV light. The average % remaining of Octopirox® was determined using the in vitro model described below.

[0106] Testing to determine UV stability of compositions The test conditions are described below.

[0107] UV irradiation was performed in an X-Rite (Macbeth Spectra Light III) chamber. The UV mode was selected for UV irradiation providing both UVA and UVB light. UV light was monitored by a UVX radiometer (UVX-36, E24195, UVP) and the intensity was 250 μw / cm for UVA. 2 , 110μw / cm for UVB 2 The chamber temperature was the same as room temperature (20±2°C). The samples were placed in a row near the center of the chamber.

[0108] procedure Each sample was placed under UV cabinet (Macbeth SpectraLight III) exposure at 37° C. for 120 minutes and transferred into liquid chromatography sample vials for analysis of Octopirox® by UPLC-UV analysis.

[0109] A Waters® ACQUITY Ultra Performance Liquid Chromatography (Waters, Manchester, UK) was used for sample analysis. MassLynx software (version 4.1) was used for instrument control and data acquisition. Separation was performed on a Waters Acquity UPLC BEHC18 column (2.1 × 50 mm, 1.7 μm particle size). Mobile phase A consisted of 0.1% formic acid in DI water and mobile phase B consisted of 0.1% formic acid in acetonitrile, programmed in gradient mode. Samples were measured by a PDA detector at an absorption wavelength of 302 nm.

[0110] The observations are summarized in Table 2. Table 2 [Table 2]

[0111] (1) Represents the average of two readings. (2) SD is the standard deviation of the mean residual percentage. (3) Compound means a compound of formula 1.

[0112] The data contained in Table 2 clearly show that the stability of piroctone olamine is significantly improved when compositions according to the invention are used in the experiments (Compositions 1-6) compared to the corresponding examples not included in the present invention (Compositions A and B not including the compound of Formula 1). The data further show that the role of the compound of Formula 1 in improving the UV stability of photolabile antidandruff agents such as piroctone olamine has now been demonstrated. The data also show that either the amide or enol form of the compound of Formula 1 is effective in improving the UV stability of photolabile antidandruff agents.

[0113] Decomposition of Octopirox® under Cool White Light Cool White Light Treatment: Cool white light (CWL) exposure was performed in an X-Rite (Macbeth) Spectra Light III chamber. The CWL mode was selected to provide a stable exposure that mimicked room light. The light intensity was fixed, 6 μw / cm for UVA. 2 , 1.5μw / cm for UVB 2 was estimated. The chamber temperature was the same as room temperature (20 ± 2 °C). The samples were arranged in a row near the center of the chamber. After 24 h, the samples were analyzed by LCMS (Water UPLC coupled with Quatro Micro MS), which was quantitatively measured using UPLC-UV analysis after DPS derivatization.

[0114] Separation was performed on a UPLC BEH C18 column with a mobile phase of acetonitrile / water (60 / 40, 0.1% formic acid) in isocratic elution. MS scans used electrospray ionization in positive mode.

[0115] It is observed that the amount of Octopirox® decreases, which indicates that the decomposition of Octopirox® occurs under cool white light. However, there is no compound of formula 1 detectable in the decomposition products. It can be concluded that there is no compound of formula 1 after Octopirox® is exposed to cool white light (indoor light) for a long time. The preparation of the compound of formula 1 requires exposure of Octopirox® under strong UV radiation for a sufficient time, which is different from the storage conditions of Octopirox®.

Claims

1. (i) a compound of formula 1 which may exist in amide form A or in enol form B: 【Chemistry 1】 (ii) photolabile antidandruff agents; and (iii) a cosmetically acceptable carrier; 1. A hair care composition comprising: the weight ratio of the photolabile antidandruff agent to the compound is from 1:0.1 to 1:10; the amount of the photolabile antidandruff agent is 0.1 to 10 wt. % based on the weight of the total composition; and A hair care composition, wherein the amount of the compound of formula 1 is 0.01 to 10% by weight based on the weight of the total composition.

2. The hair care composition of claim 1 further comprising a surfactant.

3. The hair care composition of claim 2 , wherein the surfactant is an anionic surfactant or a cationic surfactant.

4. 4. The hair care composition of claim 3, wherein the anionic surfactant is an alkyl sulfate and / or an alkoxylated alkyl sulfate surfactant.

5. The hair care composition of claim 4 comprising a betaine surfactant.

6. The hair care composition according to any one of claims 2 to 5, which is a shampoo.

7. 7. The hair care composition of claim 6, wherein the cationic surfactant is stearamidopropyl dimethylamine, behentrimonium chloride, or stearyl trimethyl ammonium chloride.

8. 8. A hair care composition according to claim 7 comprising from 0.5 to 10% by weight of a fatty alcohol.

9. 9. The hair care composition according to claim 7 or 8, which is a hair conditioner.

10. A method for the non-therapeutic treatment of dandruff comprising the step of applying onto the dandruff a composition according to any one of claims 1 to 9.

11. A hair care composition according to any one of claims 1 to 10 for use in the treatment or reduction of dandruff.

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