FOR MAKING AND USING THEM FIELD OF THE DISCLOSURE

The present disclosure relates to nanostructured lipid carriers (NLCs) comprising a combination of murumuru seed butter, bis-diglyceryl polyacyladipate-2, and oil. The disclosure further relates to processes for making the NLCs, compositions comprising the NLCs, and methods of using the NLCs in cosmeceutical and cosmetic applications.

BACKGROUND

Hair and skin both contain lipids that provide protective characteristics to the body. Lipids make up about 3% of the total composition of hair and provide it with a degree of impermeability. The hair cuticle contains a concentration of lipids, which are basically covalently linked fatty acids, such as stearic acid, palmitic acid, oleic acid and 18-methyleicosanoic acid (18-MEA). These fatty acids cause the hair to be hydrophobic and electrically isolating. The composition of murumuru butter is similar to the lipid composition of the external surface of the hair cuticle. Murumuru butter is rich in small-chain fatty acids such as myristic (26%), lauric (47.5%), oleic (12.6%), stearic (2.6%) and palmitic acid (6.3%).

Notwithstanding hair's natural lipid barrier, it can become damaged in a variety of ways. Hair fibers can be damaged by environmental influences such as exposure to ultra violet (UV) radiation or extreme humidity conditions (e.g. dry weather conditions), or exposure to chlorine in water; hair fibers can be damaged due to chemical treatments such as bleaching, perming, frequent washings with harsh surfactant based cleansing shampoos; and hair fibers can become damaged due to mechanical influences such as brushing/combing or due to heat such as prolonged use of heated styling appliances. Lipid loss from the cuticle results the hair fibers becoming stiff and brittle, which can cause hair breakage leading to frayed or split ends.

Like hair, the surface of the skin also contains lipids that are critical to its barrier function. A lack of barrier function in the skin can lead to breakouts, dehydration, sensitization, pigmentation and aging. Common disruptors of the epidermal barrier integrity can range from hydroxy acids and soaps to stress. Healing the skin can be the first step to improving the barrier layer, and an essential component is replacing depleted lipids. Skin has been a target site of drug application. However, the skin, and in particular the stratum corneum, poses a formidable barrier to drug and other small molecule penetration, thereby limiting topical and transdermal bioavailability. Skin penetration enhancement techniques have been developed to improve bioavailability and increase the range of drugs for which topical and transdermal delivery is a viable option. Enhancement techniques, however, have focused on drug selection, prodrugs and ion-pairs, supersaturated drug solutions, eutectic systems, complexation, liposomes, vesicles and particles.

WO03059244 describes a cosmetic or pharmaceutical composition containing oil extracted from Murumuru seeds. Solid lipid nanoparticles for epidermal targets are described in the Chen et al., Podophyllotoxin-Loaded Solid Lipid Nanoparticles for Epidermal Targeting, J. CONTROL RELEASE, 10;1 10(2):296-306 (2006). These solid lipid nanoparticles are composed of 0.5% poloxamer 188 (Pluronic F68), 1 .5% soy lecithin (P-NLS), and 2% polysorbate 80 (Tween 80) (T- NLS), and are prepared with organic solvents to stabilize the initial ingredients (POD, tripalmitin and soy lecithin) by high pressure homogenization at 800 bar and 5 cycles. US 2004/0109894 is related to the manufacture of polymeric nanoparticles (Eudragit S 100) encapsulated in pH sensitive microspheres and BR1 100513-0 A2 is related to a process for the production of polymeric nanocapsules by combining the interfacial polymerization in s/fr/ with the production of a nanoemulsion by phase inversion. The process uses monomers derived from acrylic acid, activators, initiators, and a vegetable component.

SUMMARY OF THE DISCLOSURE

The present disclosure relates to nanostructured lipid carriers (NLCs) comprising a combination of at least three components: murumuru seed butter, bis- diglyceryl polyacyladipate-2, and oil. The NLCs are unique in that they have a strong affinity for substances such as hair fibers; they attach to hair fibers and even penetrate the hair fibers to a certain degree. The NLCs can deliver their contents to hair and skin, as they have the ability to penetrate the hair and skin due in part to their small size. The NLCs typically have an average diameter of about160 to about 250 nm and a zeta potential ofabout +30 mV to about +75 mV.

The NLCs are lipohilic. Therefore, lipophilic active agents (in addition to the three lipids that form the basic structure of the NLCs) can be incorporated into the NLCs. For example, an organic UV protective agent can be incorporated into the NLCs to increase the sun protective factor (SPF) of the NLCs beyond the surprising SPF already exhibited by the NLCs or by the oil in the NLC without the addition of an additional organic UV protective agent.

The NLCs are often dispersed in an aqueous medium with a surfactant. This resulting composition itself can function as a cosmetic composition such as a hair cosmetic or hair care composition, or as a cosmeceutical composition, or it can serve as a component (ingredient) of a cosmetic composition such as a hair cosmetic or hair care composition or as a cosmeceutical. Often, the dispersion is an emulsion. The compositions of the disclosure typically include: (a) murumuru seed butter; (b) bis-diglyceryl polyacyladipate-2; (c) oil; (d) a surfactant; and (e) water. The amounts of these components can vary greatly. For example, based on the total weight of the composition, the murumuru seed butter may be present in an amount of about 0.5 to about 15 wt.%, the bis-diglyceryl polyacyladipate-2 may be present in an amount of about 0.3 to about 10 wt.%, the oil may be present in an amount of about 0.01 to about 20 wt.% of an oil, and the surfactant may be present in an amount of 0.01 to 5 wt.%.

The amount of bis-diglyceryl polyacyladipate-2 in the NLCs is often greater than the amount of the oil. Furthermore, the ratio amount of murumuru seed butter to the amount of bis-diglyceryl polyacyladipate-2 is typically from about 1 .5:1 to about 4:1 , from about 2:1 to about 3:1 , or about 2.3:1 .

The oil component of the NLCs is typically liquid at room temperature and is often natural oil, for example, a plant-based or vegetal oil. Non-limiting examples of plant-based or vegetal oils include buriti oil, coconut oil, Brazil nut oil, passionfruit oil, andiroba oil, assai oil, argan oil, avocado oil, chamomile oil, and sunflower oil. In some cases, the oil is buriti oil.

The NLCs and the compositions comprising the NLCs may be used in methods for protecting hair or skin from environmental damage unrelated to UV radiation damage. Environmental damage as used herein refers to damage such as that caused by chemicals from the environement, pollution or dry weather conditions. Moreover, the NLCs and the compositions comprising the NLCs may be used to deliver an active agent (typically a lipophilic active agent) to the hair, skin, or body. The active agent may be, for example, a cosmetically active agent.

The instant disclosure further relates to processes for preparing NLCs, the process typically involving: (i) combining murumuru seed butter and bis-diglyceryl polyacyladipate-2;

(ii) heating the combination of the murumuru seed butter and bis- diglyceryl polyacyladipate-2 to a temperature above their melting temperatures and melting the combination;

(iii) combining the melted combination of (ii) with an oil;

(iv) adding the combination of (iii) to a mixture of water and a surfactant;

(v) subjecting the product of (iv) to a homogenization process;

(vi) cooling the homogenate; and

(vii) obtaining NLCs.

The murumuru seed butter and the bis-diglyceryl polyacyladipate-2 are combined and heated in step (ii). They are heated to a temperature above the melting point of both of the lipids, for example, to a temperature of 45 to 55°C. Also, in some instances, the combination of the murumuru seed butter, the bis- diglyceryl polyacyladipate-2, and the oil of (iii) is maintained at a temperature of at least 1 0°C above the melting temperatures of the murumuru seed butter and the bis-diglyceryl polyacyladipate-2 until the combination of (iii) is added to the mixture of the surfactant and the water in step (iv).

With respect to the homogenization process of (v), it may be carried out at a pressure of about 300 to about 800 bar and a temperature of about 40 to about 70°C. The homogenization process results in the formation of a homogenate. In some cases, it may be useful to repeat the homogenization process, optionally at the same or different pressures and/or temperatures. The homogenization process may be repeated from two to five times (i.e., two to five cycles). In some instances, a subsequent homogenization process may be carried out at a pressure of about 30 to about 80 bar and a temperature of about 40 to about 70°C.

The present disclosure further relates to NLCs obtained by the process described above and to cosmetic compositions comprising the NLCs, for example, in hair care products. These NLCs and the compositions comprising them may be applied to hair and skin in methods for protecting the hair and skin from environmental damage unrelated to UV radiation damage, and for delivering an active ingredient to the hair or skin. BRIEF DESCRIPTION OF THE DRAWINGS

Implementations of the present technology will now be described, by way of example only, with reference to the attached figures, wherein:

FIG. 1 provides images obtained by confocal microscopy showing differences between particles in various stages of the manufacturing process, i.e., pre-emulsion (a), after a first homogenization process (b), after a second homogenization process (c), and after a third homogenization process (d);

FIG. 2 provides images obtained by confocal microscopy of an untreated hair fiber (a) and a hair fiber treated with the NLCs (b);

FIG.3 provides images generated by cryomicroscopy of NLCs;

FIG.4 provides images obtained by high-resolution scanning electronic microscopy (SEM) showing the difference in the surface of a non-treated hair fiber (a) with the surface of hair fiber treated with NLCs (b); and

FIG. 5 provides more detailed, close-up (enlarged) images of the surfaces of the hair fibers of Figure 4(a) and (b).

It should be understood that the various aspects are not limited to the arrangements and instrumentality shown in the drawings.

DETAILED DESCRIPTION OF THE DISCLOSURE

The present disclosure relates to nanostructured lipid carriers (NLCs) comprising a combination of at least three lipids: murumuru seed butter, bis-diglyceryl polyacyladipate-2, and oil. Typically, the NLCs are dispersed in an aqueous carrier that is cosmetically acceptable. More specifically, the compositions may comprise:

(a) murumuru seed butter;

(b) bis-diglyceryl polyacyladipate-2;

(c) oil;

(d) a surfactant; and

(e) water.

The average diameter of the NLCs may vary, but in some cases, the average diameter is about 160 to about 250 nm, about 170 to about 240 nm, or about 180 to about 230 nm. Furthermore, the NLCs often have a zeta potential of about +30 mV to about +75 mV, about +45 mV to about +75 mV, about +15 mV to about +75 mV, 0 mV to about +75 mV, about +15 mV to about +75 mV, about +40 mV to about +75 mV, about +45 to about +70 mV, or about +50 to about +65 mV. The amount of each component in the NLCs or the compositions comprising them can vary greatly. For example, the amount of murumuru seed butter is often present in an amount greater than the amount of bi-diglyceryl polyacladipate- 2 and greater than the amount of oil; it may also be greater than the amount of both the bis-diglyceryl polyacladipate-2 and oil. For example, the ratio of the amount of murumuru seed butter to bis-diglyceryl polyacyladipate-2 may be about 1 .5:1 to about 4:1 , about 2:1 to about 3:1 or about 2.3:1 . Furthermore, the amount of murumuru seed butter may be in an amount of about 0.5 to about 15 wt.%, about 0.5 to about 12 wt.%, about 0.5 to about 10 wt.%, about 0.5 to about 8 wt.%, about 0.5 to about 6 wt.%, about 0.5 to about 4 wt.%, about 1 to about 15 wt.%, about 1 to about 12 wt.%, about 1 to about 10 wt.%, about 1 to about 8 wt.%, about 1 to about 6 wt.%, or about 1 to about 4 wt.%, based on the total weight of the compositions.

The amount of bis-diglyceryl polyacyladipate-2 may be in an amount of about 0.3 to about 10 wt.%, about 0.3 to about 9 wt.%, about 0.3 to about 8 wt.%, about 0.3 to about 7 wt.%, about 0.3 to about 6 wt.%, about 0.3 to about 5 wt.%, about 0.3 to about 4 wt.%, about 0.3 to about 3 wt.%, about 0.5 to about 10 wt.%, about 0.5 to about 9 wt.%, about 0.5 to about 8 wt.%, about 0.5 to about 7 wt.%, about 0.5 to about 6 wt.%, about 0.5 to about 5 wt.%, about 0.5 to about 4 wt.%, or about 0.5 to about 3 wt.%, based on the total weight of the composition.

As set forth above, the NLCs typically include an oil, the oil usually being a liquid at room temperature. In some cases, the oil is a natural oil, such as a plant-based or vegetal oil. Non-limiting examples of oils include buriti oil, coconut oil, Brazil nut oil, passionfruit oil, andiroba oil, assai oil, argan oil, avocado oil, chamomile oil, sunflower oil, or a combination thereof. In some cases, the oil is buriti oil.

The amount of oil may be in an amount of about 0.01 to about 20 wt.%, about 0.01 to about 10 wt.%, about 0.01 to about 8 wt.%, about 0.01 to about 6 wt.%, about 0.01 to about 4 wt.%, about 0.01 to about 3 wt.%, about 0.05 to about 10 wt.%, about 0.05 to about 8 wt.%, about 0.05 to about 6 wt.%, about 0.05 to about 4 wt.%, about 0.05 to about 3 wt.%, about 0.1 to about 0.01 to about 10 wt.%, about 0.1 to about 8 wt.%, about 0.1 to about 6 wt.%, about 0.1 to about 4 wt.%, or about 0.1 to about 3 wt.%, based on the total weight of the composition.

The surfactant may be a cationic surfactant, a nonionic surfactant, or a combination thereof. In some cases, the surfactant is a cationic surfactant such as a primary, secondary, or tertiary fatty amine salt, quaternary ammonium salt, or mixtures thereof. Nonlimiting examples of cationic surfactants include behenalkonium chloride, benzethonium chloride, cetylpyridinium chloride, behentrimonium chloride, lauralkonium chloride, cetalkonium chloride, cetrimonium bromide, cetrimonium chloride, cethylamine hydrofluoride, chlorallylmethenamine chloride (Quaternium-15), distearyldimonium chloride (Quaternium-5), dodecyl dimethyl ethylbenzyl ammonium chloride(Quaternium-14), Quaternium-22, Quaternium-26, Quaternium-18 hectorite, dimethylaminoethylchloride hydrochloride, cysteine hydrochloride, diethanolammonium POE (10) oletyl ether phosphate, diethanolammonium POE (3)oleyl ether phosphate, tallow alkonium chloride, dimethyl dioctadecylammoniumbentonite, stearalkonium chloride, domiphen bromide, denatonium benzoate, myristalkonium chloride, laurtrimonium chloride, ethylenediamine dihydrochloride, guanidine hydrochloride, pyridoxine HCI, iofetamine hydrochloride, meglumine hydrochloride, methylbenzethonium chloride, myrtrimonium bromide, oleyltrimonium chloride, polyquaternium-1 , procainehydrochloride, cocobetaine, stearalkonium bentonite, stearalkoniumhectonite, stearyl trihydroxyethyl propylenediamine dihydrofluoride, tallowtrimonium chloride, and hexadecyltri methyl ammonium bromide. In some cases, the cationic surfactant may be cetrimonium chloride, behentrimonium chloride, hexadecyltrimethylamonium chloride, or a mixture thereof.

As mentioned above, in some cases, the surfactant may be a nonionic surfactant. Non-limiting examples nonionic surfactants include a copolymer of ethylene oxide and propylene oxide, a condensate of ethylene oxide and/or of propylene oxide with fatty alcohols, fatty alcohols, a polyethoxylated fatty amide, a polyglycerolated fatty amide, an ethoxylated fatty acid ester of sorbitan, a fatty acid ester of sucrose, a fatty acid ester of polyethylene glycol, an alkylpolyglycoside, an N- alkylglucamine derivative, an amine oxide, or an N-acylaminopropylmorpholine oxide. In some cases the nonionic surfactant is a (poly)ethoxylated fatty alcohol, a glycerolated fatty alcohol, an alkylpolyglycoside, or a combination thereof.

The amount of surfactant chosen from a cationic surfactant, a nonionic surfactant, or a combination thereof may be about 0.01 to about 5 wt.%, about 0.01 to about 4 wt.%, about 0.01 to about 3 wt.%, about 0.01 to about 2 wt.%, about 0.05 to about 5 wt.%, about 0.05 to about 4 wt.%, about 0.05 to about 3 wt.%, about 0.05 to about 2 wt.%, about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.%, about 0.1 to about 3 wt.%, or about 0.1 to about 2 wt.%. The NLCs and compositions containing the NLCs of the present disclosure may contain other surfactants in addition to the above-mentioned cationic or nonionic surfactants such as an anionic surfactant, an amphoteric surfactant or zwitterionic surfactant.

The NLCs may, in some instances, include an active agent, often a lipophilic active agent. The lipophilic agent can be dissolved, dispersed, or encapsulated in the NLC. Note, however, that an active agent, such as a hydrophilic active agent, may alternatively or additionally be dissolved, dispersed, or encapsulated in the aqueous carrier of compositions comprising the NLCs.

In some cases, the lipophilic active agent is an aminophenol derivative, a salicylic acid derivative, an N,N'-di(arylmethylene) ethylenediaminetriacetate derivative, a 2-amino-4-alkylaminopyrimidine 3-oxide derivative, a flavonoid, retinol, retinol derivatives, a carotenoid, a fragrance, an essential oil, a hormone, a vitamin, a ceramide, a UV screening agent, or a mixture thereof.

The instant disclosure describes and encompasses processes for preparing NLCs and compositions comprising the NLCs. The processes typically include:

(i) combining murumuru seed butter and bis-diglyceryl polyacyladipate-2;

(ii) heating the combination of the murumuru seed butter and bis- diglyceryl polyacyladipate-2 to a temperature above their melting temperatures and melting the combination;

(iii) combining the melted combination of (ii) with an oil;

(iv) adding the combination of (iii) to a mixture of water and a surfactant;

(v) subjecting the product of (iv) to a homogenization process;

(vi) cooling the homogenate; and

(vii) obtaining the NLCs.

The murumuru seed butter and the bis-diglyceryl polyacyladipate-2 are combined and heated in step (ii). They are heated to a temperature above the melting point of both of the lipids, for example, to a temperature of about 45 to about 55°C. Also, in some instances, the combination of the murumuru seed butter, the bis- diglyceryl polyacyladipate-2, and the oil of (iii) is maintained at a temperature of at least 10°C above the melting temperatures of the murumuru seed butter and the bis- diglyceryl polyacyladipate-2 until the combination of (iii) is added to the mixture of the surfactant and the water in step (iv).

With respect to the homogenization process of (v), it may be carried out at a pressure of about 300 to about 800 bar and a temperature of about 40 to about 70°C. In some cases, it may be useful to repeat the homogenization process, optionally at the same or different pressures and/or temperatures. The homogenization process may be repeated from two to five times (i.e., two to five cycles). In some instances, a subsequent homogenization process may be carried out at a pressure of about 30 to about 80 bar and a temperature of about 40 to about 70°C.

The amounts and ratios for the components are as set forth above, as well as the types of oils, surfactants, etc.

The instant disclosure further relates specifically to the NLCs and compositions comprising the NLCs obtained by the processes described herein. These compositions may be, for example, cosmetic compositions, and may be used in methods for treating the hair, skin, or body. In some cases the compositions are hair-care compositions and may be used in methods for protecting the hair from damage, such as environmental damage that is unrelated to UV radiation damage.

More exhaustive but non-limiting lists of components useful in the hair care compositions disclosed herein are presented below.

OILS

The oil component of the NLCs is typically has melting temperature of less than 45°C, a molecular weight of at least 190, and a solubility in water of no greater than 1 part in 99 parts of water. Non-limiting example include plant-based or vegetal oils such as acai oil, almond oil, aloe vera oil, andiroba oil, annatto oil, avocado oil, babassu oil, borage oil, brazil nut oil, buriti oil, camelina oil, coffee oil, copaiba oil, emu oil, passion fruit oil, almond oil, castor oil, coconut oil, grapeseed oil, jojoba oil, macadamia nut oil, rose hip oil, ajwain oil, angelic root oil, anise oil, aragan oil, asafetida, balsam oil, basil oil, bay oil, bergamot oil, black pepper essential oil, buchu oil, birch oil, camphor, cannabis oil, caraway oil, cardamom seed oil, carrot seed oil, chamomile oil, calamus root oil, cinnamon oil, citronella oil, clary sage, clove leaf oil, coffee, coriander, costmary oil, cranberry seed oil, cubeb, cumin oil, cypress, cypriol, curry leaf, davana oil, dill oil, elecampane, eucalyptus oil, fennel seed oil, fenugreek oil, fir, frankincense oil, galangal, geranium oil, ginger oil, goldenrod, grapefruit oil, grapeseed oil, henna oil, helichrysum, horseradish oil, hyssop, Idaho tansy, jasmine oil, juniper berry oil, lavender oil, lemon oil, lemongrass, marjoram, melaleuca, lemon balm oil, mountain savory, mugwort oil, mustard oil, myrrh oil, myrtle, neem tree oil, neroli, nutmeg, orange oil, oregano oil, orris oil, palo santo, parsley oil, patchouli oil, perilla oil, pennyroyal oil, peppermint oil, petitgrain, pine oil, plum oil, ravensara, red cedar, roman chamomile, rose oil, rosehip oil, rosemary oil, rosewood oil, sandalwood oil, sassafras oil, savory oil, schisandra oil, spikenard, spruce, star anise oil, tangerine, tarragon oil, tea tree oil, thyme oil, tsuga oil, turmeric, valerian, vetiver oil, western red cedar, wintergreen, yarrow oil, ylang-ylang, and zedoary oil.

In certain embodiments of the present disclosure, the oil is a vegetal oil chosen from buriti oil.

LIPOPHILIC ACTIVE AGENTS

The term "lipophilic active agent" refers to an active agent that is capable of being dissolved in a fatty phase or solubilized in colloidal form (for example, in micellar form) in a fatty phase.

The lipophilic active agent may include anti-ageing active agents, anti- wrinkle active agents, moisturizers or humectants, depigmenting active agents, active agents for combating free radicals (radical oxygen species), nutritive active agents, protective active agents, restructuring active agents, firming active agents, slimming active agents, anti-acne active agents, exfoliative active agents, emollient active agents or alternatively active agents for treating skin diseases, such as mycoses, dermatitides, psoriasis, and the like.

Non-limiting examples of lipophilic active agents which can be used in accordance with the disclosure include organic UV screening agents such as para- aminobenzoic acid derivatives, salicylic derivatives, cinnamic derivatives, benzophenones and aminobenzophenones, anthranillic derivatives, β, β- diphenylacrylate derivatives, benzylidenecamphor derivatives, phenylbenzimidazole derivatives, benzotriazole derivatives, triazine derivatives, bisresorcinyl triazines, imidazoline derivatives, benzalmalonate derivatives, 4,4-diarylbutadiene derivatives, benzoxazole derivatives, merocyanines, malonitrile or malonate diphenyl butadiene derivatives, chalcones and mixtures thereof.

In some cases, the lipophilic active agent may be retinol (vitamin A) or derivatives thereof, tocopherol (vitamin E) or derivatives thereof, essential fatty acids, ceramides, essential oils, or salicylic acid, or derivatives thereof. SURFACTANTS

CATIONIC SURFACTANTS

The term "cationic surfactant" means a surfactant that is positively charged when it is contained in the composition according to the disclosure. This surfactant may bear one or more positive permanent charges or may contain one or more functions that are cationizable in the composition according to the disclosure.

Non-limiting examples of cationic surfactants include behenalkonium chloride, benzethonium chloride, cetylpyridinium chloride, behentrimonium chloride, lauralkonium chloride, cetalkonium chloride, cetrimonium bromide, cetrimonium chloride, cethylamine hydrofluoride, chlorallylmethenamine chloride (Quaternium-15), distearyldimonium chloride (Quaternium-5), dodecyl dimethyl ethylbenzyl ammonium chloride(Quaternium-14), Quaternium-22, Quaternium-26, Quaternium-18 hectorite, dimethylaminoethylchloride hydrochloride, cysteine hydrochloride, diethanolammonium POE (10) oletyl ether phosphate, diethanolammonium POE (3)oleyl ether phosphate, tallow alkonium chloride, dimethyl dioctadecylammoniumbentonite, stearalkonium chloride, domiphen bromide, denatonium benzoate, myristalkonium chloride, laurtrimonium chloride, ethylenediamine dihydrochloride, guanidine hydrochloride, pyridoxine HCI, iofetamine hydrochloride, meglumine hydrochloride, methylbenzethonium chloride, myrtrimonium bromide, oleyltrimonium chloride, polyquaternium-1 , procainehydrochloride, cocobetaine, stearalkonium bentonite, stearalkoniumhectonite, stearyl trihydroxyethyl propylenediamine dihydrofluoride, tallowtrimonium chloride, and hexadecyltrimethyl ammonium bromide.

The cationic surfactant(s) may be chosen from optionally polyoxyalkylenated, primary, secondary or tertiary fatty amines, or salts thereof, and quaternary ammonium salts, and mixtures thereof.

The fatty amines generally comprise at least one C ₈ -C ₃ o hydrocarbon- based chain.

Examples of quaternary ammonium salts that may especially be mentioned include: those corresponding to the general formula (III) below:

¾ Rio

N

\

(III) in which the groups R ₈ to R-π , which may be identical or different, represent a linear or branched, saturated or unsaturated aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups Rs to Rn denoting a group comprising from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms. The aliphatic groups may comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens. The aliphatic groups are chosen, for example, from C1-C30 alkyl, C2-C30 alkenyl, C1-C30 alkoxy, polyoxy(C2-C6)alkylene, C1-C30 alkylamide, (Ci2-C22)alkylamido(C2-C6)alkyl, (C12- C ₂ 2)alkyl acetate and Ci -C ₃₀ hydroxyalkyl groups; X is an anion chosen from the group of halides, phosphates, acetates, lactates, (CrC ₄ )alkyl sulfates, and (d- C ₄ )alkyl- or (CrC ₄ )alkylarylsulfonates.

Among the quaternary ammonium salts of formula (III), those that are preferred are, on the one hand, tetraalkylammonium salts, for instance dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltnmethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts, or, on the other hand, oleocetyldimethylhydroxyethylammonium salts, palmitylamidopropyltrimethylammonium salts, stearamidopropyltrimethylammonium salts and stearamidopropyldimethylcetearylammonium salts.

In some cases it is useful to use salts such as the chloride salts of the following compounds:

A. a quaternary ammonium salt of imidazoline, such as, for example, those of formula (IV) below:

(IV)

in which R ₂ represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, derived for example from tallow fatty acids, R13 represents a hydrogen atom, a Ci-C ₄ alkyl group or an alkyl or alkenyl group comprising from 8 to 30 carbon atoms, R represents a C C ₄ alkyi group, Ri ₅ represents a hydrogen atom or a C C ₄ alkyi group, X ^" is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyi sulfates, alkyi- or alkylaryl-sulfonates in which the alkyi and aryl groups preferably comprise, respectively, from 1 to 20 carbon atoms and from 6 to 30 carbon atoms. R-I2 and Ri ₃ preferably denote a mixture of alkenyl or alkyi groups containing from 12 to 21 carbon atoms, derived for example from tallow fatty acids, R preferably denotes a methyl group, and R15 preferably denotes a hydrogen atom;

B. a quaternary diammonium or triammonium salt, in particular of formula (V):

(V)

in which R ₆ denotes an alkyi radical comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms, R17 IS chosen from hydrogen or an alkyi radical comprising from 1 to 4 carbon atoms or a group (Ri6a)(Ri7a)(Ri8a)N-(CH ₂ )3,

Riea, Riza, Ri8a. Rie> R ₉ , R ₂ o and R ₂ i , which may be identical or different, being chosen from hydrogen and an alkyi radical comprising from 1 to 4 carbon atoms, and X ^" is an anion chosen from the group of halides, acetates, phosphates, nitrates and methyl sulfates. Such compounds are, for example, Quaternium 89 and Quaternium 75;

C. a quaternary ammonium salt containing at least one ester function, such as those of formula (VI) below:

O

R ₂₄ '— C— (OCjy— — R ₂₃ X ^"

(VI)

in which: R22 is chosen from CrC ₆ alkyl groups and CrC ₆ hydroxyalkyl or dihydroxyalkyl groups;

R23 is chosen from:

O

R ₂ 6 ^: — C

R27, which is a linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based group, and a hydrogen atom,

R25 is chosen from:

O

Q _^ R _29j which is a linear or branched, saturated or unsaturated C1-C6 hydrocarbon-based group, and a hydrogen atom,

R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups;

r, s and t, which may be identical or different, are integers ranging from

2 to 6;

y is an integer ranging from 1 to 10;

x and z, which may be identical or different, are integers ranging from 0 to 10;

X is a simple or complex, organic or mineral anion;

with the proviso that the sum x+y+z is from 1 to 15, that when x is 0 then R _n denotes R27, and that when z is 0 then R25 denotes R29.

The alkyl groups R22 may be linear or branched, and more particularly linear. In some cases, R22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group. Advantageously, the sum x+y+z is from 1 to 10.

When R23 is a hydrocarbon-based group R27, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms. When R25 is an R ₂ g hydrocarbon-based group, it preferably contains 1 to 3 carbon atoms. Advantageously, R ₂₄ , R26 and R ₂ s, which may be identical or different, are chosen from linear or branched, saturated or unsaturated Cn-C ₂ i hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C-n- C21 alkyl and alkenyl groups. In some cases, x and z, which may be identical or different, have values of 0 or 1 . Likewise, in some cases y is equal to 1 . In some cases, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.

The anion X is may be a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methyl sulfate. However, use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion compatible with the ammonium containing an ester function.

The anion X is even more particularly chloride or methyl sulfate.

Use is made more particularly, in the composition according to the invention, of the ammonium salts of formula (VI) in which:

R22 denotes a methyl or ethyl group,

x and y are equal to 1 ;

z is equal to 0 or 1 ;

r, s and t are equal to 2;

R23 is chosen from:

16 , methyl, ethyl or Ci ₄ -C ₂ 2 hydrocarbon-based groups, and a hydrogen atom;

R25 is chosen from:

and a hydrogen atom;

R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups. The hydrocarbon-based groups are advantageously linear.

Mention may be made, for example, of the compounds of formula (VI) such as the diacyloxyethyldimethylammonium, diacyloxyethyl hydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium and monoacyloxyethylhydroxyethyldimethyl ammonium salts (chloride or methyl sulfate in particular), and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil, such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.

In certain embodiments, the cationic surfactant may be chosen from cetrimonium chloride, behentrimonium chloride, hexadecyltrimethylamonium chloride, or a mixture thereof.

The amount of cationic surfactant employed in the present disclosure may be from about 0.01 to about 5 wt.%, about 0.01 to about 4 wt.%, about 0.01 to about 3 wt.%, about 0.01 to about 2 wt.%, or from about 0.05 to about 5 wt.%, about 0.05 to about 4 wt.%, about 0.05 to about 3 wt.%, about 0.05 to about 2 wt.%, or from about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.%, about 0.1 to about 3 wt.%, or about 0.1 to about 2 wt.%.

NONIONIC SURFACTANTS

The nonionic surfactant may be fatty alcohols, alkoxylated alcohols, alpha-diols and (CrC ₂₄ )alkylphenols, these compounds being polyethoxylated, polypropoxylated and/or polyglycerolated, and containing at least one fatty chain comprising, for example, from 8 to 40 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to especially range from 2 to 50, and for the number of glycerol groups to especially range from 2 to 30.

Mention may also be made of copolymers of ethylene oxide and propylene oxide, optionally oxyethylenated sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyalkylenated fatty acid esters, polyoxyalkylenated fatty amides, optionally oxyalkylenated alkyl(poly)glucosides, alkylglucoside esters, derivatives of N-alkylglucamine and of N-acylmethylglucamine, aldobionamides, amine oxides and (poly)oxyalkylenated silicones.

The nonionic surfactants are more particularly chosen from monooxyalkylenated or polyoxyalkylenated and monoglycerolated or polyglycerolated nonionic surfactants, and alkyl(poly)glucosides. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.

Useful nonionic surfactants may include: oxyalkylenated (C ₈ - C2 ₄ )alkylphenols; saturated or unsaturated, linear or branched, oxyalkylenated Cs-C ₄ o alcohols; saturated or unsaturated, linear or branched, oxyalkylenated C8-C30 amides; esters of saturated or unsaturated, linear or branched, C ₈ -C ₃ o acids and of polyethylene glycols; saturated or unsaturated, oxyethylenated plant oils; condensates of ethylene oxide and/or of propylene oxide, alone or as mixtures; oxyethylenated and/or oxypropylenated silicones; and alkyl(poly)glucosides.

As examples of monoglycerolated or polyglycerolated nonionic surfactants, monoglycerolated or polyglycerolated C ₈ -C ₄₀ alcohols are useable. Mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1 .5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol. The alcohol may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohols may coexist in the form of a mixture.

The alkyl(poly)glycoside (or alkyl(polyg)lucoside) nonionic surfactant(s) may be represented by formula (VIII) below:

(VIM)

in which:

R30 represents a saturated or unsaturated, linear or branched alkyl group comprising from about 8 to 24 carbon atoms, or an alkylphenyl group in which the linear or branched alkyl group comprises from 8 to 24 carbon atoms;

R31 represents an alkylene group containing from about 2 to 4 carbon atoms,

G represents a saccharide unit comprising from 5 to 6 carbon atoms, t denotes a value ranging from 0 to 10, or from 0 to 4, and

v denotes a value ranging from 1 to 15.

In some cases, the alkyl(poly)glycoside nonionic surfactant(s) correspond to formula (VIII) in which:

R30 denotes a linear or branched, saturated or unsaturated alkyl group containing from 8 to 18 carbon atoms,

G denotes glucose, fructose or galactose, preferably glucose, t denotes a value ranging from 0 to 3, and is preferably equal to 0, and R31 and v are as defined previously.

The degree of polymerization of the alkyl(poly)glucoside nonionic surfactant(s), as represented, for example, by the index v in formula (VIII), ranges on average from 1 to 15, or from 1 to 4. This degree of polymerization more particularly ranges from 1 to 2 and better still from 1 .1 to 1 .5, on average.

The glycoside bonds between the saccharide units are of 1 .6 or 1 .4 type and preferably of 1 .4 type.

Examples of compounds of alkylpolyglucoside that may especially be mentioned are decyl glucoside, lauryl glucoside, cetearyl glucoside, coco-glucoside, and caprylyl/capryl glucoside. The alkylpolyglucoside of the present disclosure may be commercially available from the company BASF under the names PLANTAREN (for example, 1200 and 2000) or PLANTACARE (for example, 810, 818, 1200, 2000, K 55, and PS 10).

The amount of nonionic surfactant employed in the present disclosure may be from about 0.01 to about 5 wt.%, about 0.01 to about 4 wt.%, about 0.01 to about 3 wt.%, about 0.01 to about 2 wt.%, or from about 0.05 to about 5 wt.%, about 0.05 to about 4 wt.%, about 0.05 to about 3 wt.%, about 0.05 to about 2 wt.%, or from about 0.1 to about 5 wt.%, about 0.1 to about 4 wt.%, about 0.1 to about 3 wt.%, or about 0.1 to about 2 wt.% or about 0.1 to about 1 wt.%.

The NLCs of the present disclosure may be employed in compositions such as cosmeceutical compositions, cosmetic compositions, and personal care compositions, for example hair care compositions. Such compositions may also comprise additives chosen from cationic polymers, nonionic polymers, rheology modifiers, thickening and/or viscosity modifying agents, amphoteric or zwitterionic surfactants, anionic surfactants, nacreous agents, dyes or pigments, fragrances, mineral or synthetic oils, waxes, vitamins, proteins including ceramides, vitamins, UV- screening agents, free-radical scavengers, antidandruff agents, hair-loss counteractants, hair restorers, preserving agents, pH stabilizers and solvents, and mixtures thereof. A person skilled in the art will take care to select the optional additives and the amount thereof such that they do not harm the properties of the compositions or of the NLCs of the present disclosure.

The amphoteric or zwitterionic surfactant that may be used in compositions according to the disclosure may be derivatives of aliphatic secondary or tertiary amines, optionally quaternized, in which derivatives the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, the amine derivatives containing at least one anionic group, such as a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may be made in particular of (C ₃ - C2o)alkylbetaines such as cocoylbetaine, sulfobetaines, (C8-C2o)alkylamido(C2- C ₈ )alkylbetaines such as cocoylamidopropylbetaine or (C ₈ -C2o)alkylamido(C6-C ₈ )- alkylsulfobetaines, and mixtures thereof.

Other examples of amphoteric or zwitterionic surfactants are disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.

The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are chosen preferably from the groups CO ₂ H, CO ₂ ^" , SO ₃ H, SO ₃ ^" , OSO ₃ H, OSO ₃ ^" O ₂ PO ₂ H, O ₂ PO ₂ H and O ₂ PO ₂ ^2" .

The anionic surfactant(s) that may be used may be alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, alpha-olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosi nates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyltau rates, salts of alkyl monoesters and polyglycoside-polycarboxylic acids, acyllactylates, salts of D- galactoside uronic acids, salts of alkyl ether carboxylic acids, salts of alkyl aryl ether carboxylic acids, and salts of alkylamido ether carboxylic acids; or the non-salified forms of all of these compounds, the alkyl and acyl groups of all of these compounds containing from 6 to 24 carbon atoms and the aryl group denoting a phenyl group. Some of these compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.

The salts of C ₆ -C ₂₄ alkyl monoesters of polyglycoside-polycarboxylic acids may be chosen from C ₆ -C ₂₄ alkyl polyglycoside-citrates, C ₆ -C ₂₄ alkyl polyglycoside-tartrates and C -C,2 alkyl polyglycoside-sulfo succinates.

When the anionic surfactant(s) are in salt form, they may be chosen especially from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts, or alkaline-earth metal salts such as the magnesium salt.

Use is also made of (C6-C2 ₄ )alkyl sulfates, (C6-C2 ₄ )alkyl ether sulfates, which are optionally ethoxylated, comprising from 2 to 50 ethylene oxide units, and mixtures thereof, in particular in the form of alkali metal salts or alkaline-earth metal salts, ammonium salts or amino alcohol salts. More preferentially, the anionic surfactant(s) are chosen from (Cio-C2o)alkyl ether sulfates, and in particular sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide.

The rheology modifiers and thickening/viscosity-modifying agents that may be employed in compositions of the present disclosure may include any water- soluble or water-dispersible compound that is compatible with the compositions of the disclosure, such as acrylic polymers, non-acrylic polymers, starch, cellulose-based polymers, non-polymeric and polymeric gelling agents, and mixtures thereof.

Embodiments of the disclosure also relate to a process for treating keratinous materials, such as hair, comprising applying an effective amount of a composition as defined herein to the said keratinous materials.

Implementation of the present disclosure is provided by way of the following examples. The examples serve to illustrate the technology without being limiting in nature.

EXAMPLE 1

(Inventive Compositions)

Murumuru butter (m.p. 33-35 ^Q C) and bis-diglyceryl polyacyladipate-2 (m.p. around 35 ^Q C) are both solids at room temperature. They were melted together at a temperature of 45 ^Q C. The melted combination of murumuru butter and bis- diglyceryl polyacyladipate-2 was then added to buriti oil, which is a liquid at room temperature. The liquid combination of the three fatty compounds was added to an aqueous solution (water) containing 0.7% of cetrimonium chloride or behentrimonium chloride (0.5 wt.% of the total composition) at the same temperature of about 45 ^Q C and mixed at 15,000 rpm using an Ultra-Turrax dispersing device, forming a pre- emulsion.

The pre-emulsion was then subjected to first homogenization at a pressure of 700 bar, followed by a second homogenization at a pressure of 70 bar. The first and second homogenizations were repeated for three cycles. After completing the homogenization cycles, the homogenate was cooled in an ice bath at 15 ^Q C. The resulting NLCs had an average diameter of 160-250 nm and zeta potential of +40 mV and +75 mV. The composition remained stable for at least 180 days at room temperature.

Figure 1 shows images obtained by confocal microscopy, showing differences between particles in the different stages of the manufacturing process. Figure 1 (a) is an image of the pre-emulsion; Figure 1 (b) is an image after a first homogenization cycle (a first homogenization at a pressure of 700 bar, followed by a second homogenization at a pressure of 70 bar); Figure 1 (c) is an image after a second homogenization cycle; and Figure 1 (d); is an image after a third homogenization cycle. As the homogenization cycles are repeated, the NLCs become smaller and more uniform in. Table 2 shows sizes (nm), polydispersity rate (PDI), and zeta potential (mV) for the various stages.

Table 1

EXAMPLE 2

(Crystallinity Evaluations)

Differential Scanning Calorimetry (DSC) was used to study the crystallinity of the NLCs. Table 1 compares the properties of the NLCs with each of the individual lipid components. It reports the melting temperature (T _me iting), crystallization temperature (T _cr yst), melting enthalpy (AH _me mng) and crystallization enthalpy (AH _cryst ). Table 2

The data show that the melting and crystallization enthalpies of the pure lipid murumuru are much higher than the enthalpy of the NLCs. A higher melting enthalpy represents more internal order, i.e., a more rigid crystalline structure. The NLCs have lower enthalpy and therefore less crystallinity, thereby allowing an active agent to be easily retained within the amorphous gaps in the material. The low crystallinity also contributes to improved shelf-life because the active ingredient does not separate or "leak out" from the NLCs over time.

EXAMPLE 3

(SPF Evaluations)

Table 3 provides the sun protection factor (SPF) for NLCs having different amounts of oil (buriti oil) and Table 4 shows the SPF for various oils, as reported in the literature. The data in Tables 3 and 4 show that the NLCs of the instant disclosure exhibit higher SPFs than pure buriti oil and other natural oils. The SPF of the NLCs is at least 20 (twenty) times greater than the SPF of pure Buriti oil. Thus, the NLCs themselves may be used to provide protection from ultraviolet radiation, or can be used to carry or encapsulate additional ultraviolet light absorbing agents (sunscreen agents).

Table 3

Nanoparticles SPF

Pure buriti oil (literature) 1 .0 ± 0.1

Pure buriti oil (experimental) 1 .18 Nanoparticles SPF

NLCs (6.0 g of solid lipids) of murumuru with

10.15

10% buriti oil

NLCs ( 12.0 g of solid lipids) of murumuru with

21 .82

10% buriti oil

NLCs ( 12.0 g of solid lipids) of murumuru with

22.92

20% buriti oil

Table 4 provides the sun protection factor (SPF), calculated spectrophotometry, for other oils.

Table 4

EXAMPLE 4

(Hair Treatment Studies)

The inventive composition (Formula 1 ) of Example 1 is applied to hair using the following procedure. For each gram of hair, 0.15 grams of the composition of Examples 1 and 2 is applied to hair swatches. The composition is spread along the swatches from the roots to the ends in a homogenous manner. The composition is then massaged into the hair by passing two fingers five times through the hair, without creating knots. If knots form, the swatches are combed with a wide-tooth comb followed by a fine-tooth comb. The swatches are then dried under a drier at 60°C for ten minutes for each gram of hair.

Figure 2 provides images obtained by confocal microscopy of an untreated hair fiber (Figure 2(a)) and a hair fiber treated with the NLCs of Example 1 (Figure 2(b)). Confocal microscopy was performed using a Zeiss LSM 780-NLO confocal on an Axio Observer Z.1 microscope (Carl Zeiss AG, Germany) equipped with a 60 x oil immersion lens. The NLC with Murumuru butter, Bis-diglyceryl polyacyladipate-2 and Buriti, using as Cetrimonium chloride as surfactant are marked with a fluorescent dye, Rhodamine-PE in order to follow the NLC on hair's surface. Figure 2(b) shows that the NLCs adhered to the surface of the hair fiber and even, to some extent, penetrated the inner part of the hair fiber. This demonstrates that the NLCs have high affinity and adherence to hair fibers. Accordingly, the NLCs are useful for protecting hair from damage, for repairing already damaged hair, and for carrying an active ingredient to or into the hair.

Figures 3(a) and (b) provide images of the NLCs generated by cryomicroscopy and using Electron microscopy model JEM-2100 (JEOL, Japan), LaB6, 200KV equipped with camera F-416 (TVIPS, Germany) 16 MPixel. The figures show the presence of circular particles (NLCs) having a diameter of about 15- 140 nm. The NLCs did not aggregate and retained this individuality.

Figures 4(a) and (b) provide images obtained by high-resolution scanning electronic microscopy (SEM). Analyses were performed on a microscope and JEOL (JSM-6360LV), using an acceleration voltage of 20 kV. The SEM images show the difference between the untreated hair swatches (only washing with distilled water) and the hair swatches that have treated with Murumuru's NLC for 2 minutes and then washed with distilled water to remove excess of NLC. The images show the difference in the surface of a non-treated hair fiber (Figure 4(a)) with the surface of hair fiber treated with NLCs (Figure 4(b)). The hair fiber treated with NLCs shows better surface homogeneity and surface recovery than the untreated hair fiber.

Figures 5(a) and (b) are more detailed, close-up (enlarged) images of the surfaces of the hair fibers of Figure 4(a) and (b). These images show that the untreated hair fiber has nothing on its surface; whereas the treated hair fiber has NLCs attached.

The foregoing description illustrates and describes the disclosure. Additionally, the disclosure shows and describes only the preferred embodiments but, as mentioned above, it is to be understood that it is capable to use in various other combinations, modifications, and environments and is capable of changes or modifications within the scope of the invention concepts as expressed herein, commensurate with the above teachings and/or the skill or knowledge of the relevant art. The embodiments described herein above are further intended to explain best modes known by applicant and to enable others skilled in the art to utilize the disclosure in such, or other, embodiments and with the various modifications required by the particular applications or uses thereof. Accordingly, the description is not intended to limit the invention to the form disclosed herein. Also, it is intended to the appended claims be construed to include alternative embodiments.

As used herein, the terms "comprising," "having," and "including" are used in their open, non-limiting sense.

The terms "a," "an," and "the" are understood to encompass the plural as well as the singular.

The expression "at least one" means one or more and thus includes individual components as well as mixtures/combinations.

All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc.

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions may be modified in all instances by the term "about," meaning within 10% of the indicated number (e.g. "about 10%" means 9% - 1 1 % and "about 2%" means 1 .8% - 2.2%), such as within 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1 %, according to various embodiments. "Keratinous substrates" or "keratinous materials" as used herein, includes, but is not limited to keratin fibers such as hair on the human head and hair comprising eyelashes. "Keratinous substrates" or "keratinous materials" as used herein, may also refer to the skin such as lips, finger nails or toe nails, and the scalp. As used herein, the term "applying a composition onto "keratinous substrates" includes "applying a composition onto "keratinous substrates" or "keratin materials" such as hair on a human head with at least one of the compositions of the disclosure, in any manner.

All publications and patent applications cited in this specification are herein incorporated by reference, and for any and all purposes, as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. In the event of an inconsistency between the present disclosure and any publications or patent application incorporated herein by reference, the present disclosure controls.