New compositions and methods for shaping fibers

Abstract

The present disclosure relates to a method for modifying the shape of permeable fibers, such as keratinous fibers, enabling in particular styling of mammalian hair fibers. The method comprises applying to the fibers a composition comprising a natural polymer and a fatty agent, both being water-insoluble and jointly polymerizable, and a water-soluble hygroscopic agent, all afore-said ingredients being small enough to permit their penetration within the fibers; leaving the composition on the fibers for sufficient time so that at least part of said materials penetrate within the fibers; and curing the water-insoluble ingredients to internally form a shapeable polymer capable of maintaining the fibers in a desirable shape. Compositions adapted for such method and kits allowing to prepare the same are also disclosed.

Description

[0001] NEW COMPOSITIONS AND METHODS FOR SHAPING FIBERS CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims Paris Convention priority from Great Britain patent application GB 2415820.6 filed on October 28, 2024, the entire disclosures of which are hereby incorporated by reference, as if fully set forth herein.

[0003] FIELD

[0004] The present disclosure relates to compositions, kits, and methods for modifying the shape of permeable fibers, including for styling keratinous fibers, such as mammalian hair.

[0005] BACKGROUND

[0006] The mammalian (e.g., human) hair fiber is a layered structure, wherein the outermost layer is the cuticle, a thin protective layer made of keratin protein, surrounding a central hair shaft composed of a cortex and a medulla. The cuticle layer is built from scale-shaped cells, layered one over the other in an overlapping manner, similarly to shingles on a roof. The physical appearance and the shape of hair fibers are determined by a variety of interactions between the keratin chains within the fibers, the amino acid composition of the keratin being responsible for the types of possible interactions. Cysteine side chains allow for the formation of disulfide bonds, while other amino acids residues may form weaker interactions such as hydrogen bonds, hydrophobic interactions, ionic bonds, Coulombic interactions etc. The presence of such reactive groups in the fiber, their proportion along the fiber as well as their availability to react due to the fiber conformation, determine the occurrence of these interactions and the appearance of the fiber or of the head hair constituted by a plurality of such fibers.

[0007] The disulfide covalent bonds that may form between two thiol side-chains of two adjacent cysteine residues account for the fibers’ structure stability, durability and mechanical properties, and the breaking of these bonds by various procedures is the mechanism behind most contemporary methods of permanent hair styling (mainly straightening or waving).

[0008] One such procedure, termed “Japanese straightening”, involves reductive agents, e.g., mercaptans or sulfites, which selectively cleave the disulfide bonds, whereby the keratins mechanically relax, followed by re-oxidation of the free sulfhydryl groups, allowing for the recombination of the disulfide bonds at the end of the process, while the hair is in the conformation adapted to achieve the desired styling. Various styling means, such as hot iron or hair dryer, can be used to induce additional stress to permanently conform the hair to the desired shape (whether straight or wavy).

[0009] Another procedure for permanent styling of the hair relies on even harsher reductive agents, such as strong alkaline agents at pH higher than 11.0. Under these conditions, the disulfide bonds are cleaved in a less selective manner when the alkaline agents deeply permeate into the pH-induced swelled hair, disrupting possible rearrangement of the disulfide bonds.

[0010] Other procedures, termed “keratin straightening” and “organic straightening”, and including “Brazilian straightening”, are considered semi -permanent, and involve the massive use of aldehydes, namely, formaldehyde, formaldehyde-producing agents, or glutaraldehyde, most straightening products containing 2-10% of such chemicals. Exemplary formaldehyde-producing agents, also referred to as formaldehyde-releasing agents, include glyoxylic acid and its derivatives (e.g., glyoxyloyl carbocysteine), some of them being commonly used as preservatives. These aldehyde-based or -producing agents react with the keratin in the hairfibers, acting as cross-linkers, thus prolonging the durability of the new hair conformation and shape. Formaldehyde and glutaraldehyde are considered carcinogenic, and can cause eyes and nose irritation, as well as allergic reactions of the skin, eyes, and lungs. They are therefore considered hazardous by the Occupational Safety and Health Administration (OSHA), and hair styling products manufacturers are required to comply with a limit of 0.2 weight by weight percentage (wt.%) or less of these materials, some jurisdictions even requiring 0.1 wt.% or less, by weight of the composition. Sadly, even products marketed as “formaldehyde free” or apparently lacking formaldehyde in their list of ingredients, have been found to contain or produce this substance during the styling process (e.g., whilst heating the hair) leaving the community in doubt concerning the claimed safety of such “non-formaldehyde” containing keratin-straightening products. Reports suggest that formaldehyde may simply be replaced by formaldehyde-producing agents in such products.

[0011] Some permanent or semi-permanent straightening methods require the use of dedicated shampoos to maintain their effect over time, such products being adapted to the particular chemical reaction each such treatment may rely on to affect hair shape. In addition, such methods show little flexibility if one wishes to further change a hair color, a hair style or to revert to the natural style, such steps typically requiring either conducting a new permanent treatment, further damaging the hair, or waiting for regrowth of hair.

[0012] The amino acids making up the keratin protein of hair fibers also contain side-chains capable of forming non-covalent weaker bonds, such as hydrogen bonds that may form between polar and / or charged side chains in the presence of water molecules. Such hydrogen bonds can form between the amino acids on the outer surface of the cuticle scales, as well as on the internal part of the scales or beneath them. Breaking of these hydrogen bonds upon exposure of the hair to heat (e.g., by a flat iron, a curling iron or a salon or handheld hair dryer, thus allowing removal of the water from the hair), and their reformation by drying or cooling, provides for a temporary hair styling. While such methods do not involve reagents damaging to the hair, their effect is transient, due to the sensitivity of the fibers so shaped to water, including to ambient relative humidity.

[0013] The classification of hair styling methods between permanent, semi -permanent or temporary typically depends on the number of shampoos it may take for the hair to regain its native shape. Permanent methods may be so harsh as to require growth of new hair fibers and whilst some non-transient styling may be voluntarily reversed, such methods may by themselves be damaging.

[0014] In WO 2021 / 224784, WO 2021 / 224785, WO 2021 / 224786, WO 2021 / 224794, WO 2021 / 224789, WO 2021 / 224793 and WO 2023 / 021455, the Applicant has already proposed diverse hair styling methods, which reduce the need for hair-damaging and hazardous reagents, and advantageously provide long-lasting style and shape for the hair. Interested readers are referred to these patent applications of the Applicant, the contents of which are incorporated by reference for all purposes, as if fully set herein

[0015] These methods rely on various water-insoluble monomers, which are small enough to penetrate within the hair fibers, where they can polymerize into shapeable water-insoluble polymers. New compositions including curable hair penetrating monomers may still be beneficial.

[0016] SUMMARY

[0017] The present disclosure relates to compositions, kits and methods comprising or using the same, for styling of (e.g., mammalian hair) fibers developed in order to overcome, inter alia, at least some of the drawbacks associated with traditional methods of hair styling and providing a further alternative to the novel methods previously developed by the Applicant. As used herein “styling” includes any action modifying the fibers’ shape in a visually detectable and desirable manner, with respect to hair fibers it includes straightening or relaxing of hair, if wavy, curly or coiled; or conversely curling of hair, if the hair is relatively straighter than desired; hence any increase or decrease of the natural tendency of the hair fibers to curl. When the styling is intended to achieve intermediate relaxation of hair coils, it can be assimilated for instance to a method of controlling frizz in the mammalian hair.

[0018] While predominantly described with respect to the styling of mammalian hair fibers, in particular with respect to human hair, the present invention may serve for providing a desired shape to other permeable fibers. Shaping of such fibers can address an esthetic purpose, a functional one (e.g., shaped fibers being easier to weave than more randomly arranged ones), or both. Permeable fibers can be natural, plant-derived (e.g., bamboo, cotton, hemp, linen, etc.) or animal-derived (e.g., wool, silk, feathers, etc.), or synthetic (or semi-synthetic e.g., cellulose based fibers, such as cupro, rayon, lyocell and modal, etc.).

[0019] There is provided in one aspect of the present disclosure a composition for styling (e.g., mammalian hair) fibers as hereinafter set forth in more detail and claimed in Claim 13 of the appended claims and claims depending therefrom. Briefly, constituents of the composition which include water-insoluble polymerizable constituents (jointly referred to as curable natural polymers and fatty agents, CNPFAs) (and optionally water-soluble hygroscopic agents (WHAs)) are selected to penetrate within the (e.g., hair) fibers, where the polymerizable constituents can react one with another so as to internally form a heat-shapeable polymer, said polymerization being triggered or facilitated by application of energy. The composition may therefore also be referred to as a curable composition, or a heat curable composition when the energy enhancing polymerization is thermal. In other words, there is provided a curable composition for use in the shaping of permeable fibers, the constituents of the compositions penetrating within the fibers and forming therein a shapeable polymer.

[0020] There is provided in another aspect of the present disclosure a method of styling (e.g., mammalian hair) fibers by modifying the shape of the fibers from a native shape to a desired modified shape as hereinafter set forth in more detail and claimed in Claim 1 of the appended claims and claims depending therefrom.

[0021] There is provided in a further aspect of the present disclosure a method of re-styling or de-styling (e.g., mammalian hair) fibers treated by the present compositions or methods, hence including within the fibers a heat-shapeable polymer as herein taught and having acquired a first modified shape different from the native shape of the fibers, by adapting the first modified shape of the fibers to a desired second modified shape being same or different than the first modified shape, the second modified shape further including the native shape, as hereinafter set forth in more detail. There is provided in yet another aspect of the present disclosure a method of prolonging the artificial coloration of (e.g., mammalian hair) fibers colored by internalization of coloring agents by treating the colored fibers with the present compositions or methods, the heat-shapeable polymer as herein taught delaying the egress of the coloring agents from the colored fibers and thereby the fading of the coloring effect.

[0022] There is provided in yet a further aspect of the present disclosure a kit, combination of parts therein allowing preparing a composition for styling (e.g., mammalian hair) fibers and / or practicing a method for modifying a shape of the fibers from a native shape to a desired modified shape as hereinafter set forth in more detail and claimed in Claim 24 of the appended claims and claims depending therefrom.

[0023] Additional objects, features and advantages of the disclosure will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from the description or recognized by practicing the disclosure as described in the written description and claims hereof, as well as the appended drawings. Various features and subcombinations of embodiments of the disclosure may be employed without reference to other features and sub-combinations.

[0024] BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Some embodiments of the disclosure will now be described further, by way of example, with reference to the accompanying figures, where like reference numerals or characters indicate corresponding or like components. The description, together with the figures, makes apparent to a person having ordinary skill in the art how some embodiments of the disclosure may be practiced. The figures are for the purpose of illustrative discussion and no attempt is made to show structural details of an embodiment in more detail than is necessary for a fundamental understanding of the disclosure. For the sake of clarity and convenience of presentation, some objects depicted in the figures are not necessarily shown to scale.

[0026] In the Figures:

[0027] Figure 1 shows a simplified schematic diagram of an exemplary method for modifying the shape of fibers according to the present invention.

[0028] Figure 2 A shows a photograph of untreated curly black hair fibers.

[0029] Figure 2B shows a photograph of curly black hair fibers treated with an exemplary hair styling composition according to the present invention. Figure 3 shows an illustrative Differential Scanning Calorimetry (DSC) series of plots of thermal analysis of hair samples, including of a reference untreated hair sample, two hair samples treated by commercial methods, and one hair sample treated by a hypothetical innocuous composition according to the present invention.

[0030] Figure 4 shows an image captured by Focussed Ion Beam milling combined with Scanning Electron Microscopy (FIB-SEM), showing a cross-section of a hair fiber treated with a composition according to present teachings, Fig. 4A displaying the actual picture and Fig. 4B a schematic representation of the same.

[0031] DETAILED DESCRIPTION

[0032] Before explaining at least one embodiment in detail, it is to be understood that the disclosure is not necessarily limited in its application to the exemplary materials and / or methods set forth herein, only intended to provide an overview or framework to understanding the nature and character of the disclosure as it may be claimed. The disclosure is capable of other embodiments or of being practiced or carried out in various ways. The phraseology and terminology employed herein are for descriptive purpose and should not be regarded as limiting. For instance, while reference is often made to head hair to illustrate the advantages of the present invention for providing a desired shape to permeable fibers, it is clear that the present teachings would similarly apply to wigs, hair extensions, or eyelashes, to name a few alternatives of these particular keratinous fibers. Thus, providing a durable hair style may be to hair attached to a human subject, to wigs or hair extensions, and the terminology further includes, by way of example, providing a durable eyelash shape, to eyelashes. Moreover, keratinous (e.g., hair) fibers are not the sole permeable fibers which may benefit from shaping, for esthetical and / or functional purposes. All alternative fibers which can be penetrated or impregnated by the present composition and additional uses more pertinent to the treated fibers are encompassed.

[0033] The present disclosure relates to compositions for modifying the shape of permeable fibers, as can be used for styling hair fibers, and more particularly to curable compositions comprising in an aqueous environment at least one water-insoluble natural polymer (NP) and at least one water-insoluble fatty agent (FA) forming a lipophilic phase, the NPs and FAs being capable of jointly undergoing polymerization by any suitable reaction that creates a macromolecule (the polymerizable ingredients being also referred to as CNPFAs), the composition optionally further including at least one material that may facilitate the formation of the cured polymers and / or extend their activity, so as to prolong, for illustration, the hair styling durability afforded by the cured polymer.

[0034] Natural polymers can be resins or waxes of natural origin, isolated fractions and / or chemically processed versions of the same, or synthetic equivalents or derivatives of said materials being functionally comparable or preferable to the native materials as can be found in nature. The fatty agents (FAs) can be fatty amines (FA1s), fatty alcohols (FA2s) or fatty acids (FA3s) depending on the reactive groups attached to the aliphatic chains causing the hydrophobicity of the FAs. The material capable of enhancing the effect of the cured polymer is a water-soluble hygroscopic agent (WHA) able to bind water molecules. Such a WHA is believed to first favor penetration of the CNPFAs within the fibers, then sequester water molecules which might have otherwise detrimentally interacted with the cured polymer, with the hair keratin and / or with any other hair constituent, in a manner affecting the constrained shape enabled by the curing of the CNPFAs. The polymer formed internally to the fibers can be shaped as desired, having a thermoplastic behavior at least during their initial shaping by application of heat. The new shape afforded by the forming polymer can be reversibly modified by application of further heat, either while the polymer is still insufficiently cured to form a heat-resistant thermoset polymer or by application of heat exceeding the glass transition temperature of the polymer if sufficiently cured to behave as a thermoset polymer. The macromolecules resulting from the curing of the CNPFAs can therefore also be referred to as the shapeable polymers or the heat shapeable polymers.

[0035] Without wishing to be bound by any particular theory, the Inventors have discovered that surprisingly, the WHA(s), though being water-soluble and expected to leak out of the hair fibers readily following rinsing of treated hair or with relative ease with each shampoo, vanishing after only a few ones (e.g., less than 5, less than 4, or less than 3), are providing a protective / prolonging effect with respect to the duration of the hair styling provided by a desired shaping of the shapeable polymer. The Inventors posit that the WHAs are capable of sufficiently remaining within the hair fibers, either as isolated “water-absorbing” bodies, or in interaction with the polymers cured from the present CNPFAs, or in interaction between the cured polymers and natural constituents of the hair fibers, or in interaction with natural constituents of the hair fibers, or in any like mechanism of action or combinations thereof. This prolonged presence of the WHAs within the hair, in turn, reduces or delays the loss in styling effect, procured by the CNPFAs, otherwise normally observed over time. In other words, if a composition lacking a WHA provides for a desired hair styling resisting N washing cycles, a similar hair styling composition further including a WHA provides for a desired hair styling resisting M washing cycles, M being greater than N, all other conditions (e.g., of application) being the same.

[0036] Furthermore, the Inventors have discovered that surprisingly, compounds deemed essential to a similar polymerization process, or facilitating it, in previously developed compositions could be omitted. The present invention departs from WO 2023 / 021455 to the same Applicant, by obviating the need for the phenol-based monomers (PBMs), consequently alleviating the necessity or preference to further include some curing facilitators. Favorably, a lower number of ingredients can be used, simplifying the composition and its preparation. This can be particularly beneficial when the materials being omitted are relatively sensitive to environmental factors and / or chemical interactions with other ingredients of the composition that may cause their early depletion whether by degradation or utilization. Precautions that should be implemented in such a case can be costly and / or not fully effective over long periods of time, so that any composition that may be devoid of such susceptible materials, and avoid the challenging problems they may cause, are deemed advantageous.

[0037] General requirements

[0038] Size of permeating compounds

[0039] As a rule, materials due to penetrate or impregnate fibers should have shapes and dimensions adapted to the shape and being smaller than the dimensions of the pores, or any other type of apertures in the fibers, enabling penetration within inner parts. Without wishing to be bound by any particular theory, it is believed that smaller molecules may more easily migrate into permeable fibers than larger ones. While the physical size of molecules may depend on additional factors (such as spatial conformation and “compactness”, or lack thereof, within any particular media), the molecular weight of a compound may serve as primary feature to select materials prospectively suitable to penetrate particular fibers.

[0040] In some cases, the ingredients of the present composition intended to penetrate within the (e.g., hair) fibers (e.g., NPs, FAs, CNPFAs, WHAs, co-solvents, etc. can have an average molecular weight (MW) of at least 50 g / mol and up to 150 g / mol, up to 300 g / mol, up to 500 g / mol, or up to 1,000 g / mol. For illustration, most of the envisioned FAs and WHAs are typically in a range of 50-500 g / mol, though not limited thereby, MWs of up to 1,000 g / mol being also suitable. Notably, while the ability of molecules larger than 500 g / mol to efficiently penetrate hair fibers has remained elusive, the Applicant has found that materials having much higher MWs, as often associated with NPs, in particular if pre-polymerized with the FAs, can also be used. It is nevertheless believed that the MW of the fiber-penetrating water-insoluble ingredients of the present composition should be no more than 10,000 g / mol. For illustration, NPs may have a MW of no more than 7,500 g / mol, no more than 5,000 g / mol, no more than 3,000 g / mol, no more than 2,500 g / mol, no more than 2,000 g / mol, no more than 1,500 g / mol, or no more than 1,000 g / mol, their smallest MWs being often at least 300 g / mol, at least 400 g / mol or at least 500 g / ml. Thus, while relatively small molecules (e.g., having a MW in a range of 50-1,000 g / mol, 50-750 g / mol or 50-500 g / mol) may satisfactorily be used, present compositions may also include relatively large materials (e.g., having a MW in a range of 500-10,000 g / mol, 500-7,5000 g / mol or 500-5,000 g / mol).

[0041] The molecular weight of molecules having a known chemical formula can be calculated based on the molecular mass of its constituting atoms, in which case the average molecular weight is simply the molecular weight assigned to the specific molecule. For compounds formed of unknown or diverse chemical formulae, such as polymers, the average molecular weight of the population of related molecules can be provided by the supplier of the material, or independently determined by standard methods, such as high pressure liquid chromatography (HPLC), size-exclusion chromatography, light scattering, gel permeation chromatography (GPC), or matrix-assisted laser desorption / ionization time-of-flight mass spectroscopy MALDI-TOF MS, and some of these methods are described in ASTM D4001 or ISO 16014-3. Average molecular weight can then be estimated by number or by weight, both being encompassed herein.

[0042] Such MW may correlate with the compactness of the molecules, which in order to penetrate, for example, hair fiber should have a molecular diameter of less than 2 nm, less than 1.8 nm or less than 1.6 nm.

[0043] Water Solubility

[0044] As can be readily appreciated, materials being water-insoluble are expected to resist moisture or aqueous washes for longer periods of time than materials being water-soluble that may readily dissolve and wash away, accordingly shortening any effect they may have on the fibers. That being said, using water-insoluble materials creates formulatory hurdles and obstacles for delivery to fibers hydrophilic in nature (e.g., bleached or otherwise damaged hairs). The solubility of materials deemed water-insoluble can be of 1 wt.% or less, 0.5 wt.% or less, 0.4 wt.% or less, 0.3 wt.% or less, 0.2 wt.% or less, 0.1 wt.% or less or 0.05 wt.% or less, with respect to the weight of pure water (e.g., deionized water having a pH of about 7), and more appropriately with respect to the weight of the aqueous environment wherein they are to be disposed at the pH of the liquid. Solubility can be assessed at any temperature of relevance to the use or method of application of the composition, but is generally reported for temperatures between 15°C and 25°C, or between 20°C and 25°C, which include room temperature circa 23 °C (RT).

[0045] For illustration, one weight part or less of a relatively insoluble material would dissolve in hundred weight parts of the liquid (e.g., less than 1 g of material per 100 g of water, the total amount of the mix being 101 g and the wt.% of the material in the entire composition being about 0.99% or less). Solubility of a material in pure neutral water, or lack thereof, is a property often reported in the data sheet of a material or in pertinent handbooks. It can be assessed independently by the naked eye, by trying to dissolve known amounts of the material in pure water or an aqueous liquid of relevance, the composition formed of soluble materials being typically clear (not turbid) at room temperature (z.e., forming a single-phase composition). This matter can alternatively be quantified by measuring the refractive index of the solution, comparing it to a calibration curve with known amounts of materials in water.

[0046] Conversely, water-soluble materials, such as the WHAs, have a solubility in pure water, or in an aqueous environment wherein it is to be disposed, of 1 wt.% or more, 5 wt.% or more, 10 wt.% or more, 15 wt.% or more, 20 wt.% or more, 25 wt.% or more, 30 wt.% or more, or 35 wt.% or more. While water-soluble materials can have even higher solubilities, the WHAs generally have a solubility of 150 wt.% or less, 125 wt.% or less, 100 wt.% or less, or 75 wt.% or less, by weight of the water, or aqueous liquid, as measured at a temperature of 25°C.

[0047] Miscibility

[0048] The polymerizable ingredients (z.e., the CNPFAs), together with any compound that may be required for their proper polymerization while within the fibers, should be miscible one with another whilst at this location to enable their interactions. Compounds are deemed miscible if forming a single phase, this being assessed more easily at the level of the composition. This sought miscibility can be inherent to the materials being considered, dependent on their relative proportions, or assisted by a treatment of the mixture and / or the presence of a co-solvent. For illustration, a natural polymer solid at room temperature can be miscible with a fatty agent (e.g., a fatty amine, a fatty alcohol, and / or a fatty acid) liquid under the same conditions, the CNPFAs being optionally jointly heated to increase miscibility. Heating of the CNPFAs, if desired or required, can be performed at a temperature high enough to facilitate the formation of a single liquid phase, but sufficiently low so as to avoid polymerization of the CNPFAs prior to their application to the fibers, this process, when sought, being referred to as pre-polymerization. Compounds can be jointly miscible while in a water-insoluble phase of the composition, or conversely in the water-soluble environment, where the WHAs generally reside before entering (at least in part) the fibers.

[0049] Compounds that need not react with the CNPFAs or the WHAs, in their typically distinct phase, such as substances that may reduce, delay or prevent damages to the styling effect afforded by the formed polymer can indifferently be delivered in a same phase with the CNPFAs or with the WHAs. While in presence of suitable amounts (e.g., above 30 wt.%) of appropriate co-solvents, the present composition can entirely be in a single-phase, it is typically in the form of an oil-in-water emulsions, the “oily” lipophilic phase being constituted by the water-insoluble materials.

[0050] Volatility

[0051] When the method of treating fibers with the present compositions involves heating, it may be desired that the ingredients constituting the composition do not degrade or significantly evaporate during the process. As water is mainly serving as carrier to ingredients more pivotal to the formation of the shapeable polymer, the present considerations are mainly directed to them, either as individual ingredients or as blends. The degree of volatility of a material depends on temperature, and the materials should be selected to be relatively non-volatile at the temperature of relevance to a particular process, be it for the preparation of the composition (e.g., the materials having a boiling point above mixing temperature) or its later use.

[0052] Accordingly, to increase the likelihood of a prolonged residency on the fibers during application and styling, and within the fibers thereafter, the non-volatile materials (e.g., NPs, FAs, WHAs) can be selected to have a vapor pressure lower than the vapor pressure of water (z.e., < 2.3 kiloPascal - kPa). In some cases, a material deemed non-volatile has a vapor pressure of 1.0 kPa or less, 0.5 kPa or less, or 0.1 kPa or less, as measured at 25°C. In other cases, the non-volatile material can have a vapor pressure of 50 Pascal (Pa) or less, 25 Pa or less, 10 Pa or less or 1 Pa or less, as measured at 25°C. Usually, the vapor pressure is 1 milliPascal (mPa) or more, 10 mPa or more, or 50 mPa or more. The vapor pressure of a material, e.g., at a temperature between 15°C and 25°C, is typically provided by its manufacturer, but can be readily determined by standard methods, using for illustration Differential Thermal Analysis (DTA) or Differential Scanning Calorimetry (DSC), as described for instance in ASTM El 194, ASTM D2879, or ASTM E1782. Facilitating factors

[0053] The composition could advantageously have a pH adapted to facilitate penetration of at least part of the CNPFAs, WHAs and of any other material necessary for their suitable assembly and for the maintenance of their effects in the permeable fibers. In the case of hair fibers, the facilitating pH (contributed by the aqueous phase) may act by promoting: a) a sufficient opening of the hair scales, and / or b) a sufficient charging (e.g., as measurable by zeta potential) of the hair fibers and hair styling composition; and / or c) by providing a suitable solubility of a compound in a medium (or on the contrary a lack thereof). The pH of the composition is typically alkaline, in a range of pH 8 to pH 11, but it can be modified, if desired, to be either more alkaline having a pH between pH 9 and pH 11, or on the contrary to be acidic, in a range of pH 1 to pH 3.5 or pH 4, or mild acidic to mild alkaline, in a range of pH 5 to pH 8, in which case pH adjusting agents or pH buffering agents can be added to the composition at any concentration adapted to maintain the pH in the desired range. In other words, a pH is deemed to favor penetration into hair fibers if being in ranges other than the isoelectric point of the hair, which may slightly vary between 3.5 and 5, 4 and 5, or 3.5 and 4, depending on the hair fibers and their health status.

[0054] While pH may provide for a sufficient opening of apertures controlling the relative permeability of fibers, this should not be construed as conditioning penetration of the polymerizable ingredients within the fibers to this sole mechanism.

[0055] Before detailing particular compounds suitable for the present methods and compositions, it is stressed that beyond the above-mentioned ability of the CNPFAs (and of any agent facilitating their polymerization) to penetrate within the fibers and to be miscible with one another once and / or as long as the curing is set to proceed, the materials (including the WHAs preventing a water-induced damage to the styling effect and any other desirable substances) need more generally to be compatible with the compositions as a whole, their methods of preparation and their methods of use. By “compatible” it is meant that the natural polymers, the fatty agents (e.g., the fatty amines, the fatty alcohols, or the fatty acids), the water-soluble hygroscopic agents, or any other desirable ingredients of the present compositions (e.g., cosolvents or other additives), do not negatively affect the efficacy of any other compound, or the ability to prepare or use the final composition. Compatibility can be chemical, physical or both and may depend on relative amount. For illustration, the natural polymers and the fatty agents would be compatible if each bearing functional groups able to react one with another (e.g., by acid:base interactions or reactions leading to formation of covalent bonds between the molecules) so as to polymerize into larger macromolecules; a co-solvent would be compatible if having a rate of volatility slow enough for the polymerization to proceed while the relevant materials are in a same phase. Materials would be compatible if not affected by the pH of the composition, or a temperature they might be subjected to during the preparation of the composition or its use (e.g., for hair styling). Materials particularly suitable may furthermore ensure the stability of the composition, or avoid its destabilization, in absence of dedicated additives (e.g., dispersants, emulsifiers, and the like) otherwise permissible in the composition.

[0056] Preferably, the materials used in the compositions should be approved for their intended use, or at a concentration permissible therefor. For illustration, when the compositions are intended for styling human hairs, the materials should advantageously have regulatory approval from relevant authorities preferably be cosmetically acceptable. Ingredients, compositions or formulations made therefrom, are deemed “cosmetically acceptable” if suitable for use in contact with keratinous fibers, in particular human hair, without undue toxicity, instability, irritation, allergic response, and the like. Some ingredients may be “cosmetically acceptable” if present at relatively low concentration according to relevant regulations. Materials being “cosmetically acceptable” or “pharmaceutically acceptable” according to reputable pharmacopeia are clearly commercialized as such by their suppliers.

[0057] Notably, the materials used in the present compositions and their respective proportions can be selected so as to avoid toxic materials or deleterious chemical reactions leading to the formation of toxic products. Considering the particular case of styling of human hairs, the method including heating of hair fibers treated by the present compositions, they should therefore preferably contain less than 0.1 wt.% of small reactive aldehydes (SRA) or materials that may release such a concentration of SRAs while not being aldehyde by themselves. The SRAs (and their precursors) to be avoided can be formaldehyde, formaldehyde-forming chemicals (e.g., diazolidinyl urea, DMDM hydantoin, formalin, glyoxylic acid, imidazolidinyl urea, methylene glycol, Quatemium-15 etc.), glutaraldehyde, glutaraldehyde-forming chemicals (e.g., 2-alkoxy-3,4-dihydropyran), glyceraldehyde, and glyceraldehyde-forming chemicals (e.g., dihydroxyacetone). SRAs whose parent compounds are suitable for present compositions are understandably excluded from prospective derivatives of such substances, when the composition is to be applied to fibers intolerant to the SRAs. For instance, one exemplary WHA is urea, and its permissible derivatives exclude diazolidinyl urea or imidazolidinyl urea, when SRAs are to be avoided in the composition. While SRA levels of 0.1 wt.% can be tolerated by regulation, the present compositions may contain 0.05 wt.% or less, 0.01 wt.% or less. 0.005 wt.% or less, or 0.001 wt.% or less SRA by total weight of the composition.

[0058] While not essential, the materials (e.g., the FAs and the CNPFAs) could be liquid at room temperature, to facilitate preparation and use, or if solid could be readily miscible with the liquid components of the composition (e.g., a water-insoluble NP or a water-soluble WHA solid at RT could readily dissolve in a water-insoluble FA or in water or any other aqueous medium, respectively). If a material is solid at RT (e.g., the NPs) and its dissolution into substances with which it is due to form a single phase requires heating, its melting point should be low enough for the temperature of heating adapted to selectively enhance its dissolution, without prematurely triggering curing of the CNPFAs or otherwise affect their ability to polymerize. If necessary, a non-volatile plasticizer can be included to maintain the composition, in particular the materials due to penetrate the (e.g., hair) fibers, liquid at RT, or at least at the temperature at which the composition may be applied to the fibers. As some polymerizable materials (e.g., FAs) may in addition to their ability to form the inner polymer affect properties of the composition in a manner comparable to a plasticizer, it is specified that when reference is made to a dedicated “plasticizer” added for this sole purpose, such a material is not selected to react with the NPs or FAs.

[0059] The water-insoluble natural polymers

[0060] The natural polymers (NPs), which can also be referred to as resins or waxes (when relatively more malleable near ambient temperature), typically have a water-solubility of 1 wt.% or less in neutral water (having a pH of 7) as measured at a temperature of 25°C. They are typically produced by vegetal (e.g., trees, plants) or animal (e.g., insects) life, some being continuously produced in nature (or recently so, e.g., copal resins), while others are considered as fossils (e.g., amber). Some waxes are of a more mineral origin, such as obtained during the distillation of crude oils. Natural polymers of commercial interest (e.g., shellac) may also exist in the form of synthetic chemical equivalents.

[0061] Suitable NPs are typically solid at room temperature; however, this is not essential as NPs liquid under such conditions may also be used, provided they are combined with solid NPs. The physical state of a material (e.g., liquid or solid) at any given temperature, is generally provided by the supplier of the material, but can be independently visually assessed or estimated based on the melting temperature (Tm) of the material. For illustration, materials solid at RT typically have a Tmof 25°C or more, 50°C or more, 100°C or more, the Tmof the waxes being typically lower than the Tmof the resins. Conversely, materials liquid at RT typically have a Tmlower than 25°C, being even negative as might be the case for some fatty agents, for instance their Tmcan be in a range between -50°C and 20°C, between -25°C and 17.5°C, between -5°C and 15°C, or between 0°C and 12.5°C.

[0062] In some cases, the glass transition temperature (Tg) of the natural polymers is at least -10°C, at least 0°C, at least 10°C, at least 20°C, at least 30°C, at least 40°C, or at least 50°C, such glass transition temperature generally not exceeding 120°C, and being typically lower than 110°C, lower than 100°C, or lower than 90°C. The glass transition temperature of suitable NPs can, by way of illustration, be between -10°C and 120°C, between 10°C and 100°C, between 40°C and 100°C, between 50°C and 90°C, between 30°C and 80°C, or between 30°C and 70°C. The Tgof a material can be provided by its supplier and can be independently determined by any suitable routine analytical method and for instance by differential-scanning calorimetry as described in ASTM E-1356.

[0063] Suitable NPs can advantageously be softened by heat, reverting to a more rigid and constraining structure upon cooling, hence having a thermoplastic behavior by themselves, prior to their polymerization with the fatty agents. In some cases, the softening temperature (Ts) of the natural polymers is at least 40°C, at least 50°C, or at least 60°C, such softening temperature generally not exceeding 160°C, and being typically lower than 140°C, lower than 120°C, or lower than 100°C. The softening temperature of suitable NPs (which is often provided over a short range of values corresponding to the transition phase of the material) can, by way of illustration, be between 50°C and 140°C, between 50°C and 95°C, between 55°C and 85°C, or between 60°C and 100°C. Generally, the NPs known as waxes have lower softening points than NPs known as resins. For illustration, while sandarac which is considered a relatively hard resin has a Tsnear 135-150°C, carnauba which is considered a relatively hard wax has a Tsnear 75-80°C. The Tsof a material can be provided by its supplier and can be independently determined by any suitable routine analytical method and for instance by Vicat procedure as described in ASTM D-1525.

[0064] The ability of NPs to covalently form macromolecules by themselves under ambient conditions is typically limited, if not entirely absent, and they usually have a low degree of polymerization if not subjected to appropriate curing conditions (e.g., heat).

[0065] Within the previously provided ranges of MWs generally enabling fiber permeation, the NPs are typically at the higher end, being usually, but not necessarily, larger than other ingredients of the present compositions. In some cases, the NPs have a MW between 500 g / mol and 10,000 g / mol, between 1,000 g / mol and 5,000 g / mol, or between 500 g / mol and 3,000 g / mol. As the resins and the waxes may naturally exist over a wide range of size (often due to mere aggregation or presence of different materials), the NPs can be fractionated into populations of molecules having the aforesaid MWs. Moreover, being natural substances, each batch may have slightly different contents, which can be harmonized by removal of materials most contributing to the fluctuations in composition and / or purity. Thus, the term fraction as used with respect to natural polymers may relate to exclusion by size and / or by chemical contents. For illustration, waxes may naturally be present in the resins, which can therefore be used either as inherently waxed or as dewaxed fractions.

[0066] Advantageously, suitable NPs include functional groups adapted to react with amine groups on the fatty amines, with hydroxyl groups on the fatty alcohols, with carboxyl groups on the fatty acids, or with more than one such reactive groups when present in a same fatty agent, suitable fatty materials being later detailed. The reactive groups on the NPs should be in sufficient density and / or accessibility to preferably enable a rapid enough polymerization of the NPs with the FAs. The presence of such prospective reactive groups (e.g., hydroxyl (-OH), carboxyl (-COOH), carbonyl (-C=O), olefinic (-C=C-), or aldehyde (-CHO) moieties) can be assessed, for instance, by the acid value, the hydroxyl value, the saponification value or the iodine value of the NPs, to name a few.

[0067] The acid value (AV), which indicates the acidity of a material measures the amount of sodium hydroxide (NaOH) or potassium hydroxide (KOH) expressed in milligrams (mg), required to neutralize 1 gram of the material. The AV of a material can be provided by its supplier and can be independently determined by any suitable routine analytical method allowing it to fully dissolve (e.g., in an organic solvent) and for instance by acid-base potentiometric titration, according to procedures described in ASTM D-664.

[0068] In some cases, the acid value of the NPs is between 1 and 200 mg KOH per gram of tested material, between 1 and 25 mg KOH / g, between 15 and 125 mg KOH / g, between 20 and 100 mg KOH / g, between 50 and 90 mg KOH / g, or between 10 and 50 mg KOH / g.

[0069] The saponification value (SV) represents the number of milligrams of sodium hydroxide (NaOH) or potassium hydroxide (KOH) required to saponify one gram of completely hydrolyzed material. Saponification value serves to estimate the number of carboxylic functional groups (or ester linkages) per unit mass, SV increasing with decreasing molecular weight. The SV of a material can be provided by its supplier and can be independently determined by any suitable routine analytical method allowing to fully hydrolyze a waterinsoluble material and for instance by the procedure according to ASTM D-5558, or based on the recommendations of ISO 3657.

[0070] In some cases, the saponification value of the NPs is between 20 and 250 mg KOH per gram of tested material, between 50 and 200 mg KOH / g, between 100 and 200 mg KOH / g, or between 150 and 250 mg KOH / g.

[0071] The iodine value (IV) measures the degree of unsaturation of a material by determining the amount of halogen (typically iodine), in grams, that is taken up by 100 grams of the substance under study. Saturated materials cannot take up iodine, and therefore have a iodine value of zero, whereas unsaturated materials containing double or triple bonds, which are very reactive toward iodine, have a positive iodine value increasing with the degree of unsaturation. The IV of a material can be provided by its supplier and can be independently determined by any suitable routine analytical method and for instance by the procedure according to Wijs, based on the recommendations of DIN 53241-1 or according to ASTM D-1959.

[0072] In some cases, the iodine value of the NPs is between 0 and 200 grams iodine per 100 grams of tested material ( wt.%), between 0 and 150 I2 wt.%, between 0 and 100 I2 wt.%, between 0 and 50 I2 wt.%, or between 0 and 25 I2 wt.%.

[0073] While the parameters that may characterize suitable NPs have been individually presented, resins or waxes may fulfill more than one of the aforesaid recommendations and have, for illustration, at least two, at least three, at least four (and so on till optionally all) of their MW, Tm, Tg, Ts, AV, SV and IV falling within these ranges of values. Typically, safe of the average molecular weight which may be comparable, the values displayed by waxes for any given aforesaid parameter are generally lower than the values displayed by resins for the same parameter. This is not an absolute rule since a relatively hard wax may display values higher than a relatively soft resin.

[0074] Advantageously, the reactive groups on the NPs (and their density) should prevent or reduce spontaneous self-curing (e.g., self-esterification) during storage (e.g., at room temperature or at a lower one, if refrigeration is recommended), a process often referred to as aging. The same rationale of curing inertia additionally applies to the mixture of CNPFAs which can be stored jointly in the same phase of the composition, the reactive groups on the FAs preferably having limited cross-linking with the NPs during storage (which can be performed in presence of anti-oxidants, under inert atmosphere, and / or with protection from light, or any other such conventional means of prolonging stability of a product).

[0075] The temperature at which polymerization would be significantly triggered should be high enough to provide a commercially significant lifespan to the composition being stored or transported at relatively lower temperatures. On the other hand, the temperature at which the CNPFAs would polymerize need not be too high, but reasonably adapted to the intended fibers.

[0076] In the case of hair fibers attached to a living subject, the CNPAs should preferably be capable of polymerizing at least at a temperature between 50°C and 60°C, though higher temperatures are envisioned if applied briefly enough to prevent heat related damage to hair fibers. For instance, styling irons having a heating rod shaped according to the sought effect (e.g., flattening or curling) may have a rod surface temperature of up to 230°C or even 250°C. However, they are used in a manner exposing the hair fibers only briefly (for a few seconds) to such temperatures, so the fibers do not reach the iron temperature. For instance, a flat iron may be moved (e.g., at a rate of 5 cm / sec) from the roots to the tips of the fibers while pulling the hair, one full length ironing being often called a pass.

[0077] Suitable NPs can be resins selected from a group consisting of shellac and vegetal resins including colophony resin (also known as rosin), copal resin, dammar resins, dragon blood resin, elemi resin, kauri resin, mastic resin, sandarac resin, tacamahac resin, and fractions thereof. Suitable NPs can alternatively be waxes selected from a group consisting of candelilla wax, carnauba wax, jojoba wax, kafrin wax, montan wax, olive wax, rice bran wax, sal tree wax, sugarcane wax, sunflower wax, and fractions thereof. Depending on their geographical origin, degree of maturity and level of purity, the natural polymers may satisfy the afore-said features in various manners. For illustration, and besides their analytical characteristics which can fluctuate based on the specific compounds in a particular batch and the method of extraction or treatment of the resin or wax, the NPs can have different innate shades, typically from yellowish to brownish, via reddish tints. When the innate shade of the NPs is deemed improper for its intended use (e.g., undesirably modifying the color of the fibers), a chemically processed (e.g., bleached, dewaxed) version of the same can be used.

[0078] Notably, such NPs (whether native or chemically processed) can be considered biodegradable and often officially listed as GRAS (Generally Recognized as Safe) by the FDA or similarly acceptable by other regulatory authorities. Use of such materials is therefore expected to increase compliance by environmentally conscious consumers. The NPs can be used alone or in combination with additional suitable natural polymers. For illustration, a relatively tougher resin (e.g., sandarac) can be mixed with a relatively softer one (e.g., elemi) or with a suitable wax to afford desired properties to the resulting polymer. As mentioned, they can be used as naturally available, or be supplied as fractions of NPs (e.g., to satisfy a desired MW or remove undesirable components) and / or as chemically modified (e.g., to adapt an intrinsic property of the NP to fall within preferred values, such as bleaching the NPs to render their shades lighter).

[0079] In view of their prospective sources, methods of extraction, fractionation, purification or chemical modification, the NPs may in some cases include volatile materials in more than residual amounts (e.g., more than 5 wt.%). As the presence of such materials can be detrimental during the use of present compositions, e.g., emitting odors and / or smokes during hair ironing performed at about 200-220°C, it can be desired to treat the NPs so as to reduce their presence in the raw material. For illustration, the volatile compounds, if any, can be at least partially eliminated by incubating the NPs in a vacuum chamber. This process can be performed at any temperature facilitating the volatilization of the compounds to be eliminated, while being low enough to avoid modifying the NPs. For this reason, the temperature used for such evaporation processes, if required, is typically at least 30°C below the melting temperature of the NPs. Understandably, the duration of the process may depend on the temperature and vacuum applied. For instance, evaporation may require only 2 hours if performed at 100°C but 18 hours or more if performed at 80°C or less, such illustrative conditions being suitable when the materials are subjected to a relatively mild vacuum of 1 kPa. Deeper vacuum conditions, referring to values of less than 10 Pa, less than 1 Pa, less than 0.1 Pa, can also be used, affecting in turn the temperature and duration of evaporation of volatile compounds as desired. The efficacy of this process for the removal of volatile compounds to desired levels can be assessed by measuring weight loss of the NP before and after evaporation, by TGA performed above their boiling temperature, e.g., at 220°C. The duration of the process can also be set to achieve a predetermined level of volatile compounds in the NPs, e.g., less than 5 wt.%, less than 2.5 wt.% or less than 1 wt.%.

[0080] The removal of volatile materials from the resins to a predetermined desired level may ensure that the compositions prepared therefrom are repeatedly substantially the same regardless of the batch origin or their constituting substances. However, volatile materials should not be considered deleterious per se, as fragrances and some odor masking substances typically provide their respective scents thanks to their volatility. Therefore, such materials may be tolerated or controllably added to the composition. It can be mentioned that some of the volatile compounds naturally present in some natural polymers are their corresponding essential oils (e.g., dammar essential oil being extracted from dammar resin, etc.). Essential oils, however, are not limited to the sources of the corresponding natural polymers. Interestingly, some essential oils are associated with therapeutic properties, such as antibacterial, antifungal, or anti-inflammatory properties, some being particularly pertinent for hair care (e.g., cedarwood, peppermint, rosemary, sage and tea tree essential oils have been reported to improve hair health and could be added to present compositions).

[0081] Usually, the water-insoluble natural polymer (or a combination thereof) is present in the composition at a concentration of at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, or at least 0.25 wt.% by total weight of the (e.g., hair styling) composition. In some cases, its (combined) concentration can be at most 5 wt.%, at most 3 wt.%, or at most 2 wt.%, by total weight of the composition. In particular cases, the concentration of the NP(s) is between 0.1 and 5 wt.%, between 0.15 and 3 wt.%, or between 0.2 and 2 wt.% by weight of the composition.

[0082] Typically, the composition is an oil-in-water emulsion wherein the water-insoluble ingredients constitute at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, or at least 0.25 wt.%, by total weight of the composition. In some cases, the water-insoluble ingredients constitute at most 10 wt.%, at most 5 wt.%, at most 3 wt.%, or at most 2 wt.%, by total weight of the composition. Typically, the water-insoluble ingredients constitute between 0.1 wt.% and 5 wt.%, between 0.1 wt.% and 2 wt.%, or between 0.1 wt.% and 1 wt.%, of the composition.

[0083] The water-insoluble fatty agents

[0084] The water-insoluble fatty agents (FAs) (including fatty amines (FA1), fatty alcohols (FA2) and fatty acids (FA3)) which can react with the NPs as herein disclosed to jointly polymerize as CNPFAs are all typically liquid at room temperature, or at least at an elevated temperature at which they can be mixed with the NPs to prepare the water-insoluble compartment of the present compositions or at which they are applied to the fibers so as to penetrate their inner cores. The FAs can have a single reactive group (e.g., amine, hydroxyl, or carboxyl) group per molecule, and advantageously two or more.

[0085] In other words, a suitable FA if a fatty amine FA1 can be a mono-amine, a di-amine, a tri-amine, or a poly-amine (e.g., a mid-range sized backbone fatty chain including tens of carbon atoms and bearing more than three amine groups per molecule or a large-range sized backbone polymeric chain bearing one or more amine groups per molecule), the amine groups usually being a primary amine or a secondary amine, tertiary amines being permissible but deemed relatively less reactive, wherein the nitrogen atom is directly bonded to one, two or three carbon atoms respectively (R-NH2, R’-NH-R”, or R’R”R”’-N, wherein R, R’, R” and R’” represent the aliphatic chain or portions thereof).

[0086] Similarly, when the FA is a fatty alcohol FA2, it can be a mono-ol, a di-ol, a tri-ol, or a poly-ol, the hydroxyl groups usually being a primary hydroxyl, a secondary hydroxyl, or a tertiary hydroxyl, wherein the carbon atom that is bonding with the hydroxyl group has respectively only one R group attached thereto (R-CH₂-OH), two R’ and R’ ’ groups attached thereto (R’-CHOH-R”), or three R’, R” and R’” groups (R’R”R”’-COH). Mono-ol, di-ol, tri-ol and poly-ol FA2 are also known as mono-hydric, di-hydric, tri-hydric and poly-hydric fatty alcohols.

[0087] Similarly, when the FA is a fatty acid FA3, it can be a mono-carboxylic acid or a dicarboxylic acid, the carboxyl groups usually being attached to a primary carbon, a secondary carbon, or a tertiary carbon, wherein the carbon atom that is bonding with the carboxyl group has respectively only one R group attached thereto (R-COOH), two R’ and R’ ’ groups attached thereto (R’-COOH-R”), or three R’, R” and R’” groups (R’R”R”’-COOH).

[0088] In some cases, the fatty agents may be modified to increase the relative density of the reactive groups on the fatty chain. Considering the reactive groups discussed in previous paragraphs, amination, hydroxylation or carboxylation methods may respectively increase the relative proportion of amine groups, hydroxyl groups or carboxyl groups in the fatty agent treated thereby, the fatty agent previously bearing same or different groups than those added in the process.

[0089] The fatty agents can alternatively, or additionally, be modified by any other chemical process adapted to tailor their chemical and physical properties to satisfy present teachings. All fatty agents chemically modified from natural or synthetic parent fatty agents to alter the relative proportion of reactive groups, introducing new groups and / or depleting others on the fatty chain, can be referred to as chemically modified FA derivatives or briefly “(FA) derivatives”.

[0090] For illustration, hydrogenation may be used to “unsaturate” fatty agents to produce saturated ones (or at least partially more saturated ones, if the fatty agent is poly-unsaturated). Alkylation (also known as arylation) can be used to replace an active hydrogen in the fatty chain of fatty amines, fatty alcohols or fatty acids with an aliphatic group, such as with a saturated alkyl group (e.g., methyl or ethyl), or an aliphatic-aromatic group (e.g., benzyl). The new alkyl group can be inserted at various positions along the fatty chain and / or may be inserted at more than one position on the fatty backbone. Ethoxylation (the most frequent alkoxylation procedure) is an alternative common modification of fatty agents, such a process replacing native hydroxyl or carboxyl, as found in fatty alcohols or fatty acids, by ethoxy units according to the molar excess of ethylene glycol used in the process, these new substituents forming an ethoxylated moiety which may modify the behavior of the fatty agent. Pegylation is also a possible modification of the fatty agents, any such modifications being permissible as long as not detracting from the water-insolubility required of the FAs. As fatty agents can be unsaturated, it may also be possible to reduce carbon-carbon double bonds by epoxidation, introducing epoxy groups instead, the extent of such replacements being controllable (e.g., as can be assessed by the epoxide value of the material).

[0091] Procedures to achieve the chemical modifications exemplified in the previous paragraphs are known to persons skilled in organic chemistry. Moreover, derivatives of fatty agents listed herein mainly by their fatty chain length and innate reactive groups as can be obtained by such methods, when applicable to their initial chemical structure, are commercially available or independently synthesizable. Thus, while only a few derivatives of fatty agents may be specifically discussed herein, all pertinent derivatives that fulfil the properties desired for the fatty agents are included in the respective FAs.

[0092] In some cases, the fatty agents, whether or not chemically modified to form desired derivatives, may include reactive groups of more than one type (e.g., amine and hydroxyl groups, or carboxyl and hydroxyl groups) on their backbone, provided that they remain waterinsoluble and satisfy the present requirements, these “hybrid” materials often being named according to their method of preparation, such as being a hydroxylated fatty amine, an aminated fatty alcohol, or an epoxidized fatty acid, to name a few. Such materials are often referred to as chemical derivatives of the fatty agent so modified and all groups of FAs to be detailed in the following are deemed to include pertinent derivatives. For illustration, polyethoxylated amines (e.g., POE (2) Cocoamine or Genamin® O 020) can be considered derivatives of fatty amines including both an amine function and hydroxyl groups.

[0093] Mono-amines, mono-ols or mono-carboxyl may react with reactive groups on the NPs, reducing their availability to cross-react in a self-polymerization process (when the NP may do so) or to react with other fatty agents having two or more reactive (e.g., amine, hydroxyl and / or carboxyl) groups per molecule. By this rationale the mono-amines, mono-ols or mono-carboxyl FAs can control the extent of polymerization of the NPs and inhibit the formation of too complex 3D networks resulting in a structure no longer amenable to shaping under reasonable heat conditions. Such mono-reactive fatty agents including only one reactive group per molecule can be considered as a “reactive non-volatile plasticizer” to the resulting polymer, or capping reagents or “inhibitors” regulating its formation, so as to remain shapeable. A natural polymer reacted with a mono-reactive FA has properties departing from its original characteristics as the reaction proceeds.

[0094] Fatty agents including only one reactive group can be used alone, provided that reactive groups present on the NPs can react one with another to form the shapeable polymer. If the NPs are devoid of functional groups that may cross-react one with another under the conditions they are used with the FAs, then the CNPFAs should include FAs having two or more reactive groups per molecule to enable network formation, fatty agents with a single reactive group being optionally included to block a portion of the reactive groups on the natural polymer, controlling thereby the extent of prospective cross-linking, hence the complexity of the resulting polymer and, e.g., its shapeability.

[0095] The reactive groups (regardless of number and combination therebetween, or not) are attached to a substituted or unsubstituted aliphatic chain including, depending on the reactive group and the presence of unsaturated bonds, at least 6 carbon atoms (e.g., to provide for a water-solubility not exceeding 1 wt.% in pure water at 25°C) shorter chains being typically (but not necessarily) improper. Typically, the aliphatic chain contains at most 300 carbon atoms, at most 150 carbon atoms, at most 75 carbon atoms, or at most 40 carbon atoms. Fatty chains having between 6 and 12 carbon atoms are considered medium chains, long chains having between 13 and 22 carbon atoms, and very long chains more than 22. The carbon atoms, which can be interconnected by saturated or unsaturated bonds, can be arranged as a linear open chain, a branched chain, or one including cyclic structures provided they are not aromatic rings. For illustration, the fatty chain can include a cyclo-hexyl, a cyclo-pentyl, a cyclo-butyl or a cyclopropyl group, which can be found either attached to or forming an internal part of the chain or at a terminal end of the chain (often called the omega position having assigned alpha position to the carbon atom to which the reactive group is attached when positioned on the opposite terminal end). In some cases, the reactive groups can be attached to the cyclic rings in the chain. As used hereinafter, the term “aliphatic chain” shall be deemed to include all aforesaid alternatives, and their permitted combinations, unless absent in particular chemical classes. As the number of amine, hydroxyl and / or carboxyl reactive groups on the backbone can increase the polarity of the FAs, in order to retain a desired water-insolubility, increasing the amount of polar reactive groups typically correlates with an increased amount of carbon atoms in the aliphatic chain. The degree of unsaturation of the aliphatic chain may also serve to tailor some properties of the fatty agents (e.g., decreasing their melting temperature).

[0096] Fatty amines FA1 (including their derivatives) can be characterized by their Amine Value (NV) which can be calculated based on the molecular mass of the amine functional compound and the number of nitrogen atoms in the molecule or experimentally derived by titration, such as described in ASTM D-2074, the units being provided in both cases in mg KOH / g. Typically, suitable fatty amines, have an Amine Value of at least 150 mg KOH / g, at least 175 mg KOH / g, or at least 200 mg KOH / g. Usually the NV of suitable fatty amines is at most 1,000 mg KOH / g, at most 750 mg KOH / g, or at most 500 mg KOH / g. In some cases, the NV of the fatty amines is between 150 and 750 mg KOH / g, between 175 and 500 mg KOH / g, or between 200 and 500 mg KOH / g.

[0097] Suitable mono-amine FAls can have a C8-C22 aliphatic chain and be selected from a group comprising octylamine (C₈H₁₇NH₂), decylamine (C₁₀H₂₁NH₂), dodecylamine (C₁₂H₂₅NH₂), tetradecylamine (C₁₄H₂₉NH₂), hexadecylamine (C₁₆H₃₃NH₂), octadecylamine (C₁₈H₃₇NH₂), oleylamine (C₁₈H₃₅NH₂), linoleylamine (C₁₈H₃₃NH₂), linolenylamine (C₁₈H₃₁NH₂), eicosylamine (C₂₀H₄₁NH₂), and docosylamine (C₂₂H₄₅NH₂).

[0098] Suitable di-amine FAls can have a C10-C22 aliphatic chain and be selected from a group comprising decyl-1,10-diamine (C₁₀H₂₂(NH₂)₂), dodecyl-1,12-diamine (C₁₂H₂₆(NH₂)₂), tetradecyl-1,14-diamine (C₁₄H₃₀(NH₂)₂), hexadecyl-1, 16-diamine (CI< H34(NH2)2), octadecyl-1,18-diamine (C₁₈H₃₈(NH₂)₂), oleyl diamine (C₁₈H₃₆(NH₂)₂), linoleyl diamine (C₁₈H₃₄(NH₂)₂), and eicosyl-1,20-diamine (C₂₀H₄₂(NH₂)₂).

[0099] Suitable tri-amine FAls can have a C12-C22 aliphatic chain and be selected from a group comprising tridecyl-1,3,5-triamine (C₁₃H₂₇(NH₂)₃), pentadecyl-1,3,5-triamine (C₁₅H₃₃(NH₂)₃), hexadecyl-1,3,5-triamine (C₁₆H₃₅(NH₂)₃), hexadecyl-1,4,7-triamine (C₁₆H₃₄(NH₂)₃), octadecyl-1,3,5-triamine (C₁₈H₃₉(NH₂)₃), oleyl-1,3,5-triamine (C₁₈H₃₇(NH₂)₃), linoleyl-1,3,5-triamine (C₁₈H₃₅(NH₂)₃), linolenyl-1,3,5-triamine (C₁₈H₃₃(NH₂)₃), ricinoleyl-1,3,5-triamine (C₁₈H₃₅(NH₂)₃), eicosyl-1,3,5-triamine (C₂₀H₄₃(NH₂)₃), and erucyl-1,4,7-triamine (C₂₂H₄₁(NH₂)₃). Suitable poly-amine FAls can have a C14-C22 aliphatic chain and be selected from a group comprising tetradecyl-1,2,4,6-tetraamine (C₁₄H₃₀(NH₂)₄), linolenyl-1,3,6,9-tetraamine (C₁₈H₃₁(NH₂)₄), eicosyl-1,3,6-tetraamine (C₂₀H₄₂(NH₂)₄) and docosyl-1,4,7-pentaamine (C₂₂H₄₆(NH₂)₅).

[0100] Alternatively, the FAls can have a C30-C150 aliphatic chain, the term poly-amine then referring to the polymeric nature of the backbone bearing the amine groups, rather than to the number of amine groups on the aliphatic chain. Examples of such FAs include polyethyleneimines (PEI) and polyetheramines (PEA), provided they satisfy the same requirements as the relatively shorter fatty amines.

[0101] Fatty amines including non-aromatic cyclic ring, e.g., cyclo-hexyl, cyclo-pentyl, cyclobutyl, or cyclo-propyl rings include cyclo-hexyl amine (C₆H₁₁NH₂) sparingly miscible in water, dicyclohexylamine (C₁₂H₂₂NH), n-methylcyclohexylamine (C₆H₁₁NHCH₃), 2,2- or 2,3-, 2,6-, 3,3-, or 4,4-dimethylcyclohexyl-1-amine (C₈H₁₇N), N-, 2-, or 4-ethylcyclohexyl-1-amine (C₈H₁₇N), and N, N-, or 2,6-diethylcyclohexylamine (C₁₀H₂₁N), to name a few.

[0102] Fatty amines can be purchased under their chemical names as above exemplified, as isomers or derivatives thereof, or as proprietary formulations or blends, the tradenames depending upon the supplier, such as Noram® commercialized by Arkema, Priamin™ by Cargill, Genamin® by Clariant, Farmin® by Kao, and Rofamin® by Nimac. Polyetheramines are traded under various marks such as Jeffamine® commercialized by Huntsman, the M-series being mono-amines, the D-series being di-amines and the T-series being tri-amines, higher molecular weight polypropylene oxide backbones ensuring their water-insolubility.

[0103] Fatty alcohols FA2 (including their derivatives) can be characterized by their Hydroxyl Value (HV) which correspond to the number of mg of KOH required to neutralize the acetic acid taken up on acetylation of one gram of material containing free hydroxyl groups. Standard methods are known, such as described in ASTM E-222. Typically, suitable fatty alcohols have a Hydroxyl Value of at least 150 mg KOH / g, at least 175 mg KOH / g, or at least 200 mg KOH / g. Usually the HV of suitable fatty alcohols is at most 1,000 mg KOH / g, at most 750 mg KOH / g, or at most 500 mg KOH / g. In some cases, the HV of the fatty alcohols is between 150 and 750 mg KOH / g, between 175 and 500 mg KOH / g, or between 200 and 500 mg KOH / g.

[0104] Suitable mono-ol FA2s can have a C8-C22 aliphatic chain and be selected from a group comprising saturated mono-ol such as 1-octanol (C₈H₁₈O), 1-nonanol (C₉H₂₀O), 1-decanol (C₁₀H₂₂O), 1-undecanol (C₁₁H₂₄O), 1-dodecanol (C₁₂H₂₆O) and unsaturated mono-ol such as 8- nonen-1-ol (C₉H₁₈O), 9-decen-1-ol (C₁₀H₂₀O), 10-undecen-1-ol (C₁₁H₂₂O), (Z)-octadec-9-en-1-ol (C₁₈H₃₆O), cis-cis-9,12-octadecadien-1-ol (C₁₈H₃₄O) and 3,7,11,15-tetramethyl-2-hexadecen-1-ol (C₂₀H₄₀O).

[0105] While some mono-ols fatty alcohols having longer aliphatic chain can be solid at room temperature, this does not preclude their use if the composition is to be applied and incubated at a temperature at which they are liquid, either by themselves or as a result of being mixed with additional fatty agents. For illustration, the following mono-ols which are typically more waxy or solid at room temperature may also be used under appropriate conditions: 1-tridecanol (C₁₃H₂₈O), 1-tetradecanol (C₁₄H₃₀O), 1-hexadecanol (C₁₆H₃₄O), 1-octadecanol (C₁₈H₃₈O), 1-eicosanol (C₂₀H₄₂O), and 1-docosanol (C₂₂H₄₆O).

[0106] Suitable di-ol FA2s can have a C8-C22 aliphatic chain and be selected from a group comprising 1,2-octanediol (C₈H₁₈O₂), 1,9-nonanediol (C₉H₂₀O₂), 1,2-decanediol (C₁₀H₂₂O₂), and 1,11-undecandiol (C₁₁H₂₄O₂), diols having longer chains being typically solid at room temperature but permissible under circumstances as previously described.

[0107] Fatty alcohols including non-aromatic cyclic rings include by way of illustration 2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-ol (C₁₀H₁₆O, also known as carveol), 5-methyl-2-(1-methylethylidene)-cyclohexanol (C₁₀H₁₈O, also known as pulegol), 2-isopropyl-5-methylcyclohexan-1-ol (C₁₀H₂₀O, also known as menthol), 4-(2,2,6-trimethyl-cyclohexyl)butan-2-ol (C₁₃H₂₆O, also known as tetrahydroionol), 1-octyl-cyclopentanol (C₁₃H₂₆O) and 1-dodecylcyclohexan-1-ol (C₁₈H₃₆O).

[0108] Fatty alcohols can be purchased under their chemical names as above exemplified, as isomers or derivatives thereof, or as proprietary formulations or blends, the tradenames depending upon the supplier, such as Bergarol™ commercialized by Berg+Schmidt, Kalcol™ by Kao, or diols and polyols of Kuraray, to name a few.

[0109] Fatty acids FA3 (including their derivatives) can be characterized by their Saponification Value (SV) provided in mg KOH / g. Typically, suitable fatty acids have a Saponification Value of at least 150 mg KOH / g, at least 160 mg KOH / g, or at least 170 mg KOH / g. Usually the SV of suitable fatty acids is at most 700 mg KOH / g, at most 600 mg KOH / g, or at most 500 mg KOH / g. In some cases, the SV of the fatty acids is between 150 and 700 mg KOH / g, between 160 and 600 mg KOH / g, between 170 and 500 mg KOH / g, between 170 and 400 mg KOH / g, or between 170 and 300 mg KOH / g. Typically, suitable FA3s are mono-carboxyl, di-carboxyl often being solid at RT hence appropriate for use at temperatures above their melting point. FA3s can be saturated monocarboxyl having a C5-C11 aliphatic chain such a group comprising pentanoic acid (C₅H₁₀O₂), hexanoic acid (C₆H₁₂O₂), heptanoic acid (C₇H₁₄O₂), octanoic acid (C₈H₁₆O₂), nonanoic acid (C₉H₁₈O₂), decanoic acid (C₁₀H₂₀O₂), and undecanoic acid (C₁₁H₂₂O₂). Suitable FA3s can also be unsaturated having one unsaturated bond within a C14-C22 aliphatic chain, known as decenoic acids, two unsaturated bonds within a C16-C24 aliphatic chain, known as dienoic acids, or three unsaturated bonds within a C18-C26 aliphatic chain, known as trienoic acids.

[0110] For illustration, oleic acid is a fatty acid having 18 carbons and a single double bond, this FA3 having isomers differing in the position of the double bond within the aliphatic chain and the stereo orientation of the portions of the chain preceding and following the double bond which can be cis or trans. Non-limiting examples of fatty acids sharing the C18H34O2 general formula include cis-9-octadecenoic acid, trans-9-octadecenoic acid, cis-10-octadecenoic acid, trans- 10-octadecenoic acid, cis- 11 -octadecenoic acid, trans- 11 -octadecenoic acid, cis-12-octadecenoic acid, trans- 12-octadecenoic acid, cis-13-octadecenoic acid, trans- 13 -octadecenoic acid, and so on. Similar principles apply to shorter or longer unsaturated FA3s, the number of prospective isomers typically increasing with the number of double bonds within the chain. Still considering a fatty acid having 18 carbon atoms, those including two double bonds share the C₁₈H₃₂O₂ general formula and those including three double bonds share the C₁₈H₃₀O₂ general formula. They can be exemplified by linoleic acid (C18:2), such as (9Z,12Z)-octadeca-9,12-dienoic acid and linolenic acid (C18:3), such as (9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid.

[0111] Fatty acids including non-aromatic cyclic rings include, by way of illustration, cyclohexanecarboxylic acid (C₆H₁₁COOH), cycloheptanecarboxylic acid (C₇H₁₃COOH), cyclooctanecarboxylic acid (C₈H₁₅COOH), 1-cyclooctene-1-carboxylic acid (C₈H₁₃COOH), cyclopentylundecanoic acid (C₁₅H₂₉COOH), cyclohexylundecanoic acid (C₁₆H₃₁COOH), 7-(2-octylcyclopentyl)heptanoic acid (C₁₉H₃₇COOH), cyclopropanetetradecanoic acid (C₂₅H₄₉COOH) and other fatty acids commonly found in food products better known under the trivial names of lactobacillic acid (11,12-methylene-octadecanoic acid, C₁₈H₃₅COOH), malvalic acid (7-(2-octylcyclo-propen-1-yl)heptanoic acid, C₁₇H₃₁COOH), dihydromalvalic acid (7-(2-octylcyclopropyl)heptanoic acid, C₁₇H₃₃COOH), sterculic acid (8-(2-octylcyclo-propen-1-yl)octanoic acid, C₁₈H₃₂COOH) and dihydrosterculic acid (8-(2-octylcyclopropyl)-octanoic acid, C₁₈H₃₅COOH). While the amines groups of these exemplary fatty amines, the hydroxyl groups of these exemplary fatty alcohols, or the carboxyl groups of these exemplary fatty acids, are often attached to the end-carbons of the aliphatic chain, these reactive groups of the FAs can also be attached to a carbon atom within the aliphatic chain or within a ring thereof. Similarly, when two or more reactive groups are described as positioned on specific carbon atoms, additional isomers may exist wherein the groups are differently attached to the aliphatic chain. Therefore, even when not literally listed, all existing isomers of suitable fatty agents are encompassed by the present teachings, including stereoisomers and enantiomers when applicable, provided they fulfill the requirements or recommendations as herein taught. As mentioned, suitable FAs may not only include isomers of particular agents, but also chemically modified versions of the same generally referred to as FA derivatives, provided they too fulfill the requirements or recommendations as herein taught. As used herein, reference to fatty agent(s) or FA(s) include all pertinent isomers and derivatives.

[0112] The FAs can be used alone or in combination with additional suitable fatty agents, which can be in the same or a different category. If the FAs are of different categories which may react one with the other(s), thus reducing their ability to react with the NPs, then they should be added to the NPs sequentially. By this process of successive addition, individual reactions between a particular category of FAs with the NPs through their respective reactive groups can take place before a new set of reactions with the different FAs is initiated.

[0113] For illustration of possible blends of FAs, FAs having two or more amine or hydroxyl groups per molecule to enable or facilitate the formation of 3D networks in the resulting shapeable polymer, thus acting as cross-linkers, can be used in combination with mono-amines, mono-ols and / or mono-carboxyls, which may regulate the extent of polymerization. A fatty agent being relatively viscous at room temperature (or even mildly solid) can be mixed with a different fatty agent being relatively non-viscous, the blend of FAs being liquid as desired at a temperature of relevance to preparation and use.

[0114] Notably, some fatty agents naturally exist as a mixture of individual fatty agents, as would be the case for illustration with some vegetal oils, the relative proportion of the individual FAs often varying from source or geographical area. For example, soybean oil typically consists of linoleic acid (48%-58%), oleic acid (17%-30%), palmitic acid (9%-13%), linolenic acid (4%-11%), and stearic acid (2.5%-5.0%). In case the FA consists of a mixture of different FAs, some of the afore-mentioned chemical modifications can be performed on the blend rather than on its individual constituents. Epoxidation, for example, can be carried out on whole oils (to form epoxidized e.g., canola oil, castor oil, linseed oil, soybean oil, sunflower oil, etc. such as commercialized under tradename Vikoflex® by Cargill®) in addition to being alternatively performed on their constituting FAs individually.

[0115] Usually, the water-insoluble fatty agent (or a combination thereof) is present in the composition at a concentration of at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, or at least 0.25 wt.% by total weight of the e.g., hair styling) composition. In some cases, its (combined) concentration can be at most 5 wt.%, at most 3 wt.%, or at most 2 wt.%, by total weight of the composition.

[0116] Typically, the weight per weight (w / w) ratio between the at least one water-insoluble fatty agent and the at least one water-insoluble natural polymer in the water-insoluble phase of the composition in which they are miscible is such that the respective reactive groups on the CNPFAs are at least in stoichiometric amount, to ideally enable cross-reactions between all groups theoretically available on the CNPFAs. However, this is not essential as reactive groups on each of the molecules participating in the polymerization can be hindered, in particular as curing proceeds towards the formation of more complex polymers. Moreover, the fatty agent(s) may be present in relative excess if their residual solubility in water is feared to cause some migration of the FA(s) from the water-insoluble phase into the surrounding aqueous environment.

[0117] In some cases, the w / w ratio in the water-insoluble phase of the composition is at least half-part of fatty agent(s) per one part of natural polymer(s), one part of fatty agent(s) per one part of natural polymer(s), at least one and a half part of fatty agent(s) per one part of natural polymer(s), or at least two parts of fatty agent(s) per one part of natural polymer(s). Typically, the w / w ratio does not exceed ten parts of fatty agent(s) per one part of natural polymer(s), usually being of at most five parts of fatty agent(s) per one part of natural polymer(s).

[0118] The ratio between the fatty agent(s) and the natural polymer(s) may also be selected based on their respective physico-chemical properties and their intended conditions of use. For illustration, if the composition comprising the CNPFAs is to be applied to the desired fibers at room temperature, the ratio between the FA(s) and the NP(s) can be selected so that they form a mixture advantageously liquid at said temperature.

[0119] The polymer made of curable NPFAs

[0120] As mentioned, suitable NPs can have a thermoplastic behavior, i.e., being shapeable by heat in a reversible manner. Whether or not inherently thermoplastic, the polymerization of the NPs with the FAs may result in a NPFA polymer which can be thermoplastic or behave in a thermoplastic manner, which is desired at least during the initial shaping of the fibers. Without wishing to be bound by any particular theory, this is believed to be the case when the degree of cross-linking is relatively low (e.g., lacking a measurable Tg) as further detailed below. In some cases, the composition (or its water-insoluble portion containing the polymerizable ingredients) has prior to polymerization of the CNPFAs a glass transition temperature (Tg), if any, of 20°C or less, 0°C or less, or -20°C or less.

[0121] Upon polymerization of the CNPFAs, as can be more readily assessed within a sample of the liquid composition subjected to a similar treatment in vitro, the resulting NPFA polymer develops a differing glass transition temperature (Tg), the NP being modified by the covalent bonds newly formed with the FA (or internally by self-polymerization). In such a case, the NPFA polymer behave in a thermosetting manner or has become a thermoset polymer (e.g., having a measurable Tg) as a result of dense enough cross-linking between the reactive groups. In some cases, upon complete curing, the resulting polymer has a Tg of -20°C or more, 0°C or more, at least 25°C, at least 50°C, at least 100°C, at least 150°C, or at least 200°C. Such Tg allows the polymerized NPFAs to remain intact under hot weather conditions, when washing the hair with hot water (around 45°C), or even when being in an environment of elevated temperature, such as in a sauna (around 70°C). As the synthetic polymer formed within the fibers remains, thanks to its Tg, unaffected by such conditions or treatments, so is the modified shape of the fibers achieved using compositions and methods according to the present teachings, though additional or alternative mechanisms of action may contribute to this effect.

[0122] While polymerization reactions can in principle benefit from the presence of curing facilitators in the same phase as the CNPFAs, this is not essential for the present compositions. Curing facilitators can be, in theory, cross-linkers or curing accelerators, being chemically distinct from the polymerizable ingredients. Cross-linkers refer to compounds that actively participate in the curing process, being integrated into the resulting polymer network and usually increasing the cross-linking density, while curing accelerators may alternatively catalyze or activate the curing (e.g., by lowering the polymerization temperature or increasing its rate), without necessarily becoming part of the cured polymer. Regardless of their mechanism of action, curing facilitators are typically sensitive materials and their presence in a composition often requires demanding precautions.

[0123] The present Inventors have discovered that in some circumstances polymers formed with a relatively low cross-linking density, including in absence of curing facilitators, can be suitable to provide a desirable shape to permeable fibers.

[0124] Considering the exemplary use of hair styling, this is the case in particular when the hair fibers are damaged, for instance as a result of their health status or of having been subjected to a conventional procedure deleterious to the hair, such as bleaching or coloring. Damaged hair fibers can display discontinuities in their outer surfaces, allowing for more water to penetrate the hair shafts as compared to healthy hair fibers. When the hair fibers are exposed to high temperatures (e.g., during styling with a hot flat or curly iron), the residual water which can be present within the hair cortex may undergo explosive evaporation, further enlarging the defects of the damaged hair fibers or forming new micro-pores accelerating future permeation of water, the proliferation of such voids with each elevated heating significantly detracting from the hair integrity, possibly leading to hair breakage.

[0125] Without wishing to be bound by theory, it is believed that polymers formed with a relatively low cross-linking density (e.g., in the presence of mono-reactive FAs) behave in a thermoplastic manner, namely can reversibly become softer and malleable upon heating, while being sufficiently rigid upon cooling and at ambient temperatures to maintain a desired style to the treated hair. It is believed that this relative “flowability” of polymers having a relatively low cross-linking density (as would be the case at least at the beginning of polymerization) allows them, upon heating of the hair fibers, to lock the scales, block or seal the pores or voids that may be present or have formed, especially in damaged hair. This “sealing effect” is expected to reduce water re-entry into the hair over time, thus decreasing the likelihood and / or extent of explosive evaporation of trapped water upon subsequent heating. Such reduction of water reentry can be desirable for both damaged and undamaged hair, and hence, compositions forming polymers having a thermoplastic behavior by having a relatively low cross-linking density may be applied to both hair forms. Advantageously, such sealing effect of the shapeable polymers may alternatively, or additionally, prevent egress of substances desirably found within the fibers.

[0126] Regardless of the type of natural polymers (resins and / or waxes) and fatty agents (fatty amines, alcohols and / or acids) that may cross-link so as to form within the (e.g., hair) fibers a network inter alia able to constrain them in a desired modified shape, the resulting polymer internally formed can also be referred to as a synthetic skeleton. This term is not meant to imply that the starting reagents are necessarily artificial, but that the resulting polymer is synthesized in situ, and not naturally occurring within the fibers. Simply presented, the extraneous polymer is able to “lock” the fibers in the desired shape, overcoming the innate force of the fibers otherwise allowing them to have or regain their natural shape. This “mechanical” metaphor is not intended to rule out any other or additional (e.g., chemical) mechanism of action of the polymers made of CNPFAs, enabling them to maintain any desired styling effect or shape. For instance, the polymers may alternatively or additionally act as a water-barrier, preventing, reducing or delaying the migration of water molecules from the external environment to the innermost portion of the fiber (e.g., made of keratin protein). In hair fibers, the resulting polymers may also reduce the tendency of the hair scales to open up, as can be confirmed by a reduced occurrence of frizzy hairs and / or an increased shine resulting from the relative smoothness of the hair surface thanks to the fairly closed hair scales. Water molecules undesirably reaching hair constituents styled by the present method may restore hydrogen bonds within such proteins to an extent allowing the hair fibers to gradually revert to their native shape.

[0127] The water-soluble hygroscopic agents

[0128] The water-insolubility of the polymers made of CNPFAs as aforesaid (which can have a solubility in water as high as the solubility of the FAs, if remaining in excess, but preferably as low as the solubility of the NPs, z.e., below 1 wt.%, the polymer optionally displaying intermediate values), can provide a water-barrier, preventing, reducing or delaying the migration of water molecules within the fibers. But this role can be fulfilled by additional substances, such as the water-soluble hygroscopic agents (WHAs) which may be added to the composition and serve to sequester water molecules in view of their hygroscopicity.

[0129] Without wishing to be bound by any particular theory, a WHA, being dissolved within the aqueous phase of a composition being in the form of an oil-in-water emulsion, is believed to penetrate into the fibers together with the polymerizable water-insoluble constituents (CNPFAs) of the composition, where they may have two roles. In a first phase of the method, in abundant presence of water, the hygroscopic properties of the WHAs may cause a relative swelling of the fibers, which may in turn increase the density and / or dimensions of the openings through which the polymerizable ingredients may penetrate the fibers. In a second phase of the method, upon elimination of water (e.g., during the application of thermal energy), the hygroscopic agent may crystallize, resulting in the formed polymeric network now containing crystals of the hygroscopic agent either intertwined therein or forming separate individual crystalline bodies. The crystallized state of the hygroscopic agent is believed to increase its water-absorption ability, thus enhancing its capacity to sequester and eliminate any water molecules penetrating the fibers (e.g., originating from environmental air humidity), and consequently, allowing for a long-lasting styling of the hair. Conversely, a crystallized WHA may serve as an internal reservoir of water molecules which may also desorb them under suitable conditions, for instance in a method of restyling or de-styling hair fibers previously treated and styled with the present compositions.

[0130] The water-solubility of the WHAs can be determined as previously described for the water-insoluble materials, and they typically have a solubility of more than 1 wt.%, by weight of the water and a temperature of 25°C. In some cases, the WHAs are highly soluble with a solubility of 10 wt.% or more, 15 wt.% or more, 20 wt.% or more, 30 wt.% or more, 40 wt.% or more, or 50 wt.% or more, by weight of the water. In some cases, the WHAs have similar solubilities with respect to the weight of the aqueous environment wherein they are to be disposed at the pH of the liquid, and for illustration, a WHA should not only have a solubility of more than 1 wt.% by weight of pure water, but also by weight of the aqueous phase of the composition (if an emulsion). Unless otherwise stated, all values refer to measurements made at room temperature under atmospheric pressure.

[0131] In some cases, the WHAs may be highly soluble in water, with a solubility of up to 200 wt.%, up to 150 wt.%, up to 125 wt.%, up to 100 wt.%, or up to 75 wt.%, by weight of water. In other words, up to 200 weight parts, up to 150 parts, up to 125 parts, up to 100 parts, or up to 75 parts of WHA would dissolve in 100 weight parts of water. It is stressed that the solubility of the WHA by weight of a liquid is not to be assimilated with the concentration of the WHA in the liquid containing it. For illustration, assuming the WHA and the water are the sole constituents of a mix, then the concentration of a WHA having a solubility of up to 150 wt.% by weight of pure water could be of up to 60 wt.%, per weight of the aqueous mix, this relative concentration of the WHA further decreasing as other constituents (e.g., CNPFAs) are added to form a complete composition. The solubility might be the same or slightly lower in the aqueous phases containing all water miscible materials but the WHA, the WHAs having, in some cases, a solubility of up to 180 wt.%, up to140 wt.%, up to 110 wt.%, up to 80 wt.%, or up to 50 wt.%, by weight of the composition or of an aqueous phase thereof.

[0132] Besides being water-soluble, the WHAs are required to be hygroscopic, readily taking up and retaining moisture (z.e., water molecules). There is typically, but not always, a positive correlation between the water-solubility of a material and its hygroscopicity. Thus, the latter can be independently considered and determined. The tendency of a dry material to gain weight from ambient moisture can be determined at various temperatures and relative humidities, and for any predetermined duration of time. In some cases, the hygroscopicity of the WHA is such that when a dry compound is exposed for 24 hours at a relative humidity (RH) of 75%RH and a temperature of 25°C, the WHA has a moisture absorption of 5% or more, 10% or more, or 15% or more by weight of dry WHA, as measured by a weight gain method at equilibrium.

[0133] While the hygroscopic agents used in the present compositions can be liquid at room temperature, they are advantageously solid to further increase their residency within the fibers once the liquid carrier which delivered them is eliminated from the fibers. Thus, in some cases, the WHA has a melting temperature (Tm) higher than about 25°C. When the fibers to be treated are attached to a living subject, being for instance hair fibers of a mammalian, the Tmof the WHA can be higher than the body temperature, or higher than external temperatures in extreme conditions, as it is undesirable that the WHA liquifies within the hair fibers that are in contact with the scalp, possibly leaching out of the fibers. Hence, the WHA may preferably have a Tmof 37°C or more, 40°C or more, 45°C or more, or 50°C or more. In some cases, the melting temperature Tmis lower than about 250°C, lower than about 200°C, lower than about 180°C, or lower than about 160°C.

[0134] Additionally, the WHA(s) can be selected to have a boiling temperature Tbgreater than the boiling temperature of water, so that the WHAs would not readily evaporate as the hair fibers are treated to remove water (e.g., the hair being dried). In some cases, the at least one WHA has a Tbof 100°C or more, 120°C or more, 130°C or more, or 140°C or more. In some cases, the WHA has a Tbof 350°C or less, 300°C or less, 250°C or less, or 225°C or less. The temperatures characterizing a material (e.g., Tm, Tb, etc.) are typically provided by its manufacturer, but can be readily determined by standard methods, using for illustration Differential Thermal Analysis (DTA), Thermogravimetric Analysis (TGA) or Differential Scanning Calorimetry (DSC), such as described in ASTM E794-06, or ASTM 3418.

[0135] For similar reasons (e.g., increasing the likelihood of a prolonged residency of the WHAs within the fibers), the WHA(s) can be selected to have a vapor pressure lower than the vapor pressure of water (z.e., < 2.3 kPa), preferred values being as already recited in the general requirements for non-volatile materials.

[0136] To favor the hygroscopic agents in their competition with other compounds for the binding of water molecules, a suitable WHA preferably has a hydrogen bond energy (or hydrogen bonding energy) with water molecules that is greater than the hydrogen bond energy of water molecules among themselves (in pure water). In some cases, the WHA has a hydrogen bond energy with water molecule of at least 21 kJ / mol, at least 22.5 kJ / mol, at least 25 kJ / mol, or at least 27.5 kJ / mol. In some cases, the WHA has a hydrogen bond energy with water of at most 40 kJ / mol, at most 35 kJ / mol, or at most 32.5 kJ / mol. The hydrogen bonding energy of a material can be available from literature or estimated by known computer simulations according to empirical or semi-empirical approaches, for instance by the Density Functional Theory (DFT) calculations. Experimental studies indicating the formation of hydrogen bonds and the relative strength of bonding in various hydrogen-bonded complexes typically rely on crystallography and spectroscopy, such as infra-red (IR), nuclear magnetic resonance (NMR), microwave, electronic and Raman spectroscopy. For illustration, the hydrogen bond energy between an amine group (as can be found in a WHA) and water has been reported to be of about 29 kJ / mol, whereas the hydrogen bond energy of water molecules in pure water is of about 21 kJ / mol.

[0137] It is desirable that the hygroscopic agent does not substantially affect or modify the charge of the composition, hence, a WHA that is non-ionic or non-electrolyte is preferred. Yet, an ionic hygroscopic agent may be used, in particular if present in an amount such that the zeta potential of the composition is substantially null. This is not essential, yet when the fibers and the composition have relatively similar zeta potentials (e.g., within 10 mV one from the other), the absence of strong repulsive or attractive forces is expected to promote migration of the composition via hydrophobic:hydrophobic interactions through the surface of the (e.g., hair) fibers and its retention therein.

[0138] It is further desired that the WHAs used in the present compositions (as any other material deemed suitable) has substantially no negative impact on the stability of the dispersion, such has no negative effect on the size of the emulsion droplets and / or on their size distribution, which may lead to a collapse of the emulsion (e.g., phase separation). The composition, if an emulsion, may have water-insoluble “oil” droplets not exceeding a few micrometers (e.g., having a D90 < 20 pm and / or a D50 < 10 pm, 5 pm, 2 pm, or 1 pm, parameters such as D10, D50, and D90 being measurable by Diffractive Light Scattering (DLS)).

[0139] In some cases, the water-soluble hygroscopic agent is selected from a group consisting of amides (e.g., carboxamides, including aliphatic and aromatic amides and amino acid amides, methylxanthines and purine alkaloids) and salts thereof; organic acids and salts thereof or organic salts (e.g., quaternary ammonium compounds); saturated or unsaturated heterocyclic compounds (e.g., imidazoles and oxethanes); monosaccharides (e.g., glucose, fructose, galactose or mannose); disaccharides (e.g., sucrose or lactose); and combinations thereof.

[0140] In one case, the WHA (or one of the WHAs) is a carboxamide having the general formula RC(=O)NR'R", wherein R, R', and R" each independently represent an organic group or a hydrogen atom. In some cases, R can include a second carboxamide group. For illustration, methanamide (also referred to as formamide) and urea are carboxamides wherein R is respectively H or NH2, and R’ and R” are hydrogen atoms in both cases. R, R’, and R” are typically relatively short molecular structures, for instance short linear, branched, or cyclic, substituted or unsubstituted, saturated alkyls having generally from 1 to 6 carbon atoms. Carboxamides wherein R is a short Ci-Ce alkyl as aforesaid and R’=R”=H, include a) ethanamide (also referred to as acetamide) (R=CH3), propaneamide (R=CH2CH3) and butanamide (R=CH2 CH2CH3), for illustration of short alkyls which can be branched if having a sufficient amount of carbon atoms; b) cyclopropane carboxamide, cyclobutane carboxamide, cyclopentane carboxamide and cyclohexane carboxamide, for illustration of short cyclic alkyls; and c) ethanediamide (also known as oxamide), propanediamide (also known as malonamide), butanediamide, pentanediamide and hexanedi ami de, for illustration of diamides. Carboxamides having, like urea, more than one amine group can be related to amino acid, and as such are often referred to as amino acid amides. This group of WHA compounds includes alanine amide, asparagine amide, glutamine amide, glycine amide, and proline amide. In some cases, the WHA is selected from a group comprising urea and its derivatives and isomers thereof, such as alkyl derivatives, e.g., 1,3 -dimethyl urea, betaine, caffeine, imidazole, niacinamide and D(-) pantolactone. In a particular case, the WHA is urea or a derivative and / or isomer thereof. [XXX to be amended to ensure all chemistries of new WHAS are covered SAGI]

[0141] In another case, the WHA (or one of the WHAs) is an organic acid selected from a group comprising citric acid, gluconic acid, lactic acid, malic acid, oxalic acid, salicylic acid, succinic acid, tartaric acid, and metal (e.g., Na, K, Mg) salts thereof.

[0142] It is noted that, in some cases, the WHAs of the present compositions do not substantially interfere with the pH of the composition when added at low concentrations (e.g., 1 wt.% or less by weight of the composition). At such concentrations, the pH of the composition is typically similar in presence or absence of the WHA(s), such compounds increasing the pH or decreasing the pH by half-a-log or less. For illustration, if a composition has a pH of 7.5 without the WHA(s), the addition of up to 1 wt.% of the hygroscopic agent(s) might adjust the pH to a value in a range of pH 7 to pH 8, a change in pH being in some cases of 0.4-log or less, 0.3-log or less, 0.2-log or less, or 0.1-log or less. Reverting to the illustration, a composition having a pH of 7.5 without WHA(s) may respectively have a pH in the range of 7.1-7.9, 7.2-7.8, 7.3-7.7, or 7.4-7.6, in the presence of the WHA(s) at such low concentrations. This, however, is not essential, as some WHAs may favorably contribute to achieve a pH desired for the composition (e.g., adapted to promote hair scales opening and / or facilitate hair penetration).

[0143] The WHAs may be present at any suitable concentration within the aqueous phase of the composition, the concentration preferably being sufficiently high to drive the migration of the materials to the inner portions of the fibers thanks to a gradient of concentration between the externally applied composition and the fibers. On the other hand, the WHAs should not compete with the polymerizable CNPFAs ingredients for penetration within the fibers to an extent diminishing the internal formation of the shapeable polymer. In other words, the concentration of the WHAs should be sufficiently low so as to leave room within the fibers for the NPs and FAs due to polymerize therein.

[0144] In some cases, the concentration of the water-soluble hygroscopic agent in the oil-in-water emulsion is at least 1 wt.%, at least 5 wt.%, at least 10 wt.%, at least 12.5 wt.%, at least 15 wt.%, at least 17.5 wt.%, or at least 20 wt.%, by weight of the oil-in-water emulsion. In some cases, the concentration of the WHA in the oil-in-water emulsion is at most 50 wt.%, at most 48 wt.%, at most 46 wt.%, at most 44 wt.%, at most 42 wt.%, at most 40 wt.%, at most 38 wt.%, at most 36 wt.%, or at most 34 wt.% by weight of the oil-in-water emulsion. In other cases, the concentration of the WHA in the oil-in-water emulsion is between 1 wt.% and 50 wt.%, between 5 wt.% and 50 wt.%, between 10 wt.% and 50 wt.%, between 12.5 wt.% and 48 wt.%, between 15 wt.% and 46 wt.%, between 17 wt.% and 44 wt.%, or between 20 wt.% and 42 wt.%.

[0145] Co-solvents

[0146] Water may not be the sole “liquid carrier” of the present compositions, and in some cases, the compositions can further contain at least one co-solvent. Without wishing to be bound by any particular theory, co-solvents are believed to improve the surface tension of the waterinsoluble “oil” phase so as to facilitate wetting of the fibers by the droplets of water-insoluble polymerizable materials, enhancing in turn the penetration inter alia of the CNPFAs, and / or to increase the miscibility of the natural polymers with the fatty agents. However, as such materials can be deleterious to some fibers under treating conditions that may enhance their adverse effects, it is stressed that a co-solvent is included in the compositions only if safe to the fibers to be treated therewith under the conditions set for their application to the fibers.

[0147] The at least one co-solvent that may optionally be included in the composition can be selected from Ci-Ce alcohols having at least one hydroxyl group, such as methanol, ethyl alcohol, isopropyl alcohol, 2-methyl-2-propanol, sec-butyl alcohol, t-butyl alcohol, propylene glycol, 1 -pentanol, 1,2-pentanediol, 2-hexanediol, or benzyl alcohol; water-miscible ethers such as di(propylene glycol) methyl ether, diethylene glycol monoethyl ether, dioxane, di oxolane, or 1 -methoxy -2-propanol; aprotic solvents such as ketones (e.g., methyl ethyl ketone, acetone), dimethyl sulfoxide, acetonitrile, n-methyl pyrrolidone, di-methyl carbonate or dimethylformamide; esters, such as C 12-15 alkyl benzoate; and mineral or vegetal oils, such as isoparaffinic fluids, olive oil, coconut oil or sunflower oil.

[0148] As readily appreciated by the skilled persons, some of these co-solvents can indifferently be mixed with the CNPFAs of the oil phase, with the aqueous phase, or in parts with both, during the preparation of a composition being an oil-in-water emulsion. The co-solvent can be used alone, or in combination with other suitable co-solvents.

[0149] In some cases, the (combined) concentration of the co-solvents in the oil-in-water emulsion, when present, is at least 1 wt.%, at least 3 wt.%, at least 5 wt.%, or at least 7 wt.% by weight of the oil-in-water emulsion. The maximal amount of co-solvents may depend on the CNPFAs being selected, as well as on the presence of any additional ingredients. In any event, the concentration of co-solvents is such that the composition is in the form of an emulsion. In some cases, the combined concentration of the co-solvents is at most 20 wt.%, at most 18 wt.%, or at most 15 wt.% by weight of the oil-in-water emulsion, said concentration being selected or adapted to the form of the composition.

[0150] For comparison, the concentration of water in the oil-in-water emulsion is at least 40 wt.%, at least 45 wt.%, or at least 50 wt.% by weight of the oil-in-water emulsion. In some cases, the concentration of the water is at most 90 wt.%, at most 80 wt.%, at most 70 wt.%, at most 65 wt.%, or at most 60 wt.% by weight of the oil-in-water emulsion. In particular cases, the concentration of the water is between 40 and 90 wt.%, between 40 and 70 wt.%, between 40 and 65 wt.%, or between 45 and 65 wt.% by weight of the oil-in-water emulsion.

[0151] Additional ingredients

[0152] In order to facilitate the migration and / or retention of the CNPFAs to the surface of the fibers, which in turn may increase their permeation therein, there should preferably be a difference between the zeta potential of the composition and the fibers. For example, the zeta potential of the composition at its pH (or ^) should preferably be more negative or more positive than a zeta potential of the (e.g., mammalian hair) fibers (or ^h) at the same pH. In some cases, the ingredients used in the composition may provide, in addition to any other function primarily intended, sufficient charging of the composition to achieve such a gradient of zeta potential values. For instance, fatty amines, fatty alcohols, fatty acids, pH modifying agents, and / or wetting agents may contribute to suitable charging of the oil-in water emulsion. In some cases, an agent dedicated to this effect, referred to as a charge modifying agent, can be added to the composition. For illustration, a water-insoluble, non-reactive amino-silicone oils may be added to the oil phase of the emulsion to modulate its zeta potential.

[0153] In some cases, the difference between the zeta potential of the composition c and the zeta potential of the fibers

[0154]

[0155] to be treated thereby, also termed the zeta differential or delta zeta potential (A c-h) is in absolute terms at least 5 mV, at least 10 mV, at least 15 mV, at least 20 mV, at least 25 mV, at least 30 mV, or at least 40 mV. In some cases, A^c-h absolute value is within a range of 5 to 80 mV, 10 to 80 mV, 10 to 70 mV, 10 to 60 mV, 15 to 80 mV, 15 to 70 mV, 15 to 60 mV, 20 to 80 mV, 20 to 70 mV, 20 to 60 mV, 25 to 80 mV, 25 to 70 mV, 25 to 60 mV, 30 to 80 mV, 30 to 70 mV, 30 to 60 mV, 35 to 80 mV, 35 to 70 mV, or 35 to 60 mV. Such values are preferable to set an initial charge gradient driving inter alia the CNPF A(s) (e.g., as droplets) towards the fibers for their penetration therein together with the WHA(s), when present. Understandingly, such gradient decreases over time, as the materials of the compositions initially accumulates on the fiber outer surface modifying its zeta potential. This process is self-terminating, the migration from the composition to the fibers ceasing once the gradient becomes too low (e.g., when the delta zeta potential becomes lower than 5 mV). Zeta potential can be determined by standard methods using any equipment suitable for the measurement of charge of dispersed particles.

[0156] The composition may also comprise any other additive customary to compositions being similarly applied to permeable fibers. Considering for illustration hair styling compositions that can be applied to human hair, the additives can be preservatives, antioxidants, bactericides, fungicides, chelating agents, vitamins and fragrances (or odor masking agents), or any other agent customary to hair styling compositions, such as hair detangling agents and hair conditioning agents, the nature and concentration of which need not be further detailed herein.

[0157] The composition may also comprise any other additive customary to the form in which the composition is to be applied to the fibers, such as emulsifiers, wetting agents, thickening agents, or propellants, if the composition is to be sprayed, the nature and concentration of which need not be further detailed herein.

[0158] For illustration, a thickening agent can be added, generally to the aqueous phase of the oil-in-water emulsion, to provide a desired viscosity to the composition. The viscosity should be sufficiently low to allow easy application of the composition to the fibers (e.g., so as to satisfactorily coat all individual hair fibers), but high enough to remain on the fibers for sufficient time and prevent dripping. A relatively low viscosity may also facilitate penetration of the CNPFAs into the (e.g., hair) fibers by diffusion and / or capillarity. Exemplary thickening agents can be hyaluronic acid, poly(acrylamide-co-diallyl-dimethyl-ammonium chloride) copolymer (Poly-quaternium 7, e.g., by Dow Chemicals), quatemized hydroxyethyl cellulose (Poly-quaternium 10, e.g., by Dow Chemicals), hydroxypropyl methylcellulose, water soluble gums, hydroxypropyl guar (e.g., Jaguar® HP-105), SepiPlus™ S, etc. Thickening agents, if added, are typically at a concentration of at least 0.1 wt. %; at most 10 wt.%; and optionally between 0.5 wt.% and 5 wt.% by weight of the aqueous phase.

[0159] The composition, if an oil-in-water emulsion, may further contain an emulsifier, so as to facilitate the formation of the emulsion and / or to prolong its stability. In some cases, the emulsifier is a non-ionic emulsifier, preferably having a hydrophile-lipophile balance (HLB) value between 2 to 20, between 7 to 18, between 10 to 18, between 12 to 18, between 12 to 17, between 12 to 16, between 12 to 15, or between 13 to 16 on a Griffin scale. Suitable emulsifiers can be water-soluble (e.g., having an HLB value between 8 and 20), such as polysorbates (often commercialized as Tweens), ester derivatives of sorbitan (often commercialized as Spans), acrylic copolymers (e.g., commercially available as Synthalen® W2000), and combinations thereof, or oil-soluble, such as lecithin and oleic acid (e.g., having an HLB value between 2 and 8).

[0160] In order to facilitate penetration of the CNPFAs into fibers (e.g., by capillary effect), the composition should be able to properly spread over the fibers to permit adequate contact. Proper wetting of a surface can theoretically be improved by tuning the surface tension of the composition measured in milliNewton per meter (mN / m) to be lower than the surface energy of the fibers. Such properties can be determined by standard methods, and for instance according to procedures described in ASTM D1331-14, Method C.

[0161] In some cases, the compositions of the present invention have a surface tension between 25 and 60 mN / m, between 25 and 55 mN / m, between 25 and 50 mN / m, between 25 and 45 mN / m, between 25 and 40 mN / m, between 25 and 35 mN / m, or between 30 and 40 mN / m.

[0162] Wetting agents can be added to the composition, at any suitable concentration tailoring its surface tension to be within any of the afore-described suitable ranges. Exemplary wetting agents can be silicone-based, fluorine-based, carbon-based or amine-alcohols. Silicone-based wetting agents can be silicone acrylates (such as SIU 100 by Miwon Specialty Chemical). Fluorinated wetting agents can be perfluorosulfonic acids (such as perfluorooctanesulfonic acid) or perfluorocarboxylic acids (such as the perfluorooctanoic acid). Amine-functionalized silicones can also be used as wetting agents (such as amo-dimethicone or bis-aminopropyl dimethicone). Wetting agents, if added, are typically present in the composition at a concentration of at least 0.001 wt.%, at least 0.01 wt.% or at least 0.1 wt.%; at most 1.5 wt.%, at most 1.4 wt.% or at most 1.3 wt.%; and optionally between 0.001 and 1.5 wt.%, between 0.01 and 1.4 wt.% or between 0.1 and 1.3 wt.% by weight of the composition.

[0163] Last exemplary prospective additional ingredients to the present compositions are coloring agents. Depending on the fibers to be treated, and the dimensions of openings thereon that may permit penetration of materials within their inner cores, the coloring agents can be pigments or dyes. The coloring agents can be selected according to the desired final shade of the fibers (taking into consideration the initial shade of the fibers and any coloring effect the composition may have thereon in absence of coloring agents) and according to the sought duration of coloring. Typically, but not necessarily, the sought duration of coloring can be commensurate with the sought duration of styling. Pigments and dyes are too numerous for an extensive listing but persons skilled in the coloring of fibers know which agents and concentrations thereof can be conventionally used to achieve particular shades.

[0164] Considering the specific case of styling keratinous fibers (e.g., mammalian hair), numerous compendiums of suitable hair dyes are available, such as the lists maintained by regulatory authorities in each market of interest. In Europe, for instance, such materials can be found in Annex IV of Regulation (EC) No 1223 / 2009 on cosmetic products, whereas in the USA they would be included in the Listing of Color Additives maintained under the Federal Food, Drug, and Cosmetic Act (FD& C Act), which include coloring agents exempt from certification (21 CFR Part 73 Subpart C — Cosmetics) or subject to certification (21 CFR Part 74 Subpart C — Cosmetics). As the present styling method is advantageously innocuous to the hair fibers (e.g., as can be established by mechanical or thermos-physical properties of treated fibers being comparable to untreated fibers), the coloring agents to be included in the compositions, if desired, should preferably also be harmless to the fibers.

[0165] Depending on the coloring substances being selected and on their respective watersolubility, or lack thereof, the coloring agents can be added either to the water-insoluble or the water-soluble phase of the composition, or to both is suitable agents are selected. When the coloring agents are oxidative dyes comprising an often colorless precursor, called a developer, and an oxidant reacting into colored molecules trapped into the hair shaft, typically in presence of couplers, the reactivity of the coloring constituents requires that the oxidating agent is incorporated into the styling composition including suitable precursors and couplers close to the time of its application for incubation on the fibers, to prevent premature reactions.

[0166] It is believed that the polymers formed from the CNPFAs may not only prevent entry of water molecules, but also egress of coloring agents. Thus, a coloring effect of fibers treated with the present compositions is expected to last longer than a similar coloring of similar fibers, treated by a different method devoid of cured NPFAs which may delay the gradual loss of artificial coloring. This prolongation of a coloring effect can be achieved regardless of the method used for coloring the fibers in the first place.

[0167] Preparation of the composition

[0168] The single-phase compositions and oil-in-water emulsions can be prepared by any suitable method. For instance, the present compositions can be manufactured by mixing a first blend including the CNPFAs, hence including a predominant portion of the water-insoluble “oily” phase, with a second liquid, including a predominant portion of the aqueous phase in which the WHA(s) and any other water-soluble additive, when present, would be dissolved. These distinct sub-compositions, respectively forming an “oil compartment” and an “aqueous compartment”, are each said to include a predominant portion of any of the two phases, as it cannot be ruled out that some of the compounds of an oil-in-water emulsion may actually partly migrate between the two phases.

[0169] If an oil-in-water emulsion is prepared by mixing a water-insoluble compartment including the CNPFAs with an aqueous compartment including the WHAs, each may comprise an amount of respective ingredients suitable to achieve desired concentration in the final oil-in-water emulsion, upon mixing of the two compartments in set ratios.

[0170] Typically, the oil phase is dispersed as minute droplets within a continuous aqueous phase, the composition therefore forming an oil-in-water emulsion, which may additionally include an emulsifier.

[0171] The mixing and / or emulsification of the aforesaid materials can be performed by any method known in the art. While manual blending or shaking may suffice, various equipment, such as a vortex, an overhead stirrer, a frother, a whisker, a magnetic stirrer, an ultrasonic disperser, a high shear homogenizer, a sonicator and a planetary centrifugal mill, to name a few, can be used, typically providing more uniform compositions, for instance more homogenous populations of oil droplets in the aqueous phase of an oil-in-water emulsion.

[0172] The composition can be prepared by mixing or emulsifying the contents of the waterinsoluble and the water-soluble compartments soon after each of the respective parts are ready, but this step can be deferred (e.g., the mixing being performed prior to application, which can take place at any time following preparation, as long as the composition is stable and potent). For instance, if an emulsion, the composition can be applied as long as the oil droplets are within their desired size range (e.g., of no more than a few micrometers, typically less than 10 pm), and provided that the CNPFAs have not polymerized in vitro to an extent precluding their entry within the fibers.

[0173] Since, as above exemplified, a number of compounds present in the composition may contribute to any of its particular property or function, whether dedicated for that purpose as primary role or inherently contributing to achieve it, the property sought for the composition is typically monitored at equilibrium. For illustration, if it is desired that a composition according to the present teachings has a pH, a polarity, a charge, or any other property of interest, within a particular range, such property can be arbitrarily determined 12 hours after having prepared the composition or a compartment thereof (even if a similar value could have been obtained upon completion of the preparation).

[0174] Kits for the preparation of the composition

[0175] In view of the relative simplicity of the composition as herein detailed, and as shall be illustrated in the working examples, the present composition can be supplied as a ready to use composition, all desired ingredients being formulated for example as an oil-in-water emulsion having a gel-like viscosity for ease of application, such compositions being typically stable for at least a few months (e.g., 3 months or more) even when kept at room temperature, the compositions being stable for longer period of times if kept at lower temperatures (e.g., between 5°C and 20°C) and / or under stabilizing conditions (e.g., under inert atmosphere, in light blocking containers, etc.).

[0176] That being said, present compositions can alternatively be prepared when desired using a kit containing enough reagents for a final volume / weight of composition sufficient for the intended use or enough reagents to form a concentrate that can be diluted before use (e.g., with tap water).

[0177] The kit, in its simplest form, comprises:

[0178] I. a first compartment of water-insoluble materials containing at least one NP and at least one FA (which may optionally be pre-polymerized); and

[0179] II. a second compartment of water-soluble materials containing at least one of water and a WHA; wherein the mixing of said compartments’ contents produces a composition capable of forming a shapeable polymer within permeable fibers (e.g., a hair styling composition being a singlephase or oil-in-water emulsion), the composition being as described above and adapted to the method further detailed herein.

[0180] The components of the kit can be packaged and kept in the various compartments under an inert environment, preferably under an inert gas, e.g., argon or nitrogen, and / or under any other suitable conditions preventing or reducing during the storage of the kit adverse reactions that may diminish efficacy of the composition (e.g., the walls of the compartments being lightblocking). For instance, the kit should be stored at temperatures that would not induce polymerization, such as below 30°C, below 20°C or below 10°C.

[0181] The kit may further contain at least one of a co-solvent, an emulsifier, a wetting agent, a thickening agent, a pH modifying agent and a charge modifying agent, as previously detailed, or any other additives conventionally present in the compositions to be prepared therewith, which materials can be included in any one of the compartments described above, according to their respective solubility, or in separate additional compartments to ensure stability e.g., during storage of the kit. For instance, if the composition to be prepared by mixing of all compartments is to further include oxidative dyes, then the kit may include at least a third compartment for the oxidant and optionally a fourth compartment for couplers, to separate them from the color precursors that would react therewith to turn into the final coloring substance. As a rule, all materials required for the preparation of a desired composition from the kit can be disposed in same compartments (e.g., as the NPs, FAs or WHAs) or in separate compartments as needed to ensure that no deleterious (e.g., premature) reactions can take place between substances in a same compartment that would adversely affect the efficacy of the composition to be prepared by mixing of all compartments when desired.

[0182] The kit typically includes a leaflet guiding the end-user on the manner of mixing the various compartments, the order of which may depend on the nature of the ingredients and / or the contents of the respective compartments. Generally, the proposed method of mixing and application shall enable the preparation of an effective and safe composition, to be applied within a time period suitable for its potency and intended use.

[0183] The ingredients of the various compartments can be mixed, as may be instructed in such a leaflet, prior to the application of the final composition on the fibers. In such a case, the obtained composition (e.g., an oil-in-water emulsion) may be used immediately, or maintained, un-applied, for up to 3 hours, up to 2.5 hours, up to 2 hours, up to 1.5 hours or up to 1 hour, prior to its application on the (e.g., hair) fibers.

[0184] Similarly, different timing and duration for application of the composition may conceivably be suggested depending on the desired duration of styling. For instance, if a shortterm styling and / or a modest change of shape is desired, the composition may be applied for a shorter period of time than when a longer lasting styling and / or a more dramatic shape modification is desired.

[0185] Method for modifying fibers’ shapes

[0186] Having described the compositions and the materials that may be contained therein, a method for modifying the shape of fibers by curing therein polymerizable ingredients, the polymer so formed being shapeable as desired, will now be provided with reference to Figure 1. The principles detailed with respect to the compositions apply mutatis mutandis to the method and may not necessarily be repeated in the following.

[0187] In a first step (S-01) of the method, a liquid composition is applied onto individual fibers so as to entirely cover them, the composition typically being an oil-in-water emulsion comprising at least one natural polymer (NP) and at least one fatty agent (FA), both being waterinsoluble, smaller than 10,000 g / ml and able to react one with the other to form larger macromolecules, the CNPFAs being as afore-detailed. The composition may further include one or more water-soluble hygroscopic agents (WHAs) in the aqueous phase of the styling composition, or any other additives previously mentioned (e.g., thickening agents increasing the viscosity of the composition or any additives enhancing permeation). The volume or weight of composition suitable to cover all fibers depends on the amount of fibers and can be referred to as a “styling-effective amount” of the composition, which in turn also needs to include a “styling-effective amount” of CNPFAs ± WHAs. The fibers can be hair fibers, in which case the composition may also be referred to as a hair styling composition. Unless otherwise stated, the emulsion is prepared by mixing the desired water-insoluble and water-soluble compartments shortly before its application, within at most 30 minutes from its emulsification, or within at most 20 minutes, at most 10 minutes, or at most 5 minutes.

[0188] In a second step (S-02) of the method, the composition is left in contact with the fibers for a period of time enabling at least partially penetration of the CNPFAs and, when present, WHAs within the fiber shaft. This step can also be referred to as a penetration enabling or an incubation step. In some cases, the composition is allowed to remain in contact or is maintained applied on the fibers for a period of at least 5 minutes, at least 10 minutes, at least 20 minutes, at least 30 minutes, at least 35 minutes, at least 40 minutes, at least 45 minutes, or at least 50 minutes. In some cases, the time period during which the composition remains applied on the fibers, alternatively referred to as the incubation time, is at most 12 hours, at most 10 hours, at most 5 hours, at most 2 hours, or at most 1 hour. In particular cases, the composition is maintained on the fibers for a period of time between 5 minutes and 30 minutes, 10 minutes and 60 minutes, 30 minutes and 12 hours, between 30 minutes and 5 hours, between 40 minutes and 2 hours, or between 50 minutes and 2 hours.

[0189] The composition can remain applied on the fibers at an ambient temperature, but this step can alternatively be performed at an elevated temperature of at least about 30°C, or at least about 40°C. The temperature at which the composition can remain in contact with the fibers, also referred to as the incubation temperature, may depend on the heat resistance of the fibers and of the composition (so as to prevent its thermal degradation). In some cases, when the fibers are hair fibers attached to a living subject, the incubation temperature is at most about 60°C, at most about 55°C or at most about 50°C. In particular cases, the liquid composition is maintained on the fibers at a temperature in a range between 15°C and 25°C, between 25°C and 60°C, between 25°C and 55°C, or between 25°C and 50°C. While working at elevated temperatures is believed to promote the migration of the CNPFAs within the fibers, e.g., by relatively softening the fiber and / or increasing their permeability, this is permissible provided that the composition does not dry during the process, the elimination of the liquid carrier adversely affecting the ability of the CNPFAs to penetrate into the fibers.

[0190] When the incubation is performed for relatively prolonged periods of time and / or at relatively elevated temperatures, means can be implemented to prevent or delay evaporation of the composition. For illustration, hair can be wrapped in protective foils or otherwise placed into a relatively sealed environment (e.g., under a shower cap).

[0191] After said penetration-enabling incubation, in a third step (S-03) of the method, the fibers can be rinsed to remove excess composition, if required for proper transfer of energy and / or shaping of the fibers at a subsequent step.

[0192] In a fourth step (S-04) of the method, energy is applied to the fibers so as to at least partially cure the CNPFAs having partially penetrated within the fibers. The energy can be thermal energy, which can be applied to the fibers by conduction (e.g., flat iron), convection (e.g., hot air blower) or radiation (e.g., IR radiation when the fibers are not attached to living subjects). This step can also be referred to as a curing or polymerization step.

[0193] Besides the sought polymerization of the CNPFAs into a shapeable polymer, this step can also modify the fibers so as to facilitate their reshaping by the polymer. Considering hair fibers for illustration, their wavy appearance is inter alia due to the presence of hydrogen bonds, heating of the keratinous fibers enabling breakage of these bonds (e.g., by elimination of water molecules) and a relaxation of the waves, or relative straightening of the fibers. In absence of any treatment, such reshaping of the fibers by mere drying would have been transient, the hydrogen bonds gradually reforming upon exposure to water, even in the form of environmental humidity. In the present case, the existence of polymerizable ingredients within the hair fibers at the time of hydrogen bond breakage is believed to enable alternative interactions between the broken bonds on the fibers and these materials, which may reduce the quantity of hydrogen bonds that could be subsequently reconstituted. This is in addition to the fact that shapeable polymers formed in the fibers, even without being bonded to previously broken hydrogen bonds, are believed to prevent or diminish access of water (either ambient or applied during wetting) to the fibers, thereby reducing or delaying the ability of hydrogen bonds to form again, Flat or curling irons may directly apply to the (e.g., hair) fibers elevated temperatures of about 160°C to 200°C, depending on the equipment being used, such temperatures enabling sufficient breakage of hydrogen bonds within a few minutes, while promoting curing of thermally curable NPFAs. As the fibers are typically held in contact with hot surfaces only briefly during each pass of the iron along the entire fibers, they (e.g., the hairs) may not reach the temperature of the ironing rod which can typically be set to be higher, e.g., between 120°C and 260°C, between 190°C and 230°C, or between 200°C and 220°C, some ironing equipment allowing to modulate temperature according to hair thickness. Conventional hot air blowers (e.g., hand held or salon hair dryers) typically result in relatively lower temperatures, e.g., between 50°C and 120°C, which may depend on the equipment used and on their distance from the fibers, this in turn requiring relatively longer period of times to achieve a desired breakage of hydrogen bonds and / or curing of the CNPFAs.

[0194] Typically, the fibers are heated up to a temperature of at least 40°C, at least 50°C, at least 70°C, at least 80°C, or at least 100°C, for no more than 5 seconds per segment of fibers when the temperature is elevated. The total duration of time of this step may naturally depend on the amount (e.g., surface area, thickness) of fibers to be treated, the initial shape of the fibers and the new sought one, relatively mild modification requiring less time than a relatively more dramatic change of shape, the heat being applied and such factors a skilled person may readily appreciate. For example, heating of the fibers could take less than 5 minutes, usually 1-2 minutes, for hair swatches of 5 g, when a heating iron set to a temperature of 220°C proceeds from one end of the swatch to the other and the fibers are subjected to multiple passes (30-50) of the flat iron. Depending on hair length, it may take up to 2 hrs to treat in their entirety hair disposed on human head, shorter hairs requiring only 1 hr or 1.5 hrs.

[0195] Usually, the temperature applied to achieve at least partial curing of the CNPFAs during step S-04 is in a range between 80°C and 220°C, between 100°C and 220°C, between 120°C and 220°C, or between 140°C and 200°C. It should be appreciated that the temperature provided by a heating device is generally higher than the temperature perceived by the fibers. While given a long enough residence time (period during which the segment of fibers is exposed to the heat), the temperature of the fibers could eventually reach the temperature of heating, this is not generally the case, thus while using a heating device set at 220°C may seem extreme, the fibers (depending on duration of contact, speed of passes) could reach a temperature of no more than 180°C, no more than 160°C, no more than 140°C, no more than 120°C, or no more than 100°C.

[0196] The thermal energy of step S-04 can be applied while styling the fibers into the desired shape, e.g., by a hair dryer, or a flat or curling iron, so as to modify their native shape. This step, during which the hair fibers are mechanically constrained in a dynamic or static way to modify their shape (e.g., being pulled over a comb or brush, rolled on a roller, or contacted by a styling iron), can therefore alternatively be referred to as the styling step. Having achieved enough modification of the fiber’s shape while constraining them as aforesaid, one may wish to continue applying a same or different heat without further contact with the fibers (e.g., using an overhead hair dryer hood, after having used a styling hot iron).

[0197] Regardless of the exact procedure selected to apply energy to the fibers, the polymerization is deemed partial, since not all reactive groups present on the NPs and the FAs are necessarily engaged in cross-linking upon conclusion of this step. While typically incomplete, the extent of partial polymerization should nevertheless be sufficient for the formation of a shapeable polymer within the fibers.

[0198] When polymerization is effected while the fibers are in a desired modified shape, the polymer resulting from the curing of the CNPFAs may maintain the fibers in the modified shape or delay their ability to regain native (un-modified) shape. In a fifth step of the method (S-05), the fibers now shape-modified can be washed. That may be recommended if the preceding steps did not include removal of excess composition but could be superfluous if satisfactory rinsing was performed or if the styling step involved mechanical removal of the previously applied composition. Post-styling washing is not a step essential to the modification of the shape, but, considering for instance full head hair or clothes, a procedure periodically performed. In some cases, it may be desired to postpone a first wash to take place at least 12 hrs, at least 24 hrs, at least 36 hrs, or at least 48 hrs after the completion of the styling step, as it is believed that polymerization may spontaneously continue following the energy trigger received during this step. Usually, washing of hair styled according to the present method takes place within at most a week from styling. Hair styled according to the invention can be washed with any shampoo, not being restricted to the use of a particular one to avoid ruining the styling effect, as often necessary for conventional methods.

[0199] Another step that can be optional is presented in Figure 1 as S-00 and relates to pretreatment of the fibers before applying the composition. For illustration, the fibers can be cleaned and / or dried. A cleaning pre-treatment seeks to remove any residual materials that may adversely affect the shaping method, such as dirt, grease, or any product often found on the fibers (e.g., residues of hair products on hair fibers). This can be done by applying any suitable cleaning products, such as sodium lauryl sulfate, this washing being followed by the rinsing of the fibers with excess water. A drying pre-treatment, which may follow rinsing or be independently performed, seeks to eliminate traces of rinsing water or residual moisture that may be present in the fibers. This however is not essential, as present compositions can be applied to wet fibers as well.

[0200] Alternatively, or additionally, the fibers can be subjected to a chemical pre-treatment (e.g., incubation with a pre-treating composition) or a physical pre-treatment (e.g., plasma treatment) that may, for instance, provide the fibers with desired surface properties facilitating penetration of the CNPFAs, protect the fibers from conditions (e.g., heat) to which they can be subjected in subsequent steps, facilitate the performance of steps of the present methods, and / or enhance the properties of the compositions.

[0201] For illustration a heat-protective formulation that may optionally be applied to the fibers before the application of the composition can contain or consist of oils having a relatively high smoking point at a temperature above the one applied for styling, such as silicone oils. Alternatively, the heat-protecting oils can be added to the CNPFAs, oils non-miscible with the CNPFAs being able to leach out of the composition to protect the polymerization process and / or the fibers during styling.

[0202] Not all possible steps are presented in Figure 1. For illustration, while step S-01 relates to the application of the composition being ready -to-use, the composition too can be pre-treated before use. For illustration, the CNPFAs can be pre-polymerized, that is to say heated to a temperature favoring their polymerization, the temperature and duration of the prepolymerization step being such that the macro-molecules that may form, at the expense of the building blocks, during this optional step, still satisfy the requirements set for materials due to penetrate within the fibers (e.g., having a MW of no more than 10,000 g / mol, etc.).

[0203] The conditions for pre-polymerization, if performed, can depend on the type of NPs and FAs intended to jointly polymerize. They may also depend on the entity performing this optional step. Typically, if performed by the manufacturer of the composition, the process can take more time and be performed at relatively lower temperature, whereas if the end-user of the composition is the one treating the CNPFA compartment before its mixing with an aqueous phase and their application to the fibers, the process should be shorter which generally requires relatively higher temperatures.

[0204] In some cases, pre-polymerization can be performed at a temperature between 20°C and 60°C, between 25°C and 60°C, between 30°C and 60°C, or between 40°C and 60°C, or at higher temperatures, such as between 100°C and 150°C or between 150°C and 200°C. Typically, the duration of pre-polymerization does not exceed 24 hours, 18 hours or 12 hours, when performed at relatively mild temperature, but can be shortened if performed at relatively higher temperatures (e.g., between 150°C and 200°C) which may require less than 8 hours, less than 5 hours or less than 4 hours, generally requiring at least 5 minutes, at least 10 minutes, at least 20 minutes, at least 30 minutes, at least 40 minutes, at least 50 minutes, at least 60 minutes, at least 120 minutes or at least 180 minutes of heating. Following pre-polymerization, the prepolymerized compartment can be combined with the aqueous compartment of the composition, additives being optionally added to each of them.

[0205] The extent of polymerization of the CNPFAs, either during step S-04 or a pre-polymerization step, if performed, can be estimated by suitable routine analytical methods, which can be generic, such as monitoring an increasing viscosity or a release of water molecules (e.g., by Karl Fischer titration), or specific to the chemical formulae of the CNPFAs and the groups they may jointly form (or individually lose) as the polymerization proceeds. The extent of reaction can for example be assessed by Fourier Transform Infrared Spectroscopy (FTIR) or titration procedures determining the acid value of the material (which decreases with increased cross-linking), the mixture of the CNFPAs without any treatment serving as baseline reference. Such analysis can be performed on materials readily available in vitro during the performance of the method, or on suitable extracts, if sought on materials to be found within the fibers.

[0206] While for simplicity the method was described in terms of breakage of hydrogen bonds and subsequent blockage of the broken bonds by attachment to CNPFAs or the formation therefrom of a shapeable polymer which may interact, or not, with constituents of the fibers, this is not meant to rule out any additional rationale underlying the observed styling effect.

[0207] The present methods provide for a durable modified shape, this matter being monitored by the number of shampoo washes the fibers may resist without the styled shape being affected in a significantly detectable manner. In some cases, the compositions, as tested in a hair styling method, provide long lasting modification of the fibers’ shape, as evidenced by the ability of the treated hair to withstand 5 or more shampoo washes, 10 or more shampoo washes, 20 or more shampoo washes, 30 or more shampoo washes, 40 or more shampoo washes, or 50 or more shampoo washes, each such washes being also termed a wash cycle.

[0208] While it cannot be ruled out that part of this “wash resistance” results from residual disseminated coating on the fibers’ outer surfaces, the Inventors posit that as such an external coating tends to wear out relatively rapidly with washes, the ability to durably modify the shape of the fibers can be attributed predominantly to the internal polymerization of the CNPFAs. It is to be noted that this transient scattered coating is relatively thin, usually not exceeding an initial thickness of 1 pm, often being less than 0.5 pm thick, which in itself distinguishes hair fibers treated according to the present teachings from conventional styling methods relying on continuous external coatings of a few microns to constrain the fibers in a desirable shape. Without wishing to be bound by theory, it is believed that this transient thin coating of the hair fibers may temporarily protect the inner shaft so that the CNPFAs having penetrated therein can further their curing, strengthening their polymerization, thus extending the hair styling durability.

[0209] As used herein, a composition providing for a modified shape able to resist 5 to 9 shampoo washes can be referred to as having a short-term styling effect. A composition providing for a wash resistance of 10-49 shampoo cycles is said to provide for a semi -permanent styling, whereas compositions providing wash resistance to more than 50 shampoos can be said to provide permanent styling. The present method can accordingly be said to provide a short-term styling effect, a semi-permanent styling effect or a permanent styling effect. The rapid absence of a continuous external coat (insignificant for the present long lasting styling effects) is deemed advantageous, as methods relying on such peripheral constricting structures to durably maintain a straightened hair shape have often been found detrimental to hair health and natural look or feel.

[0210] Figure 2A shows a natural, untreated curly black hair tuft, in which twists (e.g., dips 22 and peaks 24) in the hair fibers are clearly detectable, this exemplary hair tuft being moreover relatively frizzy. A sample of similar hair, treated with a hair styling composition described in the present invention as NP3-60 and straightened with a flat iron, is shown for comparison in Figure 2B. As can be seen, the treated hair fibers show a drastic decrease in the number of twists as compared to the untreated reference. This picture is representative of straight hair as can be observed following the styling step or after any number of wash cycles following which the hair fibers are still considered wash resistant after their treatment with a composition and by a method according to present teachings.

[0211] While the present compositions and methods are particularly beneficial for long lasting hair styling, for which the alternatives are typically deleterious to the hair and often to the health, they may additionally or alternatively be used for short-term hair styling, the hair fibers regaining their native original shape following 2 to 4 shampoo washes.

[0212] The methods of the present invention are suitable for any desirable modification of shape, which with respect to hair styling can include straightening, curling, or rendering an intermediate shape, wherein the hair is relaxed to a form less wavy than its natural unmodified shape.

[0213] Advantageously, the present compositions allow restyling without necessitating application of a new composition, as long as the fibers retain sufficient amount of the shapeable polymer within their inner cores. This can be achieved by bringing the fibers to a temperature above the Tg or softening temperature Ts of the polymer formed during the first shaping, hence affording what may be referred to as “at least partial softening”. During and / or following such a step of at least partial softening, the fibers can be assigned a desired second shape, as previously done to provide them the first shape. The polymer is then allowed to regain a constraining structure adapted to retain the second shape, by allowing the temperature to decrease below its Tg or softening temperature Ts while the hairs are maintained in the desired new shape. The second shape can be same or different than the first shape. Advantageously, the present compositions allow “de-styling” when desired, by which it is meant that the fibers treated according to the present invention can regain their original shape without waiting for the effect of styling to vanish with time or for the regrowth of naturally shaped hair fibers. This can be achieved by subjecting the previously styled hair fibers to a temperature above the Tg or softening temperature Ts of the polymer in the presence of water for a sufficient amount of time for the temperature to soften the polymer, and the water to penetrate the fibers. Without wishing to be bound by theory, it is believed that that such destyling treatment could result in the softening of the polymer, thus possibly allowing a certain degree of cleavage of bonds that the polymer may have formed with moieties of the hair fibers prone to form hydrogen bonding. The presence of water during the de-styling treatment enables penetration of such molecules into the hair, resulting in the reformation of at least part of the hydrogen bonds naturally occurring in the untreated hair. Depending on the extent of reformation of the original hydrogen bonds of the hair fibers, and the form the polymer may adopt upon cooling back to a lower temperature no longer supporting its softening, the de-styling can be partial or complete, the hair accordingly returning less or more closely to its original shape. The de-styling process is believed to only affect the shape of the polymers remaining within the hair shaft, therefore, following de-styling, the hair fibers can, if desired, undergo an additional styling treatment, as previously described for restyling.

[0214] Advantageously, the present compositions and methods are suitable for the styling of growing hair. The synthetic polymer formed by a first application of the hair styling composition is expected to be located in the segments of the hair fibers available above scalp at the time of application of the CNPFAs. With time and hair growth, such segments are to be found more and more distal from the scalp, while the newly grown hair segments adjacent to the scalp would be devoid of such inner styling skeleton. It is believed that hair styling compositions applied at a later time following such hair growth would probably act mainly on the newly grown segments, the earlier treated segments being already “occupied” by previously formed synthetic polymer and crystallized WHAs. However, since as explained the existing polymer can permit restyling or de-styling of the fibers, it may functionally merge with a polymer that would be newly formed in the new segments, providing a “styling continuity” along the entire fiber, preexisting and newly grown. EXAMPLES

[0215] Materials

[0216] The materials used in the following examples are listed in Table 1 below, the average molecular weight, when known, being provided in g / mol, and for natural polymers typically consisting of various substances the MW is usually indicated as a range of values corresponding to their respective constituents. The reported properties were retrieved or estimated from the product data sheets provided by the respective suppliers. Unless otherwise stated, all materials were purchased at highest available purity level and all NPs were subjected to evaporation in vacuum chamber under conditions ensuring no more than 5 wt.% of residual volatile compounds. DS refers to Dewaxed Shellac, WS refers to naturally Waxy Shellac, TSC refers to Thermo Scientific Chemicals™ and NA or NR indicate that information is either not available or not relevant.

[0217] Table 1

[0218]

[0219]

[0220]

[0221] Equipment

[0222] Flat iron: Babyliss® I-Pro 235 Intense protect (Conair, USA)

[0223] Hair dryer: Itamar superturbo Parlux 4600 (Parlux®, Italy)

[0224] Incubator: Constant climate chamber KBF 115 (Binder™, Germany)

[0225] Overhead stirrer: JK-MSH-PRO 120W (MRC Laboratory Instruments®, Israel) Rheometer: Haake Mars III with spindle C60 mm / l° (Thermo Fisher Scientific®, Germany) Stirring hot plate: C-MAG HS 7 control (IKA®, Germany)

[0226] Vacuum chamber: Shel O Lab™ SVAC1 (Sheldon Manufacturing®, USA)

[0227] Example 1: Preparation of stock solutions

[0228] I. CNPFA stocks

[0229] Into a 50 ml Duran® Shott bottle equipped with a magnetic stirrer, and unless otherwise stated, 3.33 g of flakes or beads of a natural polymer (e.g., a shellac, colophony, copal, dammar, mastic or sandarac resin as listed in Table 1) were placed and 6.66 g of fatty agent previously dried with molecular sieves were added to cover the solid resin with the liquid. Unless otherwise stated, the fatty agent used in most experiments to follow was the fatty amine oleyl amine. Each bottle was sealed with its cap and placed on a plate heated to 160°C, the contents being stirred at 300 rpm for predetermined period of times including 15, 30, 60, 120 and 180 minutes. The shortest period was typically suitable for full miscibility of the NP with the FA, yielding a single-phase water-insoluble CNPFA stock. However, after heating for only 15 minutes, the temperature of the liquid mixture has not yet reached equilibrium circa 125°C, this typically happening after at least 30 minutes in view of the thick walls of the bottles. Thus, while in the following, the preparation of the CNPFA stock can be reported to involve heating at 160°C, this is the temperature set for the hot plate, the materials being in fact subjected to at most 125°C. Following their heating for the desired periods of time, the bottles were removed from the hot plate and placed in an incubator set at 25°C, where they were stirred for one hour to enable homogeneous cooling rate. The bottles containing the CNPFA stocks were then wrapped in aluminum foils and stored at 4-8°C until use.

[0230] While it cannot be ruled out that the NP and FA may start reacting as they are slowly dissolving one in the other during their joint heating, it is assumed that the first 15 minutes of the preparation of the water-insoluble stocks during which the temperature is still ramping up and believed insufficient for significant cross linking do not constitute a pre-polymerization of the materials, but only a dissolution of the relatively more solid resin into the relatively more liquid fatty agent. Thus, only longer heating periods shall be considered to include a prepolymerization step.

[0231] For illustration, a sample of CNPFA stock heated for 60 minutes will in fact be subject to three steps: a first one from 0 to 15’ being a dissolution step essentially devoid of significant pre-polymerization, a second one from 16’ to 30’ being a pre-polymerization step at a still ramping up temperature and a third one from 31’ to 60’ being a pre-polymerization step at a constant temperature. The time points at which the stock transit from one step to another are arbitrarily set according to the present experimental settings and can be adapted in accordance with any other setup accelerating or delaying the dissolution, and / or the time point at which the dissolved mixture reaches equilibrium.

[0232] II. Aqueous gel stocks

[0233] In a 500 ml round plastic vessel, 295.5 g (98.5 wt.%) of aqueous solution were placed, the liquid being in one case a water solution containing 40 wt.% of urea and having a pH of about 9 and in another case pure water supplemented with ammonium hydroxide to have a pH matching the pH of the urea containing solution. The vessel was placed under an overhead stirrer and the liquid was stirred at 800 rpm at room temperature. Thickeners were gradually and slowly added over a period of about 10 minutes to prevent formation of clumps. First, 3 g (1 wt.%) of Jaguar® HP-105 were incorporated in the liquid, followed by 1.5 g (0.5 wt.%) of SepiPlus™ S. Once both thickeners were suitably dispersed in the liquid, the mixture was stirred for 15 more minutes. The plastic vessels were then sealed with a plastic cap and the aqueous gels stored at room temperature until use.

[0234] One day after preparation of the gels, their dynamic viscosity at room temperature was determined using a rheometer operated at a shear rate of 40 sec-1. The viscosity of the gel stocks was found to be between 3,000 and 4,000 milliPascal second (mPa.s) depending on batch, but regardless of the presence of urea in the gel. The pH of the aqueous gels, with or without urea, was typically between 8.8 and 9.2. The gel containing only thickeners was denoted AGO and the gel containing 40 wt.% urea was denoted AG1.

[0235] Additional aqueous gel stocks were similarly prepared with 2 wt.% to 40 wt.% of alternative WHAs, the same thickeners being used at same concentrations, the pH of the gels being, if needed, corrected one day after preparation with ammonium hydroxide or citric acid to a pH of about 9.2, except for the gel prepared with pantolactone which was set to pH 6.5. Each aqueous gel was assigned an AG number as reported in Table 2, also indicating the weight percent of the WHA per total weight of the aqueous gel. The water solubility of the materials at room temperature as reported in respective product datasheet or literature is also presented in g / 100ml, alternatively termed wt.%.

[0236] Table 2

[0237]

[0238] Example 2: Preparation of oil-in-water emulsions containing CNPFAs

[0239] 25 mg, 62.5 mg, 125 mg, 187.5 mg or 250 mg of a water-insoluble CNPFA stock were added to 5 g of an aqueous gel stock placed into a 20 ml glass vial, the stocks being prepared as described in Example 1. The contents of the vials were vigorously manually mixed together using a whisker for about 10 seconds until a homogeneous emulsion was obtained. These exemplary compositions correspond to weight per weight ratio between the water insolublephase and the water-soluble-phase of 1:200, 1:80, 1:40, 1:27 and 1:20, respectively.

[0240] The compositions so prepared when the aqueous gel was AG1 or AGO are reported in Table 3, where the concentration of each component is reported in wt.% by total weight of the emulsion. As the values were rounded up to the closest two digits number, their sum may not exactly add up to 100 wt.%. Table 3

[0241]

[0242] The name of the compositions can be followed by a number indicating the time spent mixing the NP with the FA, if other than basic 15 minutes at 160°C aimed to ensure full dissolution of the materials into a single water-insoluble phase reaching at most 125°C. For illustration, a composition wherein the various ingredients are present as provided for NP3, but for which the CNPFAs were mixed under heat for 60 minutes instead of 15 minutes, can be referred to as NP3-60. Unless otherwise stated, the natural polymer used for the preparation of the CNPFAs was dewaxed beige shellac purchased from Shellac.net, listed in the first row of Table 1.

[0243] Example 3: Hair straightening using emulsions containing CNPFAs

[0244] The hair tufts used for testing the straightening ability of the present compositions, containing CNPFAs combined (or not) with a WHA provided by mixing, unless otherwise stated, 1 part of the water-insoluble CNPFAs with 50 parts of a desired aqueous gel containing or not the WHA, were curly black hair of Brazilian origin (approximately 30 cm long). Each tuft was glued together at one tip with epoxy glue, and weighed approximately 0.6-1.3 g, including the glued tip. The hair tufts that were used were virgin (z.e., without any previous treatment), but the method (schematically depicted in Figure 1 and detailed below) can similarly be used to study the effect of the compositions on bleached or colored hair as shall be detailed in Example 8. While for simplicity, in the present examples the compositions or methods can be referred to as “straightening”, a term usually describing a “complete flattening” of the hair fibers, this term is intended to encompass any significant shape modification, wherein the hair is relaxed to a form less wavy or frizzy than native shape.

[0245] Procedure:

[0246] 1. Washing of the fibers (see step S-00 in Figure 1): the curly hair tufts were washed at 38- 40°C with tap water containing 5% sodium lauryl sulfate, rinsed with excess tap water and dried using a hair dryer for 2-3 minutes at moderate heat, the cleaned hair tufts retaining their native shapes.

[0247] 2. Application of the composition (see step S-01 in Figure 1): the cleaned hair tufts were dipped in a 100 ml plastic cup containing about 15-20 g of a hair styling composition (e.g., oil-in-water emulsion), prepared as described in Example 2. A plastic film was stretched over the surface of the composition to reduce or prevent its evaporation.

[0248] 3. Incubation of the composition (see step S-02 in Figure 1): the cups containing the hair tufts samples dipped in the various compositions were maintained, unless otherwise stated, for 1 hour at room temperature, so as to enable at least partial penetration of inter alia the CNPFAs and WHAs, when present, within the hair fibers.

[0249] 4. Rinsing of the hair fibers (see step S-03 in Figure 1): the hair tufts so treated were thoroughly rinsed to eliminate excess composition from the surface of the hair fibers. Unless otherwise stated, the fibers were rinsed with tap water at a temperature of about 38-40°C for 10-20 seconds, and then dried using a hair dryer for 2-3 minutes at moderate heat.

[0250] 5. Styling of the hair fibers (see step S-04 in Figure 1): the rinsed and dried treated hair tufts were then straightened using a flat iron, at a temperature of 220°C for about 2-3 minutes (about 30-50 passes), depending on the tuft length, until the tufts were completely dried and in the desired modified shape. This step allows at least partial curing of the CNPFAs having previously penetrated within the hair fibers.

[0251] 6. Washing of the hair fibers (see step S-05 in Figure 1): one hour after being straightened, thus back to room temperature, the styled hair tufts were washed by finger-rubbing a standard shampoo on the hair fibers to ensure full tip to tip coverage and intimate contact with the hair for about 30 seconds. The shampooed hair tufts were then rinsed with tap water at a temperature of about 38-40°C, similarly “massaged” with a hair conditioner for about 30 seconds and rinsed again with tap water at the same temperature. The rinsed hair tufts were then fully dried using a hair dryer for 2-3 minutes at moderate heat. Unless otherwise stated, the standard shampoo was Shea Natural Keratin Shampoo by Saryna Key, Israel, and the hair conditioner was Pro Collection, Biotin + Repair 7, by TRESemme, Unilever, USA.

[0252] Figure 2A shows a picture of a hair tuft of curly hair before treatment by the present method, whereas Figure 2B shows a representative picture of the same hair tuft after being treated with a composition according to present teachings and straightened as above described.

[0253] While similar steps could be performed for the styling of a full head of hair on a living human subject, the last washing of the styled hair tufts performed close to the straightening step in a laboratory setting would be in this case postponed to following days.

[0254] Without wishing to be bound by any particular theory, it is believed that the activation of the polymerization process provided during the straightening step can be significant enough for curing to proceed for a while following the completion of the styling per se. Such a “postcuring” of the polymers within the fibers can inherently take place as the effects of the thermal energy applied during the styling process fade out or be actively implemented. For illustration, fibers that are not attached to a living subject, whether keratinous or not, can be post-cured by incubation at a relatively elevated temperature and / or for relatively long periods of time once they have reached their desired shape during the shaping procedure.

[0255] Example 4: Durability of the hair straightening

[0256] The hair tufts successfully straightened with the compositions of the present invention by the method described in Example 3 (which included a first post-styling washing), were subjected to a series of washings starting on the day following the styling. In each washing cycle, the hair tufts were washed with a shampoo and a conditioner, as described in Example 3. The washing cycles were performed up to twice a day, typically within at least 6 hrs one of the other, or otherwise daily.

[0257] The number of washes after which the hair tufts remained “straightened”, including any type of modified shape originally obtained at the end of the straightening procedure, is indicative of the durability of the hair styling provided by the present compositions and method. This number can also be referred to as the “wash resistance” afforded by a particular composition under the conditions it was applied and tested. Wash resistance can be visually assessed by trained operators in a qualitative manner, the result provided indicating the number of washing cycles following which changes in shape become significantly visibly detectable. Alternatively, wash resistance can be quantified, for instance by measuring the length of the hair samples after styling treatment and after any desired amount of washing cycles, and / or by counting the number of deviations from straight hair (e.g., peaks and dips) in a representative number of fibers. Length can be measured by placing the hair fiber along a ruler, without stretching or pulling the hair fiber. The number of “twists” in the hair fiber can be provided by counting the number of amplitudes (minimum and maximum) visible on the fiber. The number of twists can be normalized to the hair length, and the straightness efficiency can be calculated by dividing the normalized number of twists after treatment being considered by the normalized number of twists before such treatment (the reference). Straightness efficiency can be expressed as 100% minus the percentage of the number of twists per length after and before treatment. Straightening is deemed successful, and treated fibers wash-resistant, as long as the straightness efficiency is of 70% or more. If for illustration untreated curly hairs have 12 twists over a length of 34 cm, and a straightened sample of the same has no twist at all, then the straightening efficiency is 100%. If the treated fibers have only 1 twist over a length of 42 cm, the straightness efficiency of the composition used for styling is about 93% (100*(1 – (1 / 42) / (12 / 34))), and the treated fibers would be considered still satisfactorily straightened (or wash resistant) as long as the number of twists does not raise back to 5 or more. For illustration, if the styled or washed fibers have 4 twists over a length of 39 cm, the straightness efficiency would be of about 71% (100*(1 – (4 / 39) / (12 / 34))), 5 twists or more causing a drop to about 63%. The hair fibers are “wash resistant” as long as the measurements (e.g., length, number of twists, or straightness efficiency, before washing and at the washing cycle being considered are similar e.g., within 10% or less one from the other) or as long as trained operators are unable to detect visible changes.

[0258] Table 4 presents the wash resistance of compositions of Example 2, as applied to hair tufts treated and straightened as described in Example 3, the results being qualitatively assessed by trained operators. In following tables, the symbol > before a reported number of washing cycles indicates that the experiment is ongoing or was interrupted at this stage, so that the wash resistance afforded by these compositions may be greater, or even significantly greater, than the reported value. The time indicated as column headings refer to the length of pre-treatment of the CNPFAs during their mixing at 160°C as detailed in Example 1. Table 4

[0259]

[0260] As can be seen from the table above, all compositions containing a water-soluble hygroscopic agent, NP1 to NP5, (the WHA being urea of AG1 in the present case), provided for a wash resistance of at least twenty -five cycles by the time this experiment was terminated, supporting at least partial penetration of the CNPFAs within the hair fibers and their polymerization therein, as mere coating would typically wash away in at most 3 cycles and could not provide the observed lasting styling effect. This supports that compositions comprising weight per weight ratio between the water insoluble-phase and the water-soluble-phase at least between 1:200 and 1:20 can suitably serve to style at least healthy hairs as herein tested. In comparison, a composition lacking WHA, NP8 resisted only one washing cycle. Unless otherwise stated, all the following experiments were performed using the gel AG1 containing 40 wt.% urea and having a pH of about 9 as the aqueous compartment.

[0261] In a control experiment, hair fibers were treated only with the aqueous gel including urea AG1, without any CNPFAs able to polymerize during the styling step. The hair fibers resisted two washing cycles, supporting that urea alone has a protective role delaying water re-entry within the fibers and reformation of the hydrogen bonds responsible for the curly appearance.

[0262] In a second series of experiments, the effect of a composition according to NP3 where the CNPFAs were mixed at 160°C for 15, 30 or 60 minutes, i.e., NP3-15, NP3-30 and NP3-60, before being mixed at a weight ratio of 1:40 with AG1 was assessed for straightening of curly hairs as described. The composition prepared by mixing the CNPFAs for only 15 minutes is considered a reference which was not subjected to pre-polymerization, the performance of this step being believed to require later time points at which the mix reached plateau temperature (at ~30 minutes) believed to trigger polymerization and / or were maintained at said elevated temperature for a while (e.g., at 60 minutes) All compositions following their mixing with the aqueous gel provided for a satisfactory straightening of curly hairs and for a wash resistance of at least twenty-five cycles by the time this experiment was terminated regardless of the duration of pre-heating of the CNPFAs. These results support that while pre-polymerization of the CNPFAs is expected to prolong the styling duration, this is not essential for a semi-permanent effect.

[0263] In a third series of experiments, the effect of a composition according to NP3 where the CNPFAs were mixed at 160°C for 60 minutes, i.e., NP3-60, before being mixed at a weight ratio of 1:40 with AG1 was assessed for straightening of curly hairs as described, the Beige dewaxed shellac purchased from Shellac. Net used in previous compositions being replaced by each of the other shellac types listed in rows 2-8 of Table 1. The compositions were accordingly named from NP11 (for Super Blonde dewaxed shellac of the second row) to NP17 (for Brown waxy shellac of the eighth row). All compositions NP11 to NP17 provided for a satisfactory straightening and for a wash resistance of at least nine cycles by the time this experiment was terminated regardless of the type of shellac being tested in 1:2 ratio with oleyl amine (the CNPFAs being mixed with AG1 at 1:40).

[0264] In a fourth series of experiments, alternative natural polymers and / or fatty agents (or other solvents) were used in the preparation of the CNP(FA) water-insoluble compartment of the oil-in-water composition. The aqueous compartment was AG1 gel stock containing urea and both compartments were prepared according to Example 1 wherein the NP was dissolved in the FA (or control liquid) for 60 minutes at 160°C. The water-insoluble compartment and the aqueous gel were combined as described in Example 2 at a weight per weight ratio of 1: 100.

[0265] In a first run, the resin remained dewaxed beige shellac but oleyl amine, including one primary amine group per molecule and having an amine value of -210 mg KOH / g, was replaced either by POE (2) cocoamine, including one tertiary amine group and two terminal hydroxyl groups having an amine value of -295 mg KOH / g, or by Priamine™ 1075LQ, including two primary amine groups and having an amine value of -205 mg KOH / g, respectively referred to as NP 18 and NP19. Both compositions NP18 and NP 19 provided for a satisfactory straightening of curly hairs and for a wash resistance of up to twenty cycles by the time this experiment was terminated regardless of the FA1 being tested, supporting that various amine groups (and amine values of the FAls) may suitably interact with reactive groups on the NP.

[0266] In a second run, the resin remained dewaxed beige shellac but the fatty amine (FA1) was replaced either by a fatty alcohol (FA2) or by a fatty acid (FA3) in which the resin was miscible, namely undecane- 1, 11 -diol (FA2) or cyclohexane carboxylic acid (FA3) were used instead of oleyl amine. These compositions, referred to as NP20 and NP21, provided for a satisfactory straightening of curly hairs and for a wash resistance of at least twenty or fifteen cycles respectively by the time this experiment was terminated, supporting that hydroxyl groups as found in the fatty alcohol, carboxyl groups as found in the fatty acid and amine groups as found in the fatty amine can each react with functional groups as found in shellac to yield a shapeable polymer contributing to the ongoing straightening of the fibers.

[0267] For reference, when shellac was dissolved at 40 wt.% in a control liquid lacking these reactive groups, namely in dipropylene-glycol dibenzoate, the wash resistance afforded by treating the hair fibers for one hour with a composition prepared by mixing 0.1 g of this waterinsoluble phase in 5 g of AG1 prior to straightening of the curly hairs was of only two cycles, as can be afforded by the mere presence of the gel including urea (z.e., AGP) during similar incubation and straightening of the fibers. Thus, while self-polymerization of shellac during the process as performed in this study cannot be ruled out, it seems insufficient to significantly contribute independently to the constitution of the shapeable polymer. Likewise, when fatty agents were used as the sole constituents of the water-insoluble phase, 0.1 g of Farmin® DM2098 or Genamin® O 020 being mixed with 5 g of AG1, curly fibers similarly treated with these compositions and thereafter straightened also displayed an insignificant wash resistance of a single cycle. The Inventors believe that this control study supports the benefits or necessity of using the NPs in combination with the FAs in order to form a shapeable polymer capable of imparting wash-resistance to shaped fibers, in other words a prolonged hair styling effect.

[0268] In a third run, the fatty agent remained oleyl amine but shellac was replaced by alternative natural polymers as listed in rows 9-13 of Table 1. All resins were dissolved in the fatty agent at a 1 to 2 weight ratio for 60 minutes at 160°C and 125 mg of the resulting water-insoluble phase were mixed with 5 g of the aqueous gel AG1 including urea. The various compositions and the wash resistance they provide after having satisfactorily straighten originally curly hair samples are presented in Table 5, together with some technical data retrieved from literature characterizing the natural polymers. As these parameters may vary depending on the source of the resins and the report considered, the broadest reported ranges are provided. Table 5

[0269]

[0270] Most compositions prepared with the alternative resins other than shellac provided for a satisfactory straightening of the curly hair samples and for a wash resistance of at least fifteen cycles by the time this experiment was terminated, supporting that various natural polymers can contribute to the straightening effect. The results of NP25 prepared with mastic resin suggest that the present concentrations and conditions require optimization for this particular NP.

[0271] As resins typically have molecular weights provided over a range of values, depending on source, blends of constituting substances and method of isolation, it is difficult to provide the exact molar ratio between the NPs and FA prepared as reported above. However, as the lowest and highest MW reported for these resins is estimated to be respectively approximately 300 g / mol (e.g., colophony typically in a range of 300-400 g / mol) and 5,000 g / mol (e.g., dammar typically in a range of 1,000-5,000 g / mol) and since oleyl amine has a MW of 267.5 g / mol, present study has shown that molar ratios between the FA and the NP in a range from about 2: 1 to 40: 1 in favor of the fatty agent is suitable for the formation of a shapeable polymer.

[0272] In further experiments, different weight ratios between the NP and the FA were tested. For this purpose, Sandarac resin was mixed with Genamin® O 020 (being an ethoxylated oleyl amine) for 30 minutes at 160°C at the following respective weight percentage 30:70, 35:65, 40:60, 45:55, 50:50 and 55:45, 1 part of the CNPFA being thereafter mixed in 50 parts of gel stock AG1 containing 40 wt.% urea and having a pH of about 9. The resulting compositions were respectively designated from NP27 (for 30 wt.% NP and 70 wt.% FA) to NP32 (for 55 wt.% NP and 45 wt.% FA). All compositions provided for a satisfactory straightening of initially curly hair samples; differences being observed in the wash resistance each afforded to the hair styled therewith. While NP27 and NP32 provided for a temporary hair setting rather labile after only a few shampooing cycles, NP28 to NP31 each resisted at least 20 wash cycles by the time this experiment was terminated, the retention of original straightening seeming superior for NP31 (50 wt.% NP and 50 wt.% FA). As sandarac resin has an average MW typically in a range of 300-600 g / mol and since Genamin® O 020 has a MW of 355.6 g / mol, present study has shown that molar ratios of up to about 2: 1 in favor of the natural polymer are also suitable for the formation of a shapeable polymer.

[0273] In a side experiment NP29 (comprising 40 wt.% sandarac and 60 wt.% Genamin® O 020 in its water-insoluble phase) was compared to a control composition denoted NP29 ” in which the oily phase further comprised phenyl salicylate (CAS No. 118-55-8, purchased from Sigma-Aldrich) previously considered in WO 2023 / 021455 as one phenol-based monomer essential for the formation of the internal shapeable polymer enabling lasting styling. The waterinsoluble phase of comparative NP29” consisted of 40 wt.% sandarac, 55 wt.% Genamin® O 020 and 5 wt.% phenyl salicylate which was prepared by mixing all ingredients for 1 hour at 160°C, the temperature of the oily phase within the bottle not exceeding 125°C. 1 part of the oily phase were then mixed with 50 parts of AG1 and NP29” was applied on hair, later straightened and washed as described for NP29. By the time this comparative experiment was terminated, fibers treated by either NP29 or NP29” resisted a similar number of wash cycles, supporting that at least under the conditions of present study, current compositions were surprisingly capable of providing a straightening effect comparable to the control composition, though lacking what were previously deemed to be the pertinent building blocks of the final polymer.

[0274] Figure 4A shows a cross-section of a hair fiber treated with NP31 the straightened hair fibers being already washed 10 times. The picture was captured by a scanning electron microscope (SEM) and by focused ion beam (FIB) measurements using Zeiss Crossbeam 340 microscope. The cross section was performed with a FIB probe of ionized gallium bombarding the sample at 30 kV and 700 pA, and the image was taken at a magnification of x50K, at a voltage of 1.20 kV, and at a working distance of 4.9 mm, with the SEM column and an in-lens detector. As better seen in Figure 4B schematically representing the same cross-section 40, depots of the cured composition 44 having penetrated the fibers can be seen between the hair cuticles 42. For emphasis, the internally disposed composition 44 is marked by hatches on part of the interfaces between the hair scales.

[0275] In further experiments, alternative natural polymers and / or fatty agents were used in the preparation of the CNPFA water-insoluble compartment of the oil-in-water composition prepared as described in Example 2, some of the ingredients being tested as blends. The aqueous compartment was gel stock AG1 containing 40 wt.% urea and having a pH of about 9, and both compartments were prepared according to Example 1 wherein the NP was dissolved in the FA for 60 minutes at 160°C and the CNPFAs mixed with the aqueous gel at 1:200 weight ratio. In a first series, the ingredients tested as mixtures were the FAs. The water-insoluble compartment of the composition denoted NP33 consisted of 30 wt.% copal dissolved in a mixture of 35 wt.% Priamine™ 1075LQ and 35 wt.% oleyl amine, both fatty agents having primary amine functional groups. The water-insoluble compartment of the composition denoted NP34 consisted of 33 wt.% copal dissolved in a mixture of 56 wt.% Genamin® O 020 and 11 wt.% oleyl amine, the fatty agents being not only a mixture of two materials, but also of types of functional groups including the primary amine of oleyl amine, and the tertiary amine and hydroxyl groups of Genamin® O 020. In an alternative composition denoted NP35, sandarac was used as natural polymer at 40 wt.%, the fatty agents consisting of a similar mixture of Genamin® O 020 and oleyl amine, respectively present at 50 wt.% and 10 wt.% of the waterinsoluble compartment. All compositions NP33-NP35 including mixtures of FAs and / or FA functional groups provided for a satisfactory straightening of initially curly hairs and for a wash resistance of at least 5 washing cycles by the time this experiment was terminated.

[0276] In a second series, the ingredients tested as mixtures were the NPs. In a first run, the water-insoluble compartment of these compositions consisted of 40 wt.% of a wax and 40 wt.% of shellac dissolved in 20 wt.% of oleyl amine, the weight per weight ratio between the combined concentration of the NPs and the FA being of 4:1. The compositions comprising alternatively Candelilla wax, Carnauba wax, Montan wax or Rice bran wax were respectively denoted NP36, NP37, NP38 and NP39. In a second run, the water-insoluble compartment of these compositions consisted of 25 wt.% of a first resin, 25 wt.% of a second resin dissolved in 50 wt.% of a fatty agent, the weight per weight ratio between the combined concentration of the NPs and the FA being of 1:1. A composition including 25 wt.% copal, 25 wt.% sandarac and 50 wt.% Genamin® O 020 as water-insoluble phase was named NP40 and a composition including 25 wt.% copal, 25 wt.% dammar and 50 wt.% oleyl amine as water-insoluble phase was named NP41

[0277] All compositions NP36-NP41 comprising mixtures of resins and / or waxes and as NPs provided for a satisfactory straightening of initially curly hairs and for a wash resistance of at least 5 washing cycles by the time this experiment was terminated. The results obtained with NP33-NP41 support that ingredients of the present compositions can be used as blends to contribute to their straightening effect.

[0278] Example 5: Restyling of hair treated with compositions containing CNPFAs

[0279] Hair samples treated with compositions such as prepared in Example 2, which display a wash resistance as tested in Example 4 deemed sufficient (e.g., resisting at least 5 or 10 wash cycles or any other set number of cycles) were subjected to a restyling treatment, e.g., straightening of the hair fibers, as described in step S-04 of Example 3. This heat treatment is expected to sufficiently soften the previously formed polymer to reshape the hair fibers, in order to restyle the hair fibers, the restyling being in current experiment to the same straightened shape as provided by the original styling treatment. After the application of heat, the hair samples were allowed to cool back to room temperature, allowing the polymer to regain its stiff / unsoftened structure. Hair samples so restyled were subjected to washing cycles as described in Example 4 to assess the resistance of the reshaped polymer and the ongoing protective effect ofthe WHA.

[0280] Such an experiment was conducted with hair samples previously treated with NP29 (40 wt.% sandarac and 60 wt.% Genamin® O 020) which have been already subj ected to 10 washing cycles following their straightening. While their shape at this stage was still within criteria of wash resistance, they sufficiently deviated from original straightened shape to allow testing feasibility of restyling in a visually detectable manner. The hair samples were straightened again with a flat iron as already described and regained a perfectly straightened shape. The restyled hair samples were then subjected to washing cycles and were shown to satisfactorily resist at least 5 washing cycles by the time the experiment was terminated, supporting that hair sample treated by present compositions and methods can be restyled. This also implies that the hair samples still internally contained sufficient shapeable polymer.

[0281] Example 6: De-styling of hair treated with compositions containing CNPFAs

[0282] Hair samples treated with compositions such as prepared in Example 2, which display a wash resistance as tested in Example 4 deemed sufficient (e.g., resisting at least 5 or 10 wash cycles or any other set number of cycles) and still being in a styled (e.g., straightened) shape at the beginning of the study were subjected to a destyling treatment allowing the hairs to regain their original (unmodified, e.g., curly) shape. Understandably, destyling can be performed at any other stage following initial styling, and preferably while the polymer still has a thermoplastic behavior. Starting from samples having established wash resistance is only ensuring that the hair fibers were properly shape-modified in a lasting manner in the first place, hence including an internally formed polymer capable of maintaining a desired modified shape. The experiment was conducted with hair samples previously treated with NP31 (including 50 wt.% sandarac and 50 wt.% Genamin® O 020 in the water-insoluble phase) which have already been subjected to 10 washing cycles following the straightening of the initially curly hair, their shape at this stage still being essentially as obtained after their initial straightening. The styled hair samples were dipped in a 100 ml plastic cup containing about 15 g of water having a pH of about 6.5 pre-heated to 60°C. The cups were then placed in an oven for 5 minutes at 60°C. The appearance of the hair samples so “de-styled” was compared to the original appearance of the native untreated hair samples to assess the efficacy of the de-styling treatment and was found similar, the destyled samples having regained their original curls.

[0283] Destyling was also satisfactorily achieved with hair samples previously treated NP33 (having a water-insoluble phase made of 33 wt.% copal dissolved in a mixture of 56 wt.% Genamin® O 020 and 11 wt.% oleyl amine). The destyling experiment was performed after a single wash following the straightening procedure and the hair fibers regained their original curls.

[0284] The Inventors posit that the de-styling process does not cause the elimination of the synthetic polymer entrapped within the hair fibers, as can be checked by the ability to further re-style the hair samples, as previously described. This was confirmed by restyling the hair samples treated with NP33, straightened, washed once to confirm water-resistance, and destyled as above-described. The hair was then restyled by flat ironing as described in step S-04 of Example 3 and found to resist at least 5 washing cycles.

[0285] This supports not only the reversibility of a shape modified by present method (e.g., the ability to straighten curly hair (z.e., styling), followed, if desired, by the ability to restore original shape (z.e., de-styling), followed, if desired, by the capacity to provide a (new) shape (z.e., restyling)), but also that the polymer formed by present CNPFAs is sufficiently long lasting to permit such behavior. The durability of the styling effect, and of its reversibility, afforded by present compositions is believed to result from the internal formation and disposition of the shapeable polymer made therefrom.

[0286] Example 7: Differential Scanning Calorimetry (DSC) study of hair fibers

[0287] Keratin hair fibers demonstrate characteristic endothermic peaks in a number of thermal analytical methods, each peak being indicative of chemical changes occurring near the various temperatures. The hair samples treated according to Examples 4-6 can be analyzed by Differential Scanning Calorimetry (DSC) to assess the effect of compositions according to Example 2 on the physico-chemical properties of the hair fibers and compare them to an untreated reference of a same hair type. Such a study can be performed as detailed in Example 11 of WO 2023 / 021455, the contents of which are incorporated by reference for all purposes, as if fully set herein.

[0288] Figure 3 depicts the results of an exemplary DSC study showing how a non-damaging hair styling method, such as proposed by the present invention, may keep the hair unharmed, as opposed to traditional methods. As can be seen in the illustrative figure, the curve of a sample of hair fibers treated with a hypothetical innocuous composition would be comparable to the curve of untreated, native hair sample, indicating no significant structural changes. The solid line at the bottom of the plot depicts the curve of untreated curly black hair fibers. Two endotherms are observed in this exemplary curve, at 234.5°C and 250°C, which are the characteristic temperatures for hair fibers. The first endotherm around 234.5°C is believed to indicate the melting of a-keratin in the fiber, while the second endotherm around 250°C is believed to indicate the keratin decomposition and breaking of the di-sulfide bonds.

[0289] In contrast to the similarity between the endotherm temperatures at corresponding range on the curves when the fibers are undamaged, comparing fibers treated by conventional straightening methods known to damage the integrity of the hair fibers to same untreated fibers shows a significant deviation of about 5°C to 10°C for expected corresponding endotherms. For illustration, while the second endotherm of untreated fibers is at about 250°C, the second endotherm of fibers straightened by Japanese procedure appears at about 239°C, confirming the weakening of fibers treated by this traditional method.

[0290] Advantageously, hair fibers treated by the compositions according to the present teachings are expected to be undamaged thereby, displaying at least one endotherm temperature within 4°C, within 3 °C, within 2°C, or within 1°C from similar untreated fibers, as measured by thermal analysis.

[0291] The harmless effect of present compositions in a straightening method was proven by analyzing and comparing hair fibers either treated with NP31 (50 wt.% sandarac and 50 wt.% Genamin® O 020), the initially curled hairs being straightened by flat ironing and washed for 10 cycles as previously described to same hairs only similarly straightened and washed without prior application and incubation with a styling composition. It was found in repeat experiments that the respective endotherms at corresponding ranges of temperatures in the curves of the treated and untreated samples deviated from one another on average by no more than about 1 to 1.5°C, less than shown on the illustrative plot prepared from different hair samples.

[0292] In contrast, the DSC curves of commercial hair straightening methods (organic and Japanese) tested against the untreated reference show substantial changes from the native hair sample curve of at least about 6°C, indicating structural changes, which are to be expected when using such drastic hair styling methods.

[0293] Such measurements can alternatively be obtained from other methods of thermal analysis, such as by thermomechanical analysis (TMA) or dynamic mechanical analysis (DMA).

[0294] Example 8: Styling of hair fibers previously bleached or colored and coloration of fibers previously styled

[0295] In previous experiments, present compositions were typically applied to healthy virgin hair samples previously untreated. The purpose of present study was to show that the method is not limited by the health status of the fibers to be treated thereby, a styling effect being similarly achieved when the hair is previously altered. Two types of modifications which affect the hair samples were performed before testing the efficacy of present teachings for modifying fiber shapes.

[0296] In a first set of experiments, hair samples were previously bleached, this treatment being known to damage hair fibers. In a second set of experiments, hair samples were previously colored then styled, and conversely colored after having been first previously treated with a composition of the invention and straightened.

[0297] A tuft of curly hair previously bleached for an hour at 50°C using commercially available bleaching powder mixed with twice its weight of cream developer containing 9% hydrogen peroxide was treated with NP31 modified to include 2 parts of CNPFA for 50 parts of gel and straightened as described in Example 3. Wash resistance was assessed as described in Example 4 and was found to be of at least 5 cycles.

[0298] Hence, present method is adapted to modify the shape of hair being damaged, and not only of healthy hair. However, it seems that in such case, damaged hair being relatively more hydrophilic than hydrophobic healthy hair, the ratio of CNPFAs to aqueous gel should be increased in favor of the polymerizable ingredients as compared to a ratio that might have been sufficient for healthy hair. Without wishing to be bound by a particular theory, it is believed that the relatively increased amount of CNPFAs in the composition required for damaged hair compensates for the relatively lower affinity the materials have to the hair surface as point of entries to the inner hair shaft. Increasing the relative amount of CNPFAs to aqueous phase only seeks to maintain the time of incubation on the fibers within ranges enabling compliance for a subject treated therewith. But working at relative proportions less favorable to damaged hair is not impossible, it would only require more time for a proper gradient to form around the hair surface to trigger sufficient penetration of the polymerizable substances into the hair.

[0299] Thus, for illustration, while compositions having a weight ratio between the waterinsoluble and the water-soluble phases of 1:200 to 1:20 may be satisfactory for healthy hair fibers, it might be preferred to use weight ratios relatively favoring the CNPFA phase when the hair fibers are damaged, e.g., the water-insoluble and the water-soluble phases being at 1: 50 or more, 1:45 or more, 1:40 or more, 1:35 or more, 1:30 or more, or 1:25 or more. For the composition to remain an oil-in-water emulsion, the proportion of water phase always exceeds the proportion of oil phase, thus while in theory the weight ratio of the water-insoluble to the water-soluble phases can be down to 1:1, it is nevertheless typically of 1:5 or less, or 1:10 or less.

[0300] A tuft of virgin blond curly hair was conventionally colored using Wella Koleston Natural - Blueberry Black according to the instructions of the manufacturer and gained the intended darker shade. It was then treated with NP31 modified to include 1.5 parts of CNPFA for 50 parts of gel (colored hair being typically considered at least slightly damaged by the coloring process) and straightened as described in Example 3. Wash resistance was assessed as described in Example 4 and was found to be of at least 5 cycles. Interestingly, blond hair styled by the present method (with NP31 and washed 10 times) was also successfully colored thereafter by the same conventional coloring achieving the intended darker shade. Hence, present method is compatible with additional hair treatments, such as coloring. The fact that present method furthermore enables the development of the desired color is in contrast with some traditional styling methods which may affect the shade able to develop or having been formed prior to straightening, which typically deviates from the intended color.

[0301] Example 9: Mechanical properties of hair fibers

[0302] The non-damaging effect of the present compositions to hair fibers treated therewith can be confirmed or alternatively established by tensile testing, wherein various mechanical parameters can be compared between treated and untreated hair fibers. While fibers styled using conventional organic straightening are expected to show inferior mechanical properties compared to untreated fibers, fibers treated according to the present invention may display behavior similar or even superior to untreated fibers of similar nature. Without wishing to be bound by any particular theory, such improved properties, or at least absence of significant deterioration, are believed to stem from the presence of a polymerized version of the NPFAs within the inner parts of the hair fibers.

[0303] The hair samples treated according to Examples 3-6 or 8 can be tested for tensile resistance to assess the effect of the compositions of the present invention on mechanical properties of the hair fibers as compared to an untreated reference of a same hair type. Such a study can be performed as detailed in Example 12 of WO 2023 / 021455, the contents of which are incorporated by reference for all purposes, as if fully set herein.

[0304] Such a study was performed on initially curly hair treated with NP31 straightened and washed once as previously described. Hair samples straightened by conventional Japanese or organic method served as controls and the same untreated curly hair samples served as reference, or baseline to which all measurements were compared in the obtained stress-strain curves.

[0305] Both the Japanese and organic methods increased the modulus as compared to untreated reference, by 11.3% and 16.0% respectively, indicating that the hair fibers became relatively more deformable than virgin hair as a result of these damaging methods. In comparison, hair fibers treated by present method with NP31 displayed a modulus substantially similar to the reference, implying no alteration of the mechanical property monitored thereby, showing that hair styled according to present teachings are undamaged and more resistant to deformation than hair conventionally straightened by the control methods.

[0306] Both the Japanese and organic methods decreased the break stress point as compared to untreated reference, by 15.4% and 9.6% respectively, indicating that the hair fibers became relatively more fragile (breaking at a lower applied stress) than virgin hair as a result of these damaging methods. In comparison, hair fibers treated by present method with NP31 displayed a break stress point substantially similar to the reference, implying no alteration of the mechanical property monitored thereby, showing that hair styled according to present teachings are as stress resistant as untreated hair and less fragile than hair conventionally straightened by the control methods.

[0307] Example 10: Coloring with hair styling compositions

[0308] The styling compositions according to the present teachings may further comprise additives enabling a treatment of the fibers concomitant with their styling, such a substance being in present example a coloring agent advantageously enabling to modify the shade of the hair fibers treated with such a composition in addition to their shape. The coloring agents (including reagents due to form a color) can be conventional substances adapted for permanent or semi-permanent hair coloring, comprising a base color (also called the developer precursor) capable of penetrating into the hair, a coupler capable of reacting with the base color inside the hair to create the final dye molecule, and an oxidizing agent, which can be dispersed in the aqueous gel already having an alkaline pH. The coloring agents can alternatively be waterinsoluble and dispersed in the oily phase of the composition.

[0309] Assuming the former case, the water-insoluble phase of the composition can be prepared as previously described. The water-soluble phase of the composition additionally comprising coloring reagents can be prepared, for illustration, by adding to a gel prepared as described for AGO: 40 wt.% of urea as WHA; 5 wt.% of a base color such as 4-amino-m-cresol 2835-99-6, l-hydroxyethyl-4,5-diaminopyrazole sulfate 155601-30-2, N, N-bis(2-hydroxyethyl)-p-phenylenediamine sulfate 54381-16-7, p-aminophenol 123-30-8, p-phenylenediamine 106-50-3, p-phenylene-diamine sulfate 16245-77-5, toluene-2.5-diamine sulfate 615-50-9, or p-methylaminophenol sulfate 55-55-0; 5 wt.% of a corresponding coupler such as 2-amino-3-hydroxypyridine 16867-03-1, 4-amino-2-hydroxytoluene 2835-95-2, 2-methyl-5-hydroxy-ethylaminophenol 55302-96-0, 2-methyl-resorcinol 608-25-3, 5-amino-6-chloro-o-cresol 84540-50-1, 2-amino-4-hydroxyethyl-aminoanisole sulfate 83763-48-8, 1-naphthol 90-15-3, 2.4-diaminophenoxy-ethanol 2HC166422-95-5, 2,4-diaminophenoxyethanol sulfate 70643-20-8, m-amino-phenol 591-27-5, phenyl methyl pyrazolone 89-25-8, resorcinol 108-46-3, or 2,6-dihydroxy-ethylaminotoluene 149330-25-6; and 9 wt.% of hydrogen peroxide as oxidizing agent, all concentrations being by total weight of the aqueous phase. The oxidizing agent triggering the reaction is added last, the aqueous gel thoroughly mixed with the oily phase (e.g., at 50 parts to 1), and the resulting gel-like oil-in-water emulsion readily applied to the fibers to be treated therewith as previously described.

[0310] Alternatively, the water-soluble phase of the composition can be prepared as previously described (e.g., for AG J) and the coloring agents (e.g., Pigment Blue) added (e.g., at 10 wt.%) to the water-insoluble phase, prior to mixing the two into an oil-in-water emulsion as herein described. Regardless of the solubility of the coloring agents and the phase in which they would be disposed, to facilitate the detection of color change, the composition expected to be additionally coloring can be applied to white or blond curly hairs (e.g., for 1 hour), the rinsed hair fibers being thereafter straightened using a flat iron as described in Example 3. The success of the coloring and straightening method can be visually assessed and wash-resistance of the straightened and colored hair can then be tested as described in Example 4. Example 11: Field testing of hair styling compositions

[0311] The hair styling compositions according to the present teachings, such as prepared according to Example 2, can be tested on human volunteers having hair exceeding a length of at least 25 cm. The volunteers may have wavy to curly hair, their hair being either natively uncolored, or colored with a conventional coloring formulation. Though quantities of composition may depend on hair lengths, typically about 200 g of composition can be prepared for entirely styling head hair of one person. As established in Example 8, if the volunteers have virgin hairs not previously treated or otherwise damaged, the composition may comprise a relatively low proportion of CNPF As in the aqueous gel (e.g., a weight ratio of 1: 120) but if the hair of the volunteers was previously bleached, colored, or found damaged for any other reason, then the composition may comprise a relatively higher proportion of CNPF As in the aqueous gel (e.g., a weight ratio of 1:50). Such a study can be performed as detailed in Example 13 of WO 2023 / 021455, the contents of which are incorporated by reference for all purposes, as if fully set herein.

[0312] None of the specifically disclosed embodiments should be considered limiting, being provided for the sake of illustration. Many other alternatives, modifications and variations of such embodiments will occur to those skilled in the art based upon Applicant’s disclosure herein. Accordingly, it is intended to embrace all such alternatives, modifications and variations and to be bound only by the spirit and scope of the disclosure and any change which comes within their meaning and range of equivalency.

[0313] In the description and claims of the present disclosure, each of the verbs “comprise”, “include” and “have”, and conjugates thereof, are used to indicate that the object or objects of the verb are not necessarily a complete listing of features, members, steps, components, elements or parts of the subject or subjects of the verb. Yet, it is contemplated that the compositions of the present teachings also consist essentially of, or consist of, the recited components, and that the methods of the present teachings also consist essentially of, or consist of, the recited process steps.

[0314] As used herein, the singular form “a”, “an” and “the” include plural references and mean “at least one” or “one or more” unless the context clearly dictates otherwise. At least one of A and B is intended to mean either A or B, and may mean, in some embodiments, A and B. Unless otherwise stated, the use of the expression “and / or” between the last two members of a list of options for selection indicates that a selection of one or more of the listed options is appropriate and may be made.

[0315] As used herein, unless otherwise stated, adjectives such as “substantially”, “approximately” and “about” that modify a condition or relationship characteristic of a feature or features of an embodiment of the present technology, are to be understood to mean that the condition or characteristic is defined to within tolerances that are acceptable for operation of the embodiment for an application for which it is intended, or within variations expected from the measurement being performed and / or from the measuring instrument being used. When the term “about” and “approximately” precedes a numerical value, it is intended to indicate + / -15%, or + / -10%, or even only + / -5%, and in some instances the precise value. Furthermore, unless otherwise stated, the terms (e.g., numbers) used in this disclosure, even without such adjectives, should be construed as having tolerances which may depart from the precise meaning of the relevant term but would enable the invention or the relevant portion thereof to operate and function as described, and as understood by a person skilled in the art.

[0316] Certain marks referenced herein may be common law or registered trademarks of third parties. Use of these marks is by way of example and shall not be construed as descriptive or limit the scope of this disclosure to material associated only with such marks.

Claims

1. CLAIMS1. A method for modifying the shape of permeable fibers having a native shape, the permeable fibers optionally being mammalian hair fibers and the method being adapted for their styling, the method comprising:3.a) applying to individual fibers a composition comprising [A] a water-insoluble phase consisting of a) at least one natural polymer (NP) and b) at least one fatty agent (FA) being a fatty amine (FA1), a fatty alcohol (FA2) or a fatty acid (FA3), each being water-insoluble and all being jointly energy-curable (CNPFA), and [B] an aqueous phase comprising water and at least one water-soluble hygroscopic agent (WHA); the NP(s), FA(s) and WHAS(s) having an average molecular weight of 10,000 g / mol or less;4.b) allowing the composition to remain in contact with the fibers for an incubation period of at least 5 minutes to ensure at least partial penetration of the CNPFA(s) and WHA(s) into the fibers, the incubation step being optionally performed at an incubation temperature higher than 25°C; and5.c) applying energy to at least partially cure at least part of the CNPFA(s) within the fibers so as to obtain treated fibers, the fibers being at a temperature of at least 50°C during the curing step.

2. The method as claimed in claim 1, wherein the energy is applied while the fibers are in a desired modified shape, the modified shape being different from the native shape, the energy being convective or conductive thermal energy.

3. The method as claimed in claim 1 or claim 2, wherein the, or each, natural polymer has a water-solubility of 1 wt.% or less in neutral water as measured at a temperature of 25°C and is selected from a group consisting of a) resins including shellac, colophony resin, copal resin, dammar resins, dragon blood resin, elemi resin, kauri resin, mastic resin, sandarac resin, and tacamahac resin; b) waxes including candelilla wax, carnauba wax, jojoba wax, kafrin wax, montan wax, olive wax, rice bran wax, sal tree wax, sugarcane wax, and sunflower wax; and fractions thereof, the natural polymer being innate, chemically processed, or a synthetic equivalent and / or derivative of the same.

4. The method as claimed in any one of claim 1 to claim 3, wherein the, or each, fatty agent FA is: A) a fatty amine FA1 being a mono-amine, a di-amine, a tri-amine, or a poly-amine having a substituted or unsubstituted aliphatic chain including at least 8 carbon atoms and optionally at most 300 carbon atoms, at most 150 carbon atoms, at most 75 carbon atoms, or atmost 40 carbon atoms, the amine being a primary amine, a secondary amine or a tertiary amine; B) a fatty alcohol FA2 being a mono-ol, a di-ol, a tri-ol, or a poly-ol having a substituted or unsubstituted aliphatic chain including at least 8 carbon atoms and optionally at most 20 carbon atoms, the hydroxyl group being a primary hydroxyl, a secondary hydroxyl, or a tertiary hydroxyl; or C) a fatty acid FA3 being a mono-carboxyl having a substituted or unsubstituted aliphatic chain including at least 6 carbon atoms and optionally at most 22 carbon atoms, the carboxyl group being attached to a primary carbon, a secondary carbon, or a tertiary carbon; and the fatty agent has a water-solubility of 1 wt.% or less in neutral water as measured at a temperature of 25°C.

5. The method as claimed in any one of claim 1 to claim 4, wherein the, or each, WHA is characterized by at least one, at least two, or at least three of the following structural features: i) the WHA has a hydrogen bond energy with water of at least 21 kJ / mol, at least 22.5 kJ / mol, at least 25 kJ / mol, or at least 27.5 kJ / mol;10.ii) the WHA has a hydrogen bond energy with water of at most 40 kJ / mol, at most 35 kJ / mol, or at most 32.5 kJ / mol;11.iii) the WHA has a hydrogen bond energy with water in a range between 21 kJ / mol and 40 kJ / mol, between 22.5 kJ / mol and 35 kJ / mol, or between 27.5 kJ / mol and 32.5 kJ / mol; iv) the WHA has a solubility in water of 1 wt.% or more, 5 wt.% or more, 10 wt.% or more, 20 wt.% or more, or 30 wt.% or more, by weight of the water, as measured at a temperature of 25°C;12.v) the WHA has a solubility in water of 150 wt.% or less, 125 wt.% or less, 100 wt.% or less, or 75 wt.% or less, by weight of the water, as measured at a temperature of 25°C; vi) the WHA has a solubility in water in a range between 1 wt.% and 150 wt.%, 10 wt.% and 150 wt.%, between 15 wt.% and 125 wt.%, between 20 wt.% and 100 wt.%, or between 30 wt.% and 75 wt.%, by weight of the water, as measured at a temperature of 25°C; vii) the WHA has a solubility in the composition or in an aqueous phase thereof of 1 wt.% or more, 5 wt.% or more, 10 wt.% or more, 20 wt.% or more, or 30 wt.% or more, by weight of the composition or aqueous phase thereof, as measured at a temperature of 25°C; viii) the WHA has a solubility in the composition or in an aqueous phase thereof of 140 wt.% or less, 110 wt.% or less, 80 wt.% or less, or 50 wt.% or less, by weight of the composition or aqueous phase thereof, as measured at a temperature of 25°C; ix) the WHA has a solubility in the composition or in an aqueous phase thereof in a range between 1 wt.% and 140 wt.%, between 10 wt.% and 140 wt.%, between 15 wt.% and 110 wt.%, between 20 wt.% and 80 wt.%, or between 30 wt.% and 50 wt.%, by weight of the composition or aqueous phase thereof, as measured at a temperature of 25°C; x) the WHA has a melting temperature (Tm) of 5°C or more, 15°C or more, 25°C or more, 35°C or more, or 45°C or more;13.xi) the WHA has a melting temperature (Tm) of 200°C or less, 180°C or less, or 160°C or less;14.xii) the WHA has a melting temperature (Tm) in a range between -25°C and 200°C, between 25°C and 200°C, between 35°C and 180°C, or between 45°C and 160°C;15.xiii) the WHA has a boiling temperature Tb of 100°C or more, 120°C or more, 130°C or more, or 140°C or more;16.xiv) the WHA has a boiling temperature (Tb) of 350°C or less, 300°C or less, 250°C or less, or 225°C or less;17.xv) the WHA has a boiling temperature Tb in a range between 100°C and 350°C, between 120°C and 300°C, between 130°C and 250°C, or between 140°C and 225°C;18.xvi) the WHA has a vapor pressure of 2.3 kPa or less, 1.0 kPa or less, 0.1 kPa or less, 10 Pa or less, or 1 Pa or less, as measured at 25°C;19.xvii) the WHA has a vapor pressure of 1 mPa or more, 10 mPa or more, or 50 mPa or more, as measured at 25°C; and20.xviii)the hygroscopicity of the WHA is such that at a relative humidity of 75%RH and a temperature of 25°C, the WHA has a moisture absorption of 10% or more, by weight of dry WHA, as measured by a weight gain method at equilibrium.

6. The method as claimed in any one of claim 1 to claim 5, wherein the, or each, waterinsoluble fatty agent FA is liquid at least at a temperature between 15°C and 25°C alone or in combination of all FAs or CNPFAs.

7. The method as claimed in any one of claim 1 to claim 6, wherein the, or each, natural polymer NP and fatty agent FA are miscible one with the other, the CNPFAs being in a same phase in the composition, optionally following heating of the CNPFAs prior to their mixing with the aqueous phase, whereby the CNPFAs are adapted to jointly polymerize within the fibers.

8. The method as claimed in any one of claim 1 to claim 7, wherein the composition is an oil-in-water emulsion at least at the incubation temperature, the CNPFA(s) being in an oil phase of the emulsion and the WHA(s) being in an aqueous phase of the emulsion, the composition optionally further comprising at least one co-solvent, the at least one co-solvent being in an amount adapted for the formation of the oil-in-water emulsion and at least one cosolvent being adapted to be in a same phase as the CNPFAs within the fibers.

9. The method as claimed in any one of claim 1 to claim 8, wherein prior to applying the composition to the fibers, one or more of the following steps is performed: A- prior to mixing with the aqueous phase, the CNPFAs once forming a single phase are pre-polymerized at a temperature of at least 80°C for at least 10 minutes; and / or B- the fibers are pre-treated by at least one of: a) cleaning the fibers; and b) drying the fibers, said drying being optionally performed by heating the fibers to a temperature of at least 40°C for at least 5 minutes.

10. The method as claimed in any one of claim 1 to claim 9, further comprising following incubation step b) removing excess composition from the surface of the fibers by rinsing the fibers with a rinsing liquid and optionally drying the fibers prior to applying energy to effect at least partial curing, the rinsing liquid optionally including a detergent; and / or further comprising following curing step c), at least one of A] washing the fibers with a washing liquid, and B] conditioning the fibers with a conditioning liquid.

11. The method as claimed in any one of claim 1 to claim 10, wherein the pH of the composition enables penetration of at least a part of the CNPFA(s) and WHA(s) into the fibers, said pH being different from an isoelectric point of the fibers and optionally in a range of pH 1 to pH 3.5 or pH 5 to pH 11, and wherein the composition contains less than 0.1 wt.% of small reactive aldehydes (SRA), the SRA being selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, glutaraldehyde-forming chemicals, glyceraldehyde, and glyceraldehyde-forming chemicals.

12. The method as claimed in any one of claim 1 to claim 11, wherein the treated fibers and the untreated fibers are mammalian hair fibers and display at least one endotherm temperature within 4°C, within 3 °C, within 2°C, or within 1°C from one another as measured by thermal analysis.

13. A composition for modifying a shape of permeable fibers, the fibers optionally being mammalian hair and the composition adapted for hair styling, the composition comprising [A] a water-insoluble phase consisting of a) at least one natural polymer (NP); andb) at least one fatty agent (FA) selected from a fatty amine (FA1), a fatty alcohol (FA2) and a fatty acid (FA3); the NP(s) and FA(s) being jointly energy-curable (CNPFA(s)) and adapted to form a shapeable polymer within the fibers; and [B] an aqueous phase comprising water and at least one water-soluble hygroscopic agent (WHA);28.the NP(s), FA(s) and WHAS(s) having an average molecular weight of 10,000 g / mol or less; the water-insoluble phase being dispersed in the aqueous phase as an oil-in-water emulsion at least at a temperature selected to enable permeation of the foregoing materials within the permeable fibers.

14. The composition as claimed in claim 13, wherein the, or each, natural polymer has a water-solubility of 1 wt.% or less in water as measured at a temperature of 25°C and is selected from a group consisting of a) resins including shellac, colophony resin, copal resin, dammar resins, dragon blood resin, elemi resin, kauri resin, mastic resin, sandarac resin, and tacamahac resin; b) waxes including candelilla wax, carnauba wax, jojoba wax, kafrin wax, montan wax, olive wax, rice bran wax, sal tree wax, sugarcane wax, and sunflower wax; and fractions thereof, the natural polymer being innate, chemically processed, or a synthetic equivalent and / or derivative of the same.

15. The composition as claimed in claim 13 or claim 14, wherein the, or each, NP is independently characterized by at least one, at least two, or at least three of the following structural features:31.a- the NP has an average molecular weight between 500 g / mol and 10,000 g / mol, between 1,000 g / mol and 5,000 g / mol, or between 500 g / mol and 3,000 g / mol.32.b- the NP has a glass transition temperature (Tg) between -10°C and 120°C, between +10°C and 100°C, or between 30°C and 80°C;33.c- the NP has a softening temperature (Ts) between 40°C and 160°C, between 50°C and 120°C, or between 60°C and 100°C;34.d- the NP has an acid value (AV) between 1 mg KOH / g and 200 mg KOH / g, between 1 and 25 mg KOH / g, between 15 and 125 mg KOH / g, between 20 and 100 mg KOH / g, between 50 and 90 mg KOH / g, or between 10 and 50 mg KOH / g;35.e- the NP has a saponification value (SV) between 20 mg KOH / g and 250 mg KOH / g, between 50 mg KOH / g and 200 mg KOH / g, between 100 mg KOH / g and 200 mg KOH / g, or between 150 mg KOH / g and 250 mg KOH / g; and f- the NP has an iodine value (IV) between 0 and 200 I2 wt.%, between 0 and 150 I2 wt.%, between 0 and 100 I2 wt.%, between 0 and 50 I2 wt.%, or between 0 and 25 I2 wt.%.

16. The composition as claimed in any one of claim 13 to claim 15, wherein the, or each, water-insoluble fatty agent FA is: A) a fatty amine FA1 being a mono-amine, a di-amine, a tri-amine, or a poly-amine having a substituted or unsubstituted aliphatic chain including at least 8 carbon atoms and optionally at most 300 carbon atoms, at most 150 carbon atoms, at most 75 carbon atoms, or at most 40 carbon atoms, the amine being a primary amine, a secondary amine or a tertiary amine; B) a fatty alcohol FA2 being a mono-ol, a di-ol, a tri-ol, or a poly-ol having a substituted or unsubstituted aliphatic chain including at least 8 carbon atoms and optionally at most 22 carbon atoms, the hydroxyl group being a primary hydroxyl, a secondary hydroxyl or a tertiary hydroxyls; or C) a fatty acid FA3 being a mono-carboxyl having a substituted or unsubstituted aliphatic chain including at least 6 carbon atoms and optionally at most 22 carbon atoms, the carboxyl group being attached to a primary carbon, a secondary carbon or a tertiary carbon; and the fatty agent having a water-solubility of 1 wt.% or less in water as measured at a temperature of 25°C.

17. The composition as claimed in claim 16, wherein:38.I] the fatty amine FA1 has an amine value NV between 150 and 750 mg KOH / g and is at least one of a) a mono-amine having a C8-C22 aliphatic chain selected from a group comprising octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecyl amine, oleylamine, linoleylamine, linolenylamine, eicosylamine, and docosylamine; b) a di-amine having a C10-C22 aliphatic chain selected from a group comprising decyl- 1,10-diamine, dodecyl- 1,12-diamine, tetradecyl- 1,14-diamine, hexadecyl- 1,16-diamine, octadecyl- 1,18-diamine, oleyl diamine, linoleyl diamine, and eicosyl-l,20-diamine; c) a tri-amine having a C12-C22 aliphatic chain selected from a group comprising tridecyl-1, 3, 5-triamine, pentadecyl -1,3,5 -triamine, hexadecyl-1, 3, 5-triamine, hexadecyl-1, 4, 7-triamine, octadecyl-1, 3, 5-triamine, oleyl-1,3, 5-triamine, linoleyl-1, 3, 5-triamine, linolenyl-1, 3, 5-triamine, ricinoleyl- 1,3, 5-triamine, eicosyl-1, 3, 5-triamine, and erucyl-1, 4, 7-triamine; d) a poly-amine having a C14-C22 aliphatic chain selected from a group comprising tetradecyl- 1,2, 4, 6-tetraamine, linolenyl-1, 3, 6, 9-tetraamine, eicosyl-1, 3, 6-tetraamine and docosyl- 1, 4, 7-pentaamine; and e) a polyamine having a C30-C150 aliphatic chain selected from polyethyleneimines (PEI) and polyetheramines (PEA); derivatives and isomers thereof;39.II] the fatty alcohol FA2 has a hydroxyl value HV between 150 and 750 mg KOH / g and is at least one of a) a mono-ol having a linear or branched C8-C22 aliphatic chain selected from a group comprising 1 -octanol, 1 -nonanol, 1 -decanol, 1 -undecanol, 1 -dodecanol, 1 -tridecanol, 1-tetradecanol, 1 -hexadecanol, 1 -octadecanol, 1-eicosanol, 1 -docosanol, 8-nonen-l-ol, 9-decen-l-ol, 10-undecen-l-ol, (Z)-octadec-9-en-l-ol, cis-cis-9,12-octadecadien-l-ol, and 3,7,11,15-tetramethyl-2-hexadecen-l-ol, 1 -dodecylcyclo-hexanol and 1-octyl-cy cl opentanol; and b) a diol having a linear or branched C8-C22 aliphatic chain selected from a group comprising 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, and 1,11-undecandiol; or c) a mono-ol having a C8-C22 aliphatic chain including a ring and selected from a group comprising 2-methyl-5-(prop-l-en-2-yl)cyclohex-2-en-l-ol, 5-methyl-2-(l-methylethylidene)-cyclohexanol, 2-isopropyl-5-methylcyclohexan-l-ol, 4-(2,2,6-trimethyl-cyclohexyl)butan-2-ol, 1-octyl-cy clopentanol and 1 -dodecylcyclohexan- 1 -ol;40.III] the fatty acid FA3 has a saponification value SV between 150 and 750 mg KOH / g and is a mono-carboxyl having a C6-C26 aliphatic chain selected from a group comprising a) saturated mono-carboxyl including hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and undecanoic acid; b) unsaturated mono-carboxyl having at least one unsaturated bond including decenoic acids having one unsaturated bond within a C14-C22 aliphatic chain, dienoic acids having two unsaturated bonds within a C16-C24 aliphatic chain, and trienoic acids having three unsaturated bonds within a C18-C26 aliphatic chain; and c) cyclic fatty acids selected from a group comprising cyclohexane-carboxylic acid, cycloheptanecarboxylic acid, cyclooctane-carboxylic acid, 1 -cyclooctene- 1 -carboxylic acid, cyclopentyl-undecanoic acid, cyclohexyl-undecanoic acid, 7-(2-octylcyclopentyl)heptanoic acid, cyclopropane-tetradecanoic acid, 11,12-methylene-octadecanoic acid, 7-(2-octylcyclo-propen-l-yl)heptanoic acid, 7-(2-octylcyclopropyl)heptanoic acid, 8-(2-octylcyclo-propen-l-yl) octanoic acid, and 8-(2-octylcyclopropyl)-octanoic acid;41.and derivatives and isomers thereof.

18. The composition as claimed in any one of claim 13 to claim 17, wherein the, or each, WHA is characterized by at least one, at least two, or at least three of the following structural features:43.i) the WHA has a hydrogen bond energy with water of at least 21 kJ / mol, at least 22.5 kJ / mol, at least 25 kJ / mol, or at least 27.5 kJ / mol;44.ii) the WHA has a hydrogen bond energy with water of at most 40 kJ / mol, at most 35 kJ / mol, or at most 32.5 kJ / mol;45.iii) the WHA has a hydrogen bond energy with water in a range between 21 kJ / mol and 40 kJ / mol, between 22.5 kJ / mol and 35 kJ / mol, or between 27.5 kJ / mol and 32.5 kJ / mol; iv) the WHA has a solubility in water of 1 wt.% or more, 5 wt.% or more, 10 wt.% or more, 20 wt.% or more, or 30 wt.% or more, by weight of the water, as measured at a temperature of25°C;46.v) the WHA has a solubility in water of 150 wt.% or less, 125 wt.% or less, 100 wt.% or less, or 75 wt.% or less, by weight of the water, as measured at a temperature of 25°C; vi) the WHA has a solubility in water in a range between 1 wt.% and 150 wt.%, between 10 wt.% and 150 wt.%, between 15 wt.% and 125 wt.%, between 20 wt.% and 100 wt.%, or between 30 wt.% and 75 wt.%, by weight of the water, as measured at a temperature of 25°C;47.vii) the WHA has a solubility in the composition or in an aqueous phase thereof of 1 wt.% or more, 5 wt.% or more, 10 wt.% or more, 20 wt.% or more, or 30 wt.% or more, by weight of the composition or aqueous phase thereof, as measured at a temperature of 25°C; viii) the WHA has a solubility in the composition or in an aqueous phase thereof of 140 wt.% or less, 110 wt.% or less, 80 wt.% or less, or 50 wt.% or less, by weight of the composition or aqueous phase thereof, as measured at a temperature of 25°C;48.ix) the WHA has a solubility in the composition or in an aqueous phase thereof in a range between 1 wt.% and 140 wt.%, between 10 wt.% and 140 wt.%, between 15 wt.% and 110 wt.%, between 20 wt.% and 80 wt.%, or between 30 wt.% and 50 wt.%, by weight of the composition or aqueous phase thereof, as measured at a temperature of 25°C;49.x) the WHA has a melting temperature (Tm) of 5°C or more, 15°C or more, 25°C or more, 35°C or more, or 45°C or more;50.xi) the WHA has a melting temperature (Tm) of 200°C or less, 180°C or less, or 160°C or less;51.xii) the WHA has a melting temperature (Tm) in a range between -25°C and 200°C, between 25°C and 200°C, between 35°C and 180°C, or between 45°C and 160°C;52.xiii) the WHA has a boiling temperature (Tb) of 100°C or more, 120°C or more, 130°C or more, or 140°C or more;53.xiv) the WHA has a boiling temperature (Tb) of 350°C or less, 300°C or less, 250°C or less, or 225°C or less;54.xv) the WHA has a boiling temperature (Tb) in a range between 100°C and 350°C, between 120°C and 300°C, between 130°C and 250°C, or between 140°C and 225°C; xvi) the WHA has a vapor pressure of 2.3 kPa or less, 1.0 kPa or less, 0.1 kPa or less, 10 Pa or less, or 1 Pa or less, as measured at 25°C;55.xix) the WHA has a vapor pressure of 1 mPa or more, 10 mPa or more, or 50 mPa or more, as measured at 25°C and56.xx) the hygroscopicity of the WHA is such that at a relative humidity of 75%RH and a temperature of 25°C, the WHA has a moisture absorption of 10% or more, by weight of dry WHA, as measured by a weight gain method at equilibrium.

19. The composition as claimed in claim 18, wherein the, or each, WHA is selected from a group consisting of amides including carboxamides, methylxanthines, purine alkaloids and salts thereof; organic acids and salts thereof or organic salts; saturated or unsaturated heterocyclic compounds; monosaccharides, and disaccharides, the WHA being solid at 25°C.

20. The composition as claimed in claim 19, wherein the, or each, WHA is I) a carboxamide having the general formula RC(=O)NR'R", wherein R, R', and R" each independently represent a linear, branched or cyclic, substituted or unsubstituted, organic group not exceeding 6 carbon atoms, or a hydrogen atom, the organic group of R optionally including a second carboxamide group, said carboxamide being selected from a group consisting of urea, methanamide, ethanamide, propaneamide, butanamide; cyclopropane carboxamide, cyclobutane carboxamide, cyclopentane carboxamide; cyclohexane carboxamide; ethanediamide, propanediamide, butanediamide, pentanediamide, hexane-diamide; alanine amide, asparagine amide, glutamine amide, glycine amide, and proline amide; and isomers and derivatives thereof; or II) an organic acid selected from a group comprising citric acid, gluconic acid, lactic acid, malic acid, oxalic acid, salicylic acid, succinic acid, tartaric acid, and metal salts thereof.

21. The composition as claimed in any one of claim 13 to claim 20, wherein:60.A- a combined concentration of the at least one water-insoluble natural polymer is at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, or at least 0.25 wt.%; and optionally at most 5 wt.%, at most 3 wt.%, or at most 2 wt.%, by total weight of the composition; and / or61.B- a combined concentration of the at least one water-insoluble fatty agent is at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, or at least 0.25 wt.%; and optionally at most 5 wt.%, at most 3 wt.%, or at most 2 wt.%, by total weight of the composition; and / or62.C- a weight per weight (w / w) ratio between the at least one water-insoluble fatty agent and the at least one water-insoluble natural polymer is at least half-a-part of FA(s) per one part of NP(s), at least one part of FA(s) per one part of NP(s), at least one and a half part of FA(s) per one part of NP(s), or at least two parts of FA(s) per one part of NP(s); the w / w ratio being optionally of at most ten parts of FA(s) per one part of NP(s), or at most five parts of FA(s) per one part of NP(s); and / or63.D- a combined concentration of the at least one WHA is at least 10 wt.%, at least 12.5 wt.%, at least 15 wt.%, at least 17.5 wt.%, or at least 20 wt.%; and optionally at most 50 wt.%, at most 48 wt.%, at most 46 wt.%, at most 44 wt.%, at most 42 wt.%, at most 40 wt.%, at most 38 wt.%, at most 36 wt.%, or at most 34 wt.%, by total weight of the composition.

22. The composition as claimed in any one of claim 13 to claim 21, wherein the composition further comprises at least one A- co-solvent selected from the group consisting of: Ci-Ce alcohols having at least one hydroxyl group, water-miscible ethers, aprotic solvents, esters and mineral or vegetal oils; the co-solvent being in an amount controlling a form of the composition, the form of the composition being an oil-in-water emulsion or a single-phase composition; and / or B- additive selected from a group comprising an emulsifier, a wetting agent, a thickening agent, a pH modifying agent and a charge modifying agent; and / or C-coloring agent adapted for semi-permanent or permanent coloring including reagents therefor.

23. The composition as claimed in any one of claim 13 to claim 22, wherein the pH of the composition enables penetration of at least a part of the CNPFA(s) into the fibers, the pH being in a range of 1 to 3.5 or 5 to 11 and wherein the composition contains less than 0.1 wt.% of small reactive aldehydes (SRA), the SRA being selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, glutaraldehyde-forming chemicals, glyceraldehyde, and glyceraldehyde-forming chemicals.

24. A kit for modifying the shape of permeable fibers, the fibers optionally being mammalian hair and the kit enabling their styling, the kit comprising:67.i) a first compartment containing at least one natural polymer (NP) and at least one fatty agent (FA) being a fatty amine (FA1), a fatty alcohol (FA2) or a fatty acid (FA3), each being water-insoluble and having an average molecular weight of 10,000 g / mol or less and all being jointly energy-curable (CNPFA(s)); and68.ii) a second compartment containing at least one water-soluble hygroscopic agent (WHA) having an average molecular weight of 10,000 g / mol or less, and at least one of:69.i) water;70.ii) a co-solvent; and iii) a pH modifying agent;71.wherein the contents of the second compartment have a pH selected to increase the penetration of at least part of the CNPFA(s) into the fibers;72.wherein mixing of the compartments produces an oil-in-water emulsion; and73.wherein at least one of the CNPFA(s) of the first compartment and at least one of the WHA(s) of the second compartment is respectively a natural polymer, a fatty amine, a fatty alcohol, a fatty acid or a WHA of a composition according to any one of claim 13 to claim 23 and the oil-in-water emulsion is optionally applicable to the fibers by a method according to one of claim 1 to claim 12.

25. The kit as claimed in claim 24, further comprising one or more coloring agents, including reagents therefor, adapted for semi-permanent or permanent coloring, said agents or reagents being disposed in the first or second compartments and / or in a different compartment so as to avoid premature reaction between substances of a same compartment, the oil-in-water emulsion produced by mixing of all compartments further enabling modifying the color of the permeable fibers.

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