Improved compositions and methods for styling hair fibers

Abstract

The present disclosure relates to a method for styling mammalian hair fibers, comprising applying a hair styling composition to the hair, comprising a phenolic monomer and a water-soluble moisture absorbing agent, allowing the monomer and the water-soluble moisture absorbing agent to penetrate into the hair, and curing the monomer to form a polymer therein that can overcome the tendency of the hair to return to its natural shape. When curing is performed while the hair is modified to a desired shape, the resulting polymer can maintain the modified shape and the moisture absorbing agent can provide a long-lasting hair styling effect. Also disclosed are compositions suitable for such hair styling and kits capable of preparing the same.

Description

[Technical field]

[0001] The present disclosure relates to compositions, kits, and methods for styling keratinous fibers, such as mammalian hair. [Background technology]

[0002] Mammalian (e.g., human) hair fibers are layered structures, with the outermost layer being the cuticle, a thin protective layer of keratin protein that surrounds a central hair shaft composed of the cortex and medulla. This cuticle layer is made up of scale-like cells that overlap each other in a layered fashion, like the shingles of a roof. The physical appearance and shape of the hair fiber is determined by the various interactions between the keratin chains within the fiber, and the amino acid composition of the keratin is a factor in the types of interactions possible. Cysteine ​​side chains allow for the formation of disulfide bonds, while other amino acid residues can form weaker interactions such as hydrogen bonds, hydrophobic interactions, ionic bonds, and Coulombic interactions. The presence of such reactive groups in the fiber, their proportion along the fiber, and their capabilities due to the fiber's configuration determine the occurrence of these interactions and the appearance of the hair composed of the fiber or multiple such fibers.

[0003] Covalent disulfide bonds that can form between the thiol side chains of two adjacent cysteine ​​residues are primarily responsible for the structural stability, durability and mechanical properties of the fibers, and the disruption of these bonds by various procedures is the mechanism behind most modern methods of permanent hair styling (mainly straightening or waving).

[0004] One such procedure, called "Japanese straightening", involves the selective cleavage of disulfide bonds using reducing agents, e.g., mercaptans or sulfites, which mechanically relax the keratin, followed by reoxidization of the free sulfhydryl groups, such that the disulfide bonds are recombined at the end of the process while the hair retains a shape suitable for achieving the desired styling. Various styling tools, such as hot irons or hair dryers, can be used to induce further stress to permanently conform the hair to the desired shape, whether straight or wavy.

[0005] Another procedure for permanent styling of hair is to use stronger reducing agents, such as strong alkalis with a pH above 11.0, under which conditions disulfide bonds can be cleaved in a less selective manner as the alkalis penetrate deeper into the pH-swollen hair, disrupting possible rearrangements of disulfide bonds.

[0006] Other procedures called "keratin straightening" and "organic straightening", including "Brazilian straightening", are considered semi-permanent and involve the use of large amounts of aldehydes, namely formaldehyde, formaldehyde-generating agents, or glutaraldehyde, with most straighteners containing 2-10% of such chemical agents. Examples of formaldehyde-generating agents, also called formaldehyde-releasing agents, include glyoxylic acid and its derivatives (e.g., glyoxyloylcarbocysteine), some of which are commonly used as preservatives. These aldehyde-based or aldehyde-generating agents react with the keratin in the hair fiber and act as crosslinking agents, thus prolonging the new hair form and shape. Formaldehyde and glutaraldehyde are known to be carcinogenic and can cause eye and nose irritation, as well as allergic reactions of the skin, eyes, and lungs. As a result, these substances are considered hazardous by the Occupational Safety and Health Administration (OSHA) and hair styling product manufacturers are required to limit these substances to 0.2 weight percent (wt%) or less, and in some jurisdictions even to 0.1 wt% or less by weight of the composition. OSHA has tested several keratin treatments and found that many products contain formaldehyde in solution or off-gas formaldehyde upon heating, even when the products are marketed as "formaldehyde-free" or do not contain formaldehyde in their ingredient list, raising public doubts about the claimed safety of "non-formaldehyde" containing keratin straightening products. It has been reported that in such products, formaldehyde may simply be replaced by formaldehyde-generating agents. Although such products do penetrate to some extent into the hair fiber beneath the cuticle, they are believed to act primarily by a superficial coating, and this external protective sheath is the basis for the smoothing and lustrous benefits of this method. However, this is a temporary effect as the coating strips moisture from the hair and as the protective keratin-containing coating thins, the hair becomes brittle, dry and dull.

[0007] Some permanent or semi-permanent straightening methods require the use of specialized shampoos to maintain the effect for a long time, and such products are adapted to the specific chemical reactions that each such treatment affects the shape of the hair. Furthermore, such methods offer little flexibility if one wishes to further modify the hair color, hair style, or return to a natural style, and such procedures usually require the use of new permanent treatments that further damage the hair, or waiting for hair to regrow.

[0008] The amino acids that make up the keratin protein of hair fibers also contain side chains that can form weak non-covalent bonds, such as hydrogen bonds that can form between polar and / or charged side chains in the presence of water molecules. These hydrogen bonds form between amino acids on the outer surface of the cuticle scales and within or beneath the scales. These hydrogen bonds can be broken by heat (e.g., a flat iron or hair dryer, which can remove water from the hair) and re-formed by drying or cooling, allowing temporary hair styling. Although such methods do not use chemicals that damage the hair, their effects are temporary due to the sensitivity of the fibers so configured to water, including the relative humidity of the environment. Summary of the Invention [Problem to be solved by the invention]

[0009] The classification of hair styling methods as permanent, semi-permanent, or temporary usually depends on the number of shampoos required for the hair to resume its natural shape. Permanent methods can be harsh enough to require new hair fiber growth, and while some non-temporary styling may reverse spontaneously, such methods can themselves be damaging.

[0010] Therefore, there is a need for a hair styling method that reduces hair damage and the need for harmful reagents, while at the same time advantageously providing long-lasting hair style and shape. [Means for solving the problem]

[0011] overview The present disclosure relates, inter alia, to compositions, kits, and methods comprising or using the same for styling hair fibers, which have been developed to overcome at least some of the shortcomings associated with conventional methods of hair styling. As used herein, "styling" hair includes any act of modifying its shape in a visually detectable and desirable manner, including straightening or relaxing the hair if wavy, curly, or coiled; or conversely, curlying the hair if it is relatively straighter than desired; thus optionally increasing or decreasing the natural tendency of the hair fiber to be curly.

[0012] Advantageously, the curable compositions and methods of the present teachings allow temporary or permanent hair styling without breaking disulfide bonds in hair fibers or permanently changing their molecular structure. Thus, if a hair fiber has a certain number of sulfur bonds in its natural (unmodified) form before styling according to the present teachings, the fiber styled to have a modified form will essentially exhibit the same number of sulfur bonds. Alternatively, the harmlessness of the present compositions and methods can be evaluated by modified hair fibers that exhibit essentially the same physicochemical structure as natural hair fibers. For example, in some embodiments, the mechanical properties of the hair fibers are not impaired by the present compositions and methods, and in certain embodiments, some properties may even be improved. That the chemical structure of the hair fibers is not adversely affected can be demonstrated, for example, by thermal analysis, where modified and natural hair fibers, treated or untreated by the present compositions and methods, respectively, may exhibit at least one essentially similar endothermic temperature (determinable by various methods, such as DSC, DMA, TMA, and similar thermogravimetric methods). The endothermic temperatures of two materials or hair fibers can be considered essentially similar if they are within 4° C., 3° ​​C., 2° C., or 1° C. of each other. In certain embodiments, the endothermic temperatures of the treated and untreated fibers, which serve as references, are measured by the same thermal analysis method, with DSC being preferred.

[0013] In a first aspect of the present invention, there is provided a method of styling mammalian hair fibres by modifying the shape of the fibre from a natural shape to a desired modified shape, the method comprising: a) applying to individual hair fibers a hair styling composition to coat the hair fibers, said hair styling composition comprising at least one water-insoluble phenol-based monomer (PBM), at least one water-soluble hygroscopic agent (WHA), water, optionally one or more cure accelerators miscible with the PBM, and further optionally at least one co-polymerization agent; b) leaving the hair styling composition in contact with the hair fibers for a time sufficient to ensure at least partial penetration of the PBM(s) and WHA(s) into the hair fibers; and c) applying energy to the hair fiber to at least partially cure at least a portion of the HPM that has penetrated within the hair fiber, wherein said partial curing optionally occurs while the hair fiber is in a desired altered shape.

[0014] The pH of the composition can be selected to promote penetration of the PBM and WHA into the hair fiber, said pH being different from the isoelectric point of the fiber being treated at which penetration, if any, is minimized. In some embodiments, the pH of the hair styling composition ranges from pH 1 to pH 3.5, or from pH 5 to pH 11.

[0015] In some embodiments, prior to step a) of applying a hair styling composition comprising PBM(s) and WHA(s), one or more of the following steps are performed: A- prepolymerizing at least one PBM, and / or at least one hardening accelerator, and / or at least one copolymerization agent before mixing with water; and / or B- a) Cleansing the hair fibre; b) drying the hair fibers at a temperature and for a time sufficient to ensure severing at least a portion of the hydrogen bonds of the hair fibers; and c) applying a pre-treatment composition to the hair fibers. Pre-treating the hair fibres with at least one of the following:

[0016] As will be explained in more detail in the context of restyling and destyling, the actual styling step that gives the hair fiber treated by the method of the present invention a modified shape does not necessarily have to be performed simultaneously with the curing of the monomers that gradually form a polymer that can overcome the tendency of the hair fiber to return to a previous (e.g. unmodified / natural / alternative) shape. Once the polymer is formed in the hair fiber, its shape can be modified later when desired. This treatment method can be considered as a styling method that is not related to the chronological sequence of modifying the overall shape of the fiber, simply because the formation of the polymer in the fiber can provide volume, and this treatment method can also be considered as a styling effect that is not related to the degree of detectability of the change.

[0017] In some embodiments, the energy applied to at least partially cure at least a portion of the energy curable phenolic monomers infiltrated within the hair fiber is thermal energy, and the heat is transferred to the hair fiber by conduction (e.g., direct contact with a styling iron), convection (e.g., using a hot air blower, hair dryer), or radiation (e.g., using a ceramic far-infrared (IR) emitting hair dryer). In other embodiments, the energy applied is more generally electromagnetic (EM), and may include, for example, ultraviolet (UV) radiation in addition to the IR radiation mentioned above. Some PBMs are primarily or solely curable by thermal energy (heating), while others are primarily or solely curable by electromagnetic energy. The former may also be referred to as thermosetting monomers, and the latter as EM curable monomers. In some embodiments, the PBMs may be curable by both mechanisms, in which case they may be referred to as hybrid curable monomers.

[0018] In some embodiments, the fibers treated by the methods of the invention and the untreated fibers (or similar counterparts) exhibit at least one endothermic temperature within 4° C., within 3° C., within 2° C., or within 1° C. of each other as measured by thermal analysis.

[0019] For the sake of brevity, materials that may be useful in the preparation of hair styling compositions that may be applied in the method of the present invention for styling hair are detailed below with reference to the compositions, the desired properties of their components, and their relative proportions, these characteristics applying mutatis mutandis to the present method.

[0020] In a second aspect of the present invention, there is provided a method of restyling hair fibres having a hair shape which is a first modified hair shape achieved by a styling method or hair styling composition as further detailed herein, the restyling method comprising: A- applying energy to a hair fiber having a first shape and containing a synthetic polymer therein having a softening temperature, wherein the synthetic polymer is capable of providing a shape to the hair fiber at a temperature below its softening temperature, and the application of energy is for a time sufficient to soften the synthetic polymer within the hair fiber; and B- Terminating the application of energy while the hair fibre is in a second modified hair shape of the desired restyling, wherein the second modified hair shape is the same or different from said first shape.

[0021] In some embodiments, the fibers having the desired second shape exhibit at least one endothermic temperature within 4° C., within 3° C., within 2° C., or within 1° C. of an untreated fiber lacking the synthetic polymer, as measured by thermal analysis.

[0022] In some embodiments, the application of thermal energy for restyling in step A is carried out for at least 5 minutes at a temperature above the softening temperature of the polymer, for example at a temperature of at least 50° C. In some embodiments, the restyling temperature is high enough to further reduce the amount of residual water in the hair fiber.

[0023] In a third aspect of the present invention, there is provided a method of de-styling hair fibres having an altered hair shape achieved by the styling method or hair styling composition as further detailed herein, namely a method of styling hair fibres comprising therein a synthetic polymer having a softening temperature, said synthetic polymer being capable of imparting a shape to the hair fibre when at a temperature below its softening temperature, said de-styling method comprising: I- applying energy to the hair fiber having a first shape, wherein said application of energy is for a time sufficient to soften the synthetic polymer within the hair fiber such that the hair fiber is at least 40°C, or preferably at least 45°C, for at least 10 minutes; II- applying water during the application of said energy to allow at least partial reformation of hydrogen bonds released by the softening of the synthetic polymer; and III- Ceasing the application of said energy and water while the hair fibre is devoid of artificial restraint, so as to allow the polymer to resume its unsoftened shape while the hair fibre is in its natural unaltered shape.

[0024] In some embodiments, fibers having a natural, unmodified shape exhibit at least one endothermic temperature within 4° C., within 3° C., within 2° C., or within 1° C. of an untreated fiber lacking the synthetic polymer, as measured by thermal analysis.

[0025] The ability to restyling or de-style hair previously treated with the methods and compositions of the present invention (i.e., hair fibers containing therein a polymer synthesized in situ by crosslinking of PBM in the presence of WHA(s)) is advantageous and unexpected in the art, where conventional methods typically require application of an appropriate composition to further alter the hair shape.

[0026] As used herein, the term "treated" with respect to hair fibers refers to fibers that have been treated with a composition or by a method of the present invention, and conversely, the term "untreated" refers to hair fibers that have not been treated with a composition or by a method disclosed herein.

[0027] Hair treated by the present methods and compositions may exhibit additional advantages, such as with respect to the mechanical properties of the treated hair and / or with respect to the types of hair that can be treated. For example, while conventional styling methods generally have a detrimental effect on the mechanical properties of hair, hair fibers treated according to the present teachings may exhibit at least one tensile property (e.g., hair fiber elastic modulus, break stress, and toughness) that is at least equal to the same property in the corresponding untreated fiber. Additionally or alternatively, the present methods and compositions may be applied to hair that has already been treated by conventional hair means, such as bleaching or coloring, but where conventional styling methods may not be compatible.

[0028] In a fourth aspect of the present invention, there is provided a hair styling composition for modifying the shape of mammalian hair fibres, the hair styling composition being selected from: a) a single-phase composition, wherein the single phase comprises at least one water insoluble phenolic monomer (PBM), at least one water soluble moisture absorbent (WHA), water having a pH selected to increase the penetration of at least a portion of the PBM(s) and WHA(s) into the hair fiber, and a co-solvent, the single phase optionally further comprising one or more set accelerators miscible therewith; and b) an oil-in-water emulsion, wherein the emulsion consists of a) an oil phase comprising at least one water-insoluble phenolic monomer (PBM) and optionally one or more set accelerators miscible therewith; and b) an aqueous phase containing at least one water-soluble hygroscopic agent (WHA) and having a pH selected to increase the penetration of at least a portion of the PBM(s) and WHA(s) into the hair fiber. The hair styling compositions are further described herein and in the accompanying claims.

[0029] In some embodiments of any of the foregoing aspects, the hair styling composition comprises less than 0.2 wt% small reactive aldehyde (SRA), the SRA being selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals, based on the total weight of the composition. In other embodiments, the hair styling composition contains less than 0.1 wt%, less than 0.05 wt%, less than 0.01 wt%, less than 0.005 wt%, or less than 0.001 wt% SRA, based on the total weight of the composition.

[0030] The water-soluble moisture absorbent that may be used in any embodiment of the aforementioned aspects, or each water-soluble moisture absorbent if there is more than one, is characterized by at least one of the following features: i) the WHA is a polar non-electrolyte that does not substantially ionize when dissolved (e.g., in water or in an aqueous solution or phase); ii) the WHA is capable of forming hydrogen bonds with water molecules that are stronger than hydrogen bonds that water molecules can form between themselves, i.e., the WHA has a hydrogen bond energy with water of at least 21 kilojoules / mol (kJ / mol), at least 22.5 kJ / mol, at least 25 kJ / mol, or at least 27.5 kJ / mol; iii) 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; iv) the WHA has a hydrogen bond energy with water in the range of 21 kJ / mol to 40 kJ / mol, 22.5 kJ / mol to 35 kJ / mol, or 27.5 kJ / mol to 32.5 kJ / mol; v) the WHA has a solubility in water of 5 wt. % or more, 10 wt. % or more, 20 wt. % or more, or 30 wt. % or more, by weight of water, measured at a temperature of 25°C; vi) the WHA has a solubility in water of not more than 150% by weight, not more than 125% by weight, not more than 100% by weight, or not more than 75% by weight, measured at a temperature of 25°C; vii) the WHA has a solubility in water, measured at a temperature of 25°C, in the range of 5 wt% to 150 wt%, 10 wt% to 125 wt%, 20 wt% to 100 wt%, or 30 wt% to 75 wt%, by weight of water; viii) the WHA has a solubility in the hair styling composition or its aqueous phase of 5 wt. % or more, 10 wt. % or more, 20 wt. % or more, or 30 wt. % or more, based on the weight of the composition or its aqueous phase, measured at a temperature of 25° C.; ix) the WHA has a solubility in the hair styling composition or its aqueous phase of 140 wt.% or less, 110 wt.% or less, 80 wt.% or less, or 50 wt.% or less, based on the weight of the composition or its aqueous phase, measured at a temperature of 25°C; x) the WHA has a solubility in the hair styling composition or its aqueous phase, measured at a temperature of 25° C., based on the weight of the composition or its aqueous phase, in the range of 5 wt % to 140 wt %, 10 wt % to 110 wt %, 20 wt % to 80 wt %, or 30 wt % to 50 wt %; xi) WHA is the melting temperature T m is 25°C or higher, 35°C or higher, or 45°C or higher; xii) WHA is the melting temperature T m Melting temperature T is 200℃ or less, 180℃ or less, or 160℃ or less m Being; xiii) WHA is the melting temperature T m is in the range of 25℃~200℃, 35℃~180℃, or 45℃~160℃; xiv) WHA is the boiling temperature T b is higher than the boiling temperature of water measured at atmospheric pressure; in other words, the WHA is the boiling temperature T b is 100°C or higher, 120°C or higher, or 140°C or higher; xv) WHA is the boiling temperature T b is 300°C or less, 250°C or less, or 225°C or less; xvi) WHA is the boiling temperature Tb is in the range of 100℃ to 300℃, 120℃ to 250℃, or 140℃ to 225℃; xvii) the WHA is less volatile than water and therefore has a vapor pressure that is less than the vapor pressure of water, in other words, the WHA has a vapor pressure of 2.3 kilopascals (kPa) or less, measured at 25° C., preferably 1.0 kPa or less, 0.1 kPa or less, 10 Pa or less, or 1 Pa or less; xviii) The WHA has a vapour pressure of 1 mPa or more, 10 mPa or more, or 50 mPa or more, measured at 25°C; xix) The WHA has a vapour pressure in the range of 1 mPa to 1 kPa, 1 mPa to 0.1 kPa, 1 mPa to 50 Pa, 1 mPa to 10 Pa, or 1 mPa to 1 Pa; xx) at a concentration of 1 wt.% or less, based on the weight of the hair styling composition, the WHA does not substantially interfere with the pH of the hair styling composition, such that the pH of the hair styling composition in the presence of said concentrations of the WHA is within half a log of the pH of the hair styling composition in the absence of the WHA; and xxi) The WHA is approved by a regulatory authority for use as a cosmetic in the intended concentration in hair styling compositions.

[0031] In some embodiments, the WHA is a polar non-electrolyte that does not substantially ionize when dissolved (e.g., in a liquid that contains or consists of water). Without wishing to be bound by a particular theory, it is believed that this lack of ionization helps maintain the respective charge of the hair styling composition and the hair fibers treated therewith. The respective charge of these species can provide a zeta potential difference and gradient that favors the movement of the PBM(s) and WHA(s) to the hair surface, thereby allowing them to penetrate the hair, where they can polymerize, favoring styling as taught herein.

[0032] In some embodiments, the WHA is a polar water-soluble hygroscopic agent and satisfies at least one of the properties set forth in each of features ii)-iv) above with respect to hydrogen bond energy. In some embodiments, a WHA that satisfies features i)-iv) or ii)-iv) further satisfies at least one of the properties set forth in each of features v)-vii) above with respect to its solubility in water. In some embodiments, a WHA that satisfies features i)-iv), ii)-iv), i)-vii), or ii)-vii) further satisfies at least one of the properties set forth in each of features vii)-x) above with respect to its solubility in the hair styling composition or in the aqueous phase thereof. In some embodiments, a WHA that satisfies features i)-iv), ii)-iv), i)-vii), ii)-vii), i)-x), or ii)-x) is liquid at room temperature (about 25° C.), but can alternatively be solid, and further satisfies at least one of the properties set forth in each of features xi)-xiii) above with respect to its melting temperature. In some embodiments, a WHA satisfying features i)-iv), ii)-iv), i)-vii), ii)-vii), i)-x), ii)-x), i)-xiii), or ii)-xiii) is a solid at room temperature and further satisfies at least one of the properties set forth in each of the features xiv)-xvi) listed above with respect to its boiling temperature. In some embodiments, a WHA satisfying features i)-iv), ii)-iv), i)-vii), ii)-vii), i)-x), ii)-x), i)-xiii), ii)-xiii), i)-xvi), or ii)-xvi) is a solid at room temperature and further satisfies at least one of the properties set forth in each of the features xvii)-xix) listed above with respect to its vapor pressure. In some embodiments, a WHA satisfying characteristics i)-iv), ii)-iv), i)-vii), ii)-vii), i)-x), ii)-x), i)-xiii), ii)-xiii), i)-xvi), ii)-xvi), i)-xix), or ii)-xix) is solid at room temperature and further satisfies characteristic xx), recited above, with regard to its minimal impact on the pH of the hair styling composition.Preferably, feature xxi) regarding compatibility of the WHA regulatory status and its concentration in the hair styling composition of the present invention for cosmetic use applies to any combination of features i)-xx) or ii)-xx), and in particular to the combinations specifically envisaged in this paragraph.

[0033] When used with respect to the liquid for which a particular property of the present material (e.g., solubility or lack thereof) is being reported, the term "water" shall mean a liquid having a pH of about 7 and a viscosity of 18.2 megaohms cm at 25°C, as customary for the applicable measurement. -1 The term may refer to pure deionized or double distilled water having a resistivity of 0.1 to 0.5 wt. %, but as is clear from the context, water may refer to different grades of liquid, including tap water as conventionally used in hair styling methods.

[0034] In some embodiments, the hair styling composition further comprises a co-polymerizing agent comprising at least one functional group capable of cross-polymerizing with at least one of the PBM and the cure accelerator, the functional group being selected from: hydroxyl, carboxyl, amine, anhydride, isocyanate, isothiocyanate, and double bond.

[0035] In some embodiments, the hair styling composition further comprises at least one additive selected from the group including emulsifiers, wetting agents, thickening agents, and charge modifying agents.

[0036] In a fifth aspect of the present invention there is provided a kit for styling mammalian hair fibres, said kit comprising: a first compartment containing at least one water insoluble phenolic monomer (PBM); and At least one Water-Soluble Hygroscopic Agent (WHA): 1. Water; 2. Co-solvents; and 3. pH adjuster; and a second compartment containing at least one of Including, wherein the contents of the second compartment are a liquid having a pH selected to increase penetration of at least a portion of the PBM(s) and WHA(s) into the hair fiber; and These compartments are mixed to produce the hair styling composition as a single phase composition or an oil-in-water emulsion, as further described in the specification and claimed below.

[0037] In some embodiments, at least one PBM of the first compartment is pre-polymerized prior to being placed in the kit.

[0038] In some embodiments, the hair styling composition prepared by mixing the compartments of the kit is ready to use, while in other embodiments, the hair styling composition needs to be further diluted (e.g., with tap water) by the end user prior to mixing of the compartments and / or application to the hair fiber.

[0039] In some embodiments, at least one cure accelerator selected from a crosslinker (suitable for condensation curing and / or addition curing) and a cure accelerator is further included in the hair styling composition, kit, or method of using it. The composition and method may, in some embodiments, include two or more types of crosslinkers that allow both addition curing and condensation curing of the prepolymer in combination. Such a cure accelerator may be placed in the first or second compartment if it does not react spontaneously (e.g., at room temperature) with any one of the components of the first or second compartment, respectively. Alternatively, the cure accelerator may be placed in a separate additional compartment to be mixed with the first and second compartments during preparation of the hair styling composition as a single-phase composition or oil-in-water emulsion.

[0040] The compartments of the kit (and their respective contents) are selected to avoid or reduce any reactions that would reduce the efficacy of the product during storage of the kit at the desired storage temperature (e.g., not exceeding room temperature). In some embodiments, with or without prepolymerization of the PBM(s), the first and / or third compartments are maintained in an inert environment, preferably under an inert gas, such as argon or nitrogen. For similar reasons, the compartments can be selected to be radiation opaque or sealed against factors detrimental to the stability of the contents.

[0041] In some embodiments, the first compartment of the kit further comprises at least one auxiliary polymerization agent.

[0042] In some embodiments, the kit further comprises at least one co-solvent, which may be contained in the first, second, or another additional compartment.

[0043] In some embodiments, the kit further comprises at least one additive selected from the group including: emulsifiers, wetting agents, thickening agents, and charge control agents. If the at least one additive is oil-miscible, it may be located in the first compartment. If the at least one additive is water-miscible, it may be located in the second compartment. The additive may also be placed in a separate additional compartment.

[0044] Additional objects, features and advantages of the present disclosure will be set forth in the detailed description which follows, and in part will become readily apparent to those skilled in the art from the specification or will be learned by the practice of the present disclosure as set forth in the specification and claims, as well as the accompanying drawings. Various features and subcombinations of the embodiments of the present disclosure can be employed without reference to other features and subcombinations.

[0045] BRIEF DESCRIPTION OF THE DRAWINGS Some embodiments of the present disclosure will now be further described by way of example with reference to the accompanying drawings. Similar reference numerals or letters indicate corresponding or similar components. This specification, together with the drawings, will make clear to those skilled in the art how some embodiments of the present disclosure can be implemented. The drawings are for illustrative purposes and do not attempt to show the structural details of the more detailed embodiments, but are necessary for a basic understanding of the present disclosure. For the sake of clarity and convenience of illustration, some objects depicted in the drawings are not necessarily drawn to scale. [Brief description of the drawings]

[0046] [Figure 1] Figure 1A is an image taken by focused ion beam milling combined with scanning electron microscopy (FIB-SEM) at a voltage of 1.20 kV, showing a cross-section of a reference untreated hair fiber, and Figure 1B is an image taken with a FIB-SEM, showing a cross-section of the same reference untreated hair fiber as in Figure 1A, but at a voltage of 10 kV. [Diagram 2] Figure 2A is an image taken by FIB-SEM at a voltage of 1.20 kV, showing a cross-section of a hair fibre treated with an oil-in-water emulsion according to an embodiment of the invention, before a hair washing cycle. Figure 2A' is a schematic representation of the FIB-SEM image of Figure 2A. Figure 2B is an image taken by FIB-SEM, showing the same cross-section of the same treated hair fibre as in Figure 2A, before a hair washing cycle. This image was taken at a voltage of 10 kV. Figure 2B' is a schematic representation of the FIB-SEM image of Figure 2A. [Diagram 3] Figure 3A is an image taken by FIB-SEM at a voltage of 1.20 kV showing a cross-section of a hair fiber treated with the same oil-in-water emulsion as in Figure 2A or Figure 2B after 16 hair washes, and Figure 3B is an image taken by FIB-SEM showing the same cross-section of the same treated hair as shown in Figure 3A after 16 hair washes, this image taken at a voltage of 10 kV. [Figure 4]Figure 4A shows a photograph of an untreated curly black hair fiber, and Figure 4B shows a photograph of a curly black hair fiber treated with a hair styling composition according to one embodiment of the present invention. [Diagram 5] FIG. 5 shows a series of differential scanning calorimetry (DSC) plots of thermal analysis of hair samples, including a reference untreated hair sample, hair samples treated by two commercially available methods, and one hair sample treated with a hypothetical non-toxic composition according to one embodiment of the present invention. [Figure 6] FIG. 6 is a simplified schematic diagram of a hair styling method according to one embodiment of the present teachings. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0047] Detailed Description The present disclosure relates to a composition for styling hair fibers, and more particularly to a curable composition, comprising: a) at least one water-insoluble phenolic monomer (PBM) capable of undergoing polymerization by any suitable reaction to produce a macromolecule (e.g., polymer); and b) at least one material capable of extending the activity of the cured polymer so as to prolong the durability of the hair styling provided by the cured polymer. A material capable of enhancing the effectiveness of the cured polymer is a water-soluble hygroscopic agent (WHA) capable of binding water molecules. It is believed that such a WHA sequesters water molecules that may otherwise adversely interact with the cured polymer, hair keratin, and / or other hair components in a manner that affects the constrained shape made possible by the curing of the PBM.

[0048] Without wishing to be bound by any particular theory, the inventors have surprisingly discovered that the WHA(s) provide a protective / lengthening effect with respect to the duration of hair styling, even though they are water-soluble and are expected to run off the hair fiber relatively easily after rinsing the treated hair or after each shampooing, and disappear after only a few times (e.g., less than 5 times, less than 4 times, or less than 3 times). The inventors speculate that unexpectedly, the WHA is able to remain sufficiently within the hair fiber, either as an isolated "water-absorbing" entity, or in interaction with the polymer cured from the monomer of the present invention, or in interaction with the cured polymer and the natural components of the hair fiber, or in interaction with the natural components of the hair fiber, or in any similar mechanism of action or combination thereof. Thus, the unexpectedly long presence of the WHA in the hair reduces or delays the loss of styling effect obtained by the PBM that would normally be observed over time. In other words, if a composition lacking a WHA provides the desired hair styling that withstands N wash cycles, then a similar hair styling composition further comprising a WHA will provide the desired hair styling that withstands M additional wash cycles, where M is greater than N, all other conditions (e.g., application conditions) being equal.

[0049] The present invention is an improvement to the applicant's International Patent Publication (WO) 2021 / 224784, the contents of which are incorporated by reference for all purposes as if fully set forth herein.

[0050] As used herein, the term monomer is not meant to include only a single repeating molecule, but may include short oligomers, so long as the repeating number results in a molecular weight not exceeding 10,000 g / mol, 5,000 g / mol, or 3,000 g / mol, as deemed appropriate for the ability of any molecule to penetrate hair fibers. The hair styling composition allows for the delivery of energy curable monomers to the interior of hair fibers, along with any compounds that may be necessary for proper polymerization, while allowing such compounds to be mixed in situ with the monomers within the fibers. The compounds that are miscible with the monomers and promote their curing may be cure accelerators and / or co-solvents. Similarly, the hair styling composition allows for the delivery of moisture absorbents, preferably polar water-soluble moisture absorbents (WHA), within hair fibers.

[0051] Compounds that act within the hair fiber to promote polymerization or reduce, delay or prevent damage to the styling effect provided by the formed polymer can be delivered in the same phase as the monomers or in a separate phase. Thus, hair styling compositions according to the present teachings can be single-phase compositions or oil-in-water emulsions, both of which typically have a pH adapted to facilitate the penetration of at least some of the monomers and any other materials necessary for their proper assembly and maintenance of effect as a cured polymer. The promoting pH can act by a) promoting sufficient opening of the hair scales and / or b) promoting sufficient charging (e.g., as can be measured by zeta potential) of the hair fiber and hair styling composition; and can be either acidic, ranging from pH 1 to pH 3.5 or pH 4, or weakly acidic to weakly alkaline, ranging from pH 5 to pH 8, or alkaline, ranging from pH 8 to pH 11, preferably pH 9 to pH 11. In other words, the pH is deemed to be favorable for penetration into the hair fiber as long as it is in a range other than the isoelectric point of the hair, and may vary slightly between 3.5-5, 4-5, or 3.5-4 depending on the hair fiber and its health.

[0052] Methods for preparing and using these hair styling compositions, as well as kits that allow for the preparation of such compositions and hair styling therewith, are also described.

[0053] The principles, applications, and embodiments of the teachings herein may be better understood with reference to the accompanying specification and figures. Upon reading the specification and figures presented herein, one skilled in the art will be able to practice the present disclosure without undue effort or experimentation.

[0054] Before describing at least one embodiment in detail, it is understood that the disclosure is not necessarily limited in its application to the details of construction and the arrangement of components and / or methods set forth herein. The disclosure is capable of other embodiments or of being practiced or carried out in various ways. The phrases and terms used herein are for purposes of explanation and should not be considered limiting. For example, while hair is often mentioned to describe the advantages of the present invention, it is clear that the teachings of the present invention apply equally to wigs, hair extensions, or eyelashes, to name a few options. Thus, providing a durable hairstyle may be for hair, wigs, or hair extensions attached to a human subject, and the term further includes providing a durable eyelash shape for eyelashes, as an example.

[0055] It will be understood that both the foregoing general description and the following detailed description, including materials, methods and examples, are merely illustrative of the present disclosure and are intended to provide an overview or framework for understanding the nature and characteristics of the present disclosure as claimed, and are not intended to be necessarily limiting.

[0056] In one aspect of the present invention, a method is provided for styling a mammalian hair fiber by modifying the shape of the mammalian hair fiber.

[0057] In the first step of the method of the present invention, a liquid hair styling composition is applied onto individual hair fibers. The liquid composition is a single-phase composition or an oil-in-water emulsion comprising water and: i) at least one water-insoluble phenolic monomer (PBM) and at least one water-soluble hygroscopic agent (WHA). When the hair styling composition is provided as a single phase, a suitable co-solvent is provided in a sufficient amount to ensure miscibility of the monomer and water portions of the liquid, and the aqueous medium containing the WHA and co-solvent is further compatible with the miscibility of any other materials desired for the polymerization of the monomer (e.g., any cure accelerators, and / or co-polymerization agents) or for the morphology and applicability of the composition (e.g., humectants, thickeners, etc.). When the hair styling composition is provided as a biphasic emulsion, a co-solvent, if present, is provided to at least ensure miscibility of the monomer and any cure accelerators, where the monomer is in the oil phase of the emulsion and the WHA is in the water phase of the emulsion. Generally, the oil phase is dispersed as small droplets in a continuous aqueous phase so that the composition forms an oil-in-water emulsion, which may further include an emulsifier.

[0058] Before detailing the specific compounds suitable for the method and composition of the present invention, in addition to the above-mentioned ability of the monomers (and any agents that promote their polymerization) to penetrate into the hair fiber and be miscible with each other when and / or as long as curing is set to proceed, it is more generally necessary for the materials (including those that prevent water damage to the styling benefits provided by the resulting cured polymer, which may be present in the aqueous phase that is not miscible with the monomers) to be compatible with the styling composition, its method of preparation, and its method of use. By "compatible" is meant that the monomers, cure accelerators, co-polymerization agents, co-solvents, water-soluble hygroscopic agents, or any other compatible components of the composition do not adversely affect the effectiveness of any other compounds or the ability to prepare or use the final composition. "Compatibility" can be chemical, physical, or both, and can depend on the relative amounts. By way of example, a cure accelerator is considered compatible if it has functional groups that are compatible with cross-linking between monomers and / or otherwise accelerating the process. A co-solvent is considered compatible if it has a sufficiently slow volatilization rate that allows polymerization to proceed while the associated substances are in the same phase. A material is considered compatible if it is not affected by the pH of the composition or the temperature to which it may be subjected during preparation or use of the composition for hair styling. Although not required, all materials may be liquid at room temperature for ease of preparation and use, or if solid, may be readily miscible with the liquid components of the composition (e.g., a WHA that is solid at room temperature may be readily dissolved in water or any other aqueous medium). In addition, materials that are liquid at room temperature are believed to improve hair feel compared to solid materials. If the material is solid at room temperature and requires heating to dissolve, its melting point must be sufficiently low for the heating temperature to selectively promote its dissolution without causing the thermosetting monomer to cure faster than normal and without otherwise affecting its ability to polymerize. If desired, a plasticizer can be included to keep the hair styling composition, particularly the monomers and other hardenable components for penetrating the hair fiber, liquid at room temperature.

[0059] Returning to the premise that such compounds are usually able to penetrate into the hair fiber after the hair scales have properly opened, it is believed, without wishing to be bound by any particular theory, that smaller molecules can migrate into the fiber more easily than larger molecules. The physical size of the molecule may depend on further factors (such as the presence or absence of special structure and "compactness"), but the molecular weight of the compound may help to estimate its ability to penetrate the fiber. In some embodiments, materials for polymerization in hair fibers (e.g., monomers and crosslinkers), or for facilitating such polymerization (e.g., co-polymerization agents, cosolvents, and hardening accelerators), or for reducing, retarding, or preventing damage to the formed polymer or its effects (e.g., WHA) have an average molecular weight (MW) of 10,000 g / mol or less, 5,000 g / mol or less, 3,000 g / mol or less, 2,500 g / mol or less, 2,000 g / mol or less, 1,500 g / mol or less, or 1,000 g / mol or less.

[0060] The molecular weight of a molecule with a known chemical formula can be calculated based on the molecular weights of its constituent atoms, in which case the average molecular weight is simply the molecular weight assigned to a particular molecule. For compounds formed with unknown or diverse chemical formulas, such as polymers, the average molecular weight of a population of related molecules can be provided by the material supplier or can be determined independently 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 spectrometry (MALDI-TOF MS). Some of these methods are described in ASTM D4001 or ISO 16014-3. The average molecular weight can be estimated by number or weight, both of which are encompassed herein.

[0061] In one embodiment, at least one PBM has the general formula I: [ka] During the ceremony, R 1 , R 2 , R 3 , and R 5 are each independently a hydrogen atom, a hydroxyl, a linear, cyclic, or branched, substituted or unsubstituted C 1 ~C 20 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Aryl, C. 1 ~C 8 Aromatic esters (e.g., C 1 ~C 8 phenyl ester), or C 1 ~C 8 Non-aromatic esters (e.g., C 1 ~C 8 glycol esters); and R 4 is a hydrogen atom, a hydroxyl, or a saturated or unsaturated C X H Y alkyl, where X is an integer less than or equal to 15, and Y is equal to 2X+1-n, where n is selected from 0, 2, 4, and 6.

[0062] In some embodiments, R 1 , R 2 , R 3 , and R 5 are each independently a hydrogen atom, hydroxyl, methyl, 2-propenyl, phenyl acetate, phenyl carboxylate, ethylene glycol monoacetate, ethylene glycol monocarboxylate, or methoxy. 4 is a hydrogen atom, hydroxyl, or C 15 H 31-n alkyl, where n is selected from 0, 2, 4, and 6.

[0063] In an embodiment, the composition comprises R 4 is hydroxyl and R 1 , R 2 , R 3 , and R 5are all hydrogen atoms, and the monomer, i.e., benzene-1,3-diol, is also known as resorcinol, then the composition may further need to further comprise at least a second PBM of formula I, a second PBM other than resorcinol, and optionally a cure accelerator.

[0064] In some embodiments, at least one PBM is selected from any of the following general formulas II-V: [ka]

[0065] C of PBM 15 H 31-n The side chains are hydrocarbon (alkyl) substituents with different degrees of unsaturation, i.e., they can be saturated (n=0), monoene (n=2), diene (n=4), and triene (n=6) hydrocarbon side chains.

[0066] In some embodiments, the compound of general formula II constituting at least one of the PBMs of the composition is a cardanol derivative, which may be selected from the group consisting of 3-pentadecylphenol (n=0), 3-[pentadeca-8-enyl]phenol (n=2), 3-[penta-deca-8,11-dienyl]phenol (n=4), 3-[pentadeca-8,11,14-trienyl]phenol (n=6) and conformers thereof.

[0067] In another embodiment, the compound of general formula III constituting at least one of the PBMs of the composition is a cardol derivative, which may be selected from the group consisting of 5-pentadecylbenzene-1,3-diol (n=0), 5-[pentadeca-8-enyl]benzene-1,3-diol (n=2), 4-[pentadeca-8,11-dienyl]benzene-1,3-diol (n=4), 5-[pentadeca-8,11-dienyl]-benzene-1,3-diol (n=4), 5-[pentadeca-9,12-dienyl]-benzene-1,3-diol (n=4), 5-[pentadeca-8,11,14-trienyl]benzene-1,3-diol (n=6) and conformers thereof.

[0068] In yet another embodiment, the compound of general formula IV constituting at least one of the PBMs of the composition is a 2-methyl cardol derivative, which may be selected from the group consisting of 2-methyl-5-pentadecylbenzene-1,3-diol (n=0), 2-methyl-5-[pentadeca-8-enyl]benzene-1,3-diol (n=2), 2-methyl-5-[pentadeca-8,11-dienyl]benzene-1,3-diol (n=4), 2-methyl-5-[pentadeca-8,11,14-trienyl]benzene-1,3-diol (n=6) and conformers thereof.

[0069] In some embodiments, at least one PBM of the composition is cashew nut shell liquid (CNSL) or a component thereof.

[0070] CNSL occurs as a dark, viscous, oily liquid in the shells of cashew nuts and is obtained as a by-product during industrial processing of the nuts. The composition of CNSL is as follows: 4 The phenol compounds of the above general formulas II to IV have side chains with different degrees of non-conjugated unsaturation at one or more positions selected from at least one of the 8th, 11th or 14th carbons of the hydrocarbon side chain. [ka]

[0071] Natural CNSL also contains anacardic acids represented by the general formula VI: [ka] In the formula, C 15 H 31-n The side chains are as described above for the other components of CNSL. The amount of anacardic acid in naturally occurring CNSL is 60-70 wt%. However, technical or commercial grades of CNSL contain less than 1 wt% anacardic acid, as it is decarboxylated during the CNSL process and converted primarily to cardanol (Formula II). In certain embodiments, the CNSL used in the present invention contains less than 0.5 wt%, less than 0.3 wt%, less than 0.2 wt%, or less than 0.1 wt% anacardic acid.

[0072] The saturated and unsaturated derivatives of each of the CNSL components can be present in various amounts. For example, cardanol in CNSL can be composed of 60 wt% monoene derivatives, 10 wt% diene derivatives, and 30 wt% triene derivatives. The amounts of these derivatives can be determined using techniques such as molecular distillation, thin layer chromatography (TLC) / gas liquid chromatography (GLC), and TLC-mass spectrometry.

[0073] In some embodiments, at least one PBM is of Formula VII: [ka] During the ceremony: i.R 1 , R 2 , and R 3 At least one of the following is a linear, branched, or cyclic, substituted or unsubstituted, C 1 ~C 8 Aromatic ester or C 1 ~C 8 Carboxylate substituents formed from non-aromatic esters, R being non-carboxylate1 , R 2 and R 3 (Non-carboxylate R 1 , R 2 or R 3 (also referred to as ) is a hydrogen atom or a hydroxyl group; and ii) R 4 and R 5 are each independently a hydrogen atom or a hydroxyl group.

[0074] The PBMs of formula VII, having one hydroxyl group and one carboxylate attached to the aromatic ring, can be considered derivatives of hydroxybenzoic acid, with one of the groups being ortho, meta, or para to the other.

[0075] In some embodiments, at least one PBM in the hair styling composition has a carboxylate substituent R 1 and such PBMs are known as 2-hydroxybenzoates or salicylates, and the PBM is selected from the group including amyl salicylate, benzyl salicylate, 4-tert-butylphenyl salicylate, cyclohexyl salicylate, methyl salicylate, hexyl salicylate, octyl salicylate, phenyl salicylate, salicin, and salsalate. In some embodiments, at least one PBM in the hair styling composition is selected from the group including amyl salicylate, benzyl salicylate, 4-tert-butylphenyl salicylate, cyclohexyl salicylate, methyl salicylate, hexyl salicylate, octyl salicylate, phenyl salicylate, salicin, and salsalate. In some embodiments, the carboxylate substituent is R 2 and the PBM is selected from the group consisting of methyl 3-hydroxybenzoate and phenyl 3-hydroxybenzoate. In some embodiments, at least one PBM in the hair styling composition has a carboxylate substituent represented by R 3and PBM is selected from the group including benzyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, heptyl 4-hydroxybenzoate, methyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, and N-propyl 4-hydroxybenzoate.

[0076] The aforementioned PBMs are named according to a nomenclature appropriate for the presence of a single hydroxyl group on the aromatic ring of formula VII, but this should not be construed as limiting, and in some embodiments, the hydroxybenzoic acid ring of the PBM may be further substituted with one or more hydroxyl groups, and the relative position on the ring of the two or more hydroxyl groups to the carboxylate substituent is selected from: 2,3-dihydroxy-benzoic acid; 2,4-dihydroxy-benzoic acid; 2,5-dihydroxy-benzoic acid; 2,6-dihydroxy-benzoic acid; 3,4-dihydroxy-benzoic acid; 3,5-dihydroxy-benzoic acid; 2,3,4-trihydroxy-benzoic acid; 2,4,6-trihydroxy-benzoic acid; and 3,4,5-trihydroxy-benzoic acid, with the carboxylate group being considered as the 1-position on the ring.

[0077] Furthermore, linear, branched or cyclic C 1 ~C 8 The carboxylate groups formed with aromatic or non-aromatic esters can be further substituted with hydroxyl or amine groups along the side chain.

[0078] In certain embodiments, the at least one PBM of the hair styling composition is selected from the group including phenyl 2-hydroxybenzoate (or phenyl salicylate), benzyl salicylate, phenyl 3-hydroxybenzoate, phenyl 4-hydroxybenzoate, hexyl salicylate, 2-hydroxyethyl salicylate, phenyl 2,3-dihydroxybenzoate, phenyl 2,4-dihydroxybenzoate, phenyl 2,5-dihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, and phenyl 3,4,5-trihydroxybenzoate.

[0079] The hydroxyl (-OH) group(s) of the PBM, together with varying degrees of unsaturation of the side chains attached to the benzene aromatic ring, other than the hydroxyl groups or saturated hydrocarbons, make the PBM a highly polymerizable material capable of a variety of polymerization reactions (e.g., via condensation or addition). Without wishing to be bound by theory, it is believed that the PBM can be polymerized by condensation of its hydroxyl groups with other condensation polymerizable groups, while appropriate side chain unsaturation can, under appropriate conditions, be the basis for addition polymerization.

[0080] The PBMs described above and further detailed herein are generally oily in nature, i.e., substantially immiscible in water, and therefore, in the absence of a suitable amount of suitable co-solvent, are present in the oil phase of an oil-in-water emulsion.In some embodiments, the residual solubility of the PBMs (or any other material considered to be water-insoluble) is 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, or 0.5 wt% or less based on the weight of pure water, and more appropriately based on the weight of the aqueous environment in which they are to be placed at the pH of said liquid.In other words, 1 part by weight or less of the material will dissolve in 20 parts by weight of liquid (e.g., less than 5 g of material in 100 g of water, the total amount of the mixture is 105 g, and the wt% of the material in the entire composition is about 4.76%).Solubility can be assessed by the naked eye, and a soluble composition (e.g., a single-phase composition) is generally clear (not cloudy) at room temperature. This condition can alternatively be quantified by measuring the refractive index of the solution and comparing it to a calibration curve using known amounts of PBM in water.

[0081] The water-insoluble PBMs according to the present teachings typically form hair styling compositions that are oil-in-water emulsions, but in the presence of an appropriate amount of a suitable cosolvent (e.g., greater than 30 wt %) can alternatively form single-phase compositions.

[0082] In some embodiments, in order to accelerate polymerization, the hair styling composition (e.g., single-phase or oil-in-water emulsion) compatible with the hair styling method of the present invention further comprises, in addition to at least one PBM, ii) at least one cure accelerator selected from crosslinkers and cure accelerators. Crosslinkers refer to compounds that actively participate in the cure process and are incorporated into the resulting polymer network, while cure accelerators can alternatively or additionally catalyze or activate the cure (e.g., by lowering the polymerization temperature or increasing its speed). The cure accelerator should preferably be oil-miscible so that it is in phase with the oily monomers when polymerizing in the hair fiber. It should be noted that if a cure accelerator is used after the hair styling composition is applied to the hair, the cure accelerator used in such a process can be water-soluble, provided that the accelerator is water-based.

[0083] In some embodiments, the crosslinker can react with the monomer via a condensation cure mechanism and may be referred to as a "condensation cure crosslinker." In other embodiments, the crosslinker can react with the monomer via an addition cure mechanism and may be referred to as an "addition cure crosslinker." In some embodiments, the same cure accelerator can act both as a crosslinker (that incorporates the polymer network) and as a cure accelerator (that catalyzes its formation). Regardless of the type of monomer and cure accelerator that can crosslink to form a network within the hair fiber that can constrain the hair fiber into a desired modified shape, the resulting internally formed polymer can also be referred to as a synthetic backbone. This term does not mean that the monomers are necessarily artificial (not naturally occurring), but rather that the resulting polymer is synthesized in situ and does not naturally occur within the hair fiber. Simply put, the exogenous polymer "fixes" the hair fiber in the desired shape, allowing the fiber to overcome natural forces and otherwise assume or regain its natural shape. This "mechanical" metaphor is not intended to exclude any other or additional (e.g. chemical) mechanism of action of the polymer that allows it to maintain the desired styling effect or shape. For example, the polymer may alternatively or additionally act as a moisture barrier, preventing, reducing or delaying the transfer of water molecules from the external environment to the innermost keratin proteins. Unwanted water molecules reaching the hair components styled by the method of the present invention may undo the hydrogen bonds within such proteins to such an extent that they allow the hair fiber to gradually return to its natural shape.

[0084] In some embodiments, the crosslinking agent suitable for the hair styling composition and method of the present invention has two or more crosslinking functional groups, and the presence of these two crosslinking functional groups is sufficient to cause chain extension of the polymer, and this process can additionally or alternatively occur in the absence of a crosslinking agent if the PBM contains such a linking functional group in its chemical formula. When a polymer network with a relatively high crosslink density is desired and a crosslinking agent is included in the composition for its curing, it advantageously has three or more crosslinking functional groups, thereby increasing the density of the three-dimensional network formed. In some embodiments, the crosslinking agent is multifunctional, having four or more, five or more, six or more, seven or more, or eight or more crosslinking functional groups, and such functional groups are usually not present in excess of 10 per molecule of crosslinking agent. Additionally or alternatively, a relatively high crosslink density can be obtained by using a relatively high concentration of crosslinking agent (or a high ratio of crosslinking agent to PBM). It is expected that the polymer formed by the curing of the PBM in the hair fiber with a relatively high crosslink density will form a stronger framework for the hair styled therewith than its counterpart with a relatively low crosslink density. However, the inventors have found that in some circumstances, polymers formed with a relatively low crosslinking density are also suitable. This is especially the case when hair fibers are damaged, for example as a result of health conditions or as a result of traditional treatments that are harmful to hair, such as bleaching or coloring. Damaged hair fibers may exhibit discontinuities on their outer surface, allowing more moisture to penetrate into the hair shaft compared to healthy hair fibers. When hair fibers are exposed to high temperatures (e.g., during styling with a hot iron or drying with hot air), residual moisture that may be present in the hair cortex may undergo explosive evaporation, which may further expand the defects of the damaged hair fiber or form new micropores that accelerate the future penetration of moisture, and the increase in such voids with each high temperature heating may significantly impair the integrity of the hair and lead to hair breakage.

[0085] Without wishing to be bound by theory, it is believed that polymers formed with a relatively low crosslink density behave thermoplastically, i.e., they can reversibly soften and become malleable upon heating, while remaining sufficiently rigid upon cooling and at ambient temperature to maintain the desired style on treated hair. The relative "fluidity" of polymers with a relatively low crosslink density allows them to block or seal pores or voids that may exist or form upon heating of the hair fiber, particularly in damaged hair. This "sealing effect" is expected to reduce water re-entry into the hair over time and reduce the likelihood and / or extent of explosive evaporation of trapped water upon subsequent heating. Such reduction in water re-entry may be desirable for both damaged and undamaged hair, and therefore compositions that have a relatively low crosslink density to form polymers with thermoplastic behavior may be applied to both hair forms.

[0086] Thus, in some embodiments, if a polymer network having a relatively low crosslink density is desired, the crosslinker may be selected to have a relatively low number of crosslinking functional groups and / or may be present in the composition at a relatively low concentration (or low ratio of crosslinker to PBM).

[0087] Other characteristics that are easily understood by those skilled in the art may promote a relatively low crosslink density or conversely a relatively high crosslink density of the polymer network formed by the curable monomer as taught herein. For example, a relatively short crosslinker (e.g., having a relatively low MW) may form a polymer with denser crosslinks / tighter 3D network than a relatively long crosslinker (e.g., having a relatively high MW), which may form a looser network. It is emphasized that a single characteristic of a crosslinker alone cannot determine whether a hair styling composition prepared therewith tends to have a relatively low crosslink density / thermoplastic behavior once polymerized. Nevertheless, a relatively low concentration of a relatively long crosslinker with a relatively low crosslinking functionality is expected to favor the formation of a cured polymer with a relatively low crosslink density than one prepared using a relatively high concentration of a relatively short crosslinker with a relatively high crosslinking functionality.

[0088] As will be readily understood by those skilled in the art of crosslinker-promoted polymerization, such compounds are typically present in an amount that corresponds to at least a stoichiometric reaction between the crosslinkable groups of the monomers and the corresponding reactive groups of the crosslinker. Such a minimum amount may already have been provided for the excess of crosslinker, especially if some of the crosslinkable groups of the monomers and growing oligomers are blocked as the cure proceeds toward the formation of a more complex polymer. Nevertheless, in some embodiments, it may have been desirable to simply include such cure accelerators in excess of the stoichiometric concentration, especially if the crosslinkers can react with each other in addition to their ability to react with the monomers.

[0089] Suitable condensation-curable crosslinkers can be selected from reactive silanes having at least two silanol groups and a molecular weight of up to 1,000 g / mol, such as, for example, aminopropyltriethoxysilane (e.g., Dynasylan® AMEO), 3-isocyanatopropyltriethoxysilane, 3-aminopropyl(diethoxy)-methylsilane, methyltriethoxysilane, or N-[3-(trimethoxysilyl)-propyl]ethylenediamine; mixtures of reactive silanes and aminosilanes (e.g., Evonik Dynasylan® SIVO). 210); polybasic acids such as succinic acid, adipic acid, or citric acid; polyols such as castor oil; polyamines such as hexamethylenediamine or hexamethylenetetramine (optionally combined with a dialkyl maleate, such as dimethyl maleate, diethyl maleate, or dibutyl maleate, and their reaction products to produce active crosslinkers capable of reacting with the monomers of the invention under the conditions taught herein, via a possible Michael reaction); mono- and di-glycidyls, such as (3-glycidyloxypropyl)-trimethoxysilane or poly(ethylene glycol) diglycidyl ether; diisocyanates, such as isophorone diisocyanate or 4,4'-methylenebis(cyclohexylisocyanate); allyl compounds, such as allyl hexanoate, or 1-methyl-4-(prop-1-en-2-yl)cyclohex-1-ene (limonene); and polyphenols such as tannic acid. In a particular embodiment, the condensation curable crosslinker is aminopropyltriethoxysilane.

[0090] The multifunctional crosslinker can be a silsesquioxane with an organic glycidyl group or methacrylate group attached. Such hybrid molecules contain an inner inorganic cage core with organic groups attached to the core. There can be eight groups, which enhances the crosslinking ability and gives high density to the crosslinked polymer network. Such multifunctional crosslinkers include glycidyl POSS® Cage Mixture EP0409 or glycidyl methacrylate POSS® Cage Mixture MA0735, which are commercially available from Hybrid Plastics (USA). In certain embodiments, such hybrid crosslinkers are used in hair styling compositions with the crosslinker aminopropyltriethoxysilane.

[0091] Advantageously, although not necessarily, crosslinkers may further serve to modify the pH of the composition, promoting the opening of the scales of the cuticle of the hair fiber to which the composition containing them is applied, allowing the PBM, or a portion thereof, to penetrate into the hair shaft.

[0092] Without wishing to be bound by any particular theory, it is believed that the PBM according to the present teachings is a sufficiently small molecule (e.g., having a MW of 10,000 g / mol or less) to at least partially penetrate the fiber trunk where it can subsequently polymerize upon application of energy (e.g., heat or electromagnetic suitable for inducing polymerization of the monomers). The penetration of the PBM into the hair fiber can be observed and monitored by microscopic techniques such as FIB-SEM (e.g., Figures 2B and 3B, further referenced below). If polymerization is achieved while the hair fiber is in the desired modified shape, the resulting phenolic oligomer (PBO) and phenolic polymer (PBP) can maintain the fiber in the modified shape or retard the force of the fiber returning to its natural (unmodified) shape. Such processes are described in more detail in the following sections.

[0093] Returning to the composition that may be applied to the individual fibers as the first step of the hair styling method, the crosslinker linkers, if present, may undergo at least partial hydrolysis, for example by water, prior to combination with the PBM, notwithstanding any additional effect that they may provide. Alternatively, hydrolysis may be induced after combination of the crosslinker with the PBM, using a hydrolysis accelerator. Suitable accelerators of such hydrolysis may be acids having (or providing to the composition) a pH of 4 to 6, such as salicylic acid and lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, malic acid, tartaric acid, azelaic acid or propionic acid. The hydrolysis accelerator may be present in the composition applied to the hair fibers and / or may be applied later on the hair fibers. In any case, partial hydrolysis of the suitable crosslinker is expected to increase the activity of the crosslinker and promote the condensation that leads to the polymerization of the PBM. The hydrolysis accelerator may be considered as a type of cure accelerator.

[0094] In some embodiments, cure accelerators suitable for hair styling compositions comprising PBMs, and methods of the invention using same, are suitable for condensation polymerization, and include, for example, metal complexes with metal carboxylates such as acetylacetonates or naphthenates (e.g., those having metals: Co, Mn, Ce, Fe, Al, Zn, Zr, Se, or Cu); metal complexes with alkoxides such as aluminum tri-sec-butoxide; metal soaps such as aluminum stearate, magnesium stearate; metal salen complexes such as N,N'-bis(salicylidene)ethylenediamine complexes with Fe or Mn; strong acids such as p-toluenesulfonic acid, sulfuric acid, phosphoric acid, or sulfosuccinic acid; and strong acids such as NaOH, KOH, NH 4 The base may be selected from strong bases such as OH.

[0095] In this context, compounds are classified according to their primary role for simplicity, but it should be noted that such functions are not necessarily exclusive of others. For example, cure accelerators (e.g., aluminum tri-sec-butoxide) are commonly used as cure catalysts, but can have crosslinkable groups, in which case the cure accelerator can also function as a crosslinker and be incorporated into the formed polymer network. In another example, dibutyl maleate, which functions as an auxiliary polymerization agent, can also function as a co-solvent, increasing the miscibility of PBM with water in the aqueous phase.

[0096] In some embodiments, the PBM of the present invention may further contain at least one addition curable group, such as a conjugated or non-conjugated double bond, allowing the monomer to undergo both condensation and addition polymerization via the hydroxyl groups of the PBM. For example, when the PBM is CNSL, its R 4The non-conjugated unsaturated alkyl side chains at the 1-position allow such polymerization by addition curing under suitable conditions. Suitable conditions for addition curing may include the use of a cure accelerator in the composition to open the double bonds of the side chains to form radicals, thereby initiating addition polymerization. Alternatively, or in addition, the crosslinker itself may contain addition polymerizable groups, the activation of which leads to radical formation. Activated groups on the crosslinker can react with activated groups on the PBM, or activated molecules of the same type can react with each other. Such addition polymerizable groups that may be present in the crosslinker may be methacrylate groups (e.g., those present in silsesquioxane cage cores, such as the commercially available Glycidyl Methacryl POSS® Cage Mixture MA0735). Suitable cure accelerators for addition polymerization include organic peroxides such as benzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide; ortho- and para-methyl and 2,4-dichloro derivatives of dibenzoyl peroxide; dicumyl peroxide, alkyl peroxides (e.g., lauroyl peroxide, and 2-butanone peroxide), ketone peroxides, and diacyl peroxides.

[0097] In some embodiments, when the PBM and / or crosslinker contain at least one double bond, conjugated or non-conjugated (which makes the crosslinker suitable for addition curing with the PBM), and especially at least two double bonds (e.g., short dienes), exposure to atmospheric oxygen can induce an autoxidation reaction, resulting in the formation of radicals, allowing polymerization or crosslinking to proceed by an addition mechanism, optionally in the absence of a dedicated cure accelerator.

[0098] In some embodiments, crosslinkers suitable for addition curing are linear, branched, or cyclic alkene compounds containing up to 15 carbon atoms and containing a number of double bonds that allow for the formation of at least two radicals upon opening of the double bonds. For example, the alkene can contain at least two double bonds when located within the alkene chain (e.g., myrcene (C 10 H 16 ), geraniol, (C 10 H 18 O), Carvone (C 10 H 14 O) and farnesene (C 15 H 24 ), or short monoterpenes such as 1,5-hexadiene or 1,5-hexadiene-3,4-diol.

[0099] Additional crosslinkers having terminal double bonds at both ends of the chain include diallyl ethers (e.g., di(ethylene glycol), divinyl ether, or 2,2-bis(allyloxymethyl)-1-butanol); diallyl sulfides; diallyl esters (e.g., diallyl adipate); acrylates (e.g., ethylene glycol diacrylate, ethylene glycol dimethacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate); diallyl acetals (e.g., 3,9-divinyl-2,4,8,10-tetra-oxaspiro[5.5]undecane); triallyl cyanurate; and triallyl isocyanurate. Crosslinkers suitable for addition curing of PBMs also include substituted or unsubstituted vinyl aromatic compounds (e.g., styrene or vinyl toluene); vinyl esters (e.g., vinyl acetate, vinyl benzoate, vinyl stearate, or vinyl cinnamate); and vinyl alcohols (e.g., 10-undecen-1-ol). If a mixture of crosslinkers is used, at least one of the crosslinkers must be capable of donating two radicals, and optionally another crosslinker must be capable of donating only one radical upon double bond opening.

[0100] Polymerization of PBM by addition curing, either alone or in combination with additional components of the hair styling composition of the present invention, can be monitored by standard methods. By way of example, the iodine value of the composition is expected to decrease as double bonds open and crosslink with other monomers or suitable components. Thus, the formation of synthetic polymers in the inner portion of the hair fiber with any particular composition of the present invention can be tracked by determining the iodine value of the composition before application and curing, compared to the iodine value of the material extracted from the hair fiber after penetration into the hair fiber and curing. The material, including the synthetic inner polymer, can be extracted from the hair fiber by diffusion (e.g., by immersing the hair sample in a suitable extraction liquid such as water and / or IPA at 40-70°C for 2-12 hours) and concentrated to obtain a sample that complies with the test method. Iodine value can be measured by standard methods such as those described in ASTM D-1959.

[0101] Although compositions and methods according to the present teachings can be applied and practiced on hair fibers (e.g., on fur or wigs) isolated from a living subject, they are typically intended for application to the hair of a living mammalian subject, particularly the human scalp. Thus, in compositions capable of satisfactorily modifying the shape of hair fibers, numerous crosslinkers, cure accelerators or other agents and additives can be used, as detailed below, but all such ingredients, as well as the PBM, are preferably cosmetically acceptable. An ingredient, composition, or formulation made therefrom is considered "cosmetically acceptable" if it is suitable for use in contact with keratinous fibers, particularly human hair, without undue toxicity, instability, allergic reactions, etc. Some ingredients may be "cosmetically acceptable" if present at relatively low concentrations in accordance with relevant legislation.

[0102] When the intended hair styling composition is a single-phase composition, they are achieved when the PBM is dissolved in a continuous aqueous phase containing at least one water-soluble hygroscopic agent and a suitable co-solvent.When the intended hair styling composition is an oil-in-water emulsion, they are achieved when the PBM is emulsified as oil droplets in a continuous aqueous phase that also contains a water-soluble hygroscopic agent and may optionally further contain a suitable co-solvent.The cure accelerator, if present, must be miscible with the monomer while in the hair fiber, regardless of the phase in which they may be delivered to the hair follicle.

[0103] In some embodiments, the aqueous phase of the curable hair styling composition has a pH suitable for a) providing a suitable charge to the hair fiber and in particular the composition comprising the PBM, b) providing a suitable solubility (or conversely, lack thereof) of the compound in the medium, and / or c) providing a suitable opening of the hair scales to facilitate penetration. In some embodiments, the aqueous phase of the curable hair styling composition has an alkaline pH, although an acidic pH (e.g., in the range of about 1 to 3.5) may also enable such an effect. The choice of a non-neutral pH relative to the others may depend on the chemical nature of the monomers and cure accelerators, some of which are inherently attributable to an acidic or basic pH, and some of which are at one pH more than the other.

[0104] It should be noted that in some embodiments, the WHA of the present composition, when added at low concentrations (e.g., 1 wt% or less relative to the weight of the composition), does not substantially interfere with the pH of the composition. At such concentrations, the pH of the hair styling composition is typically similar in the presence or absence of the WHA(s) as such compounds reduce the pH or increase the pH by half a log or less. By way of illustration, if a hair styling composition has a pH of 7.5 without the WHA(s), the addition of at most 1 wt% of a moisture absorbent may adjust the pH to a value in the range of pH 7 to pH 8, with the change in pH being, in some embodiments, 0.4-log or less, 0.3-log or less, 0.2-log or less, or 0.1-log or less. Returning to the figure, a composition having a pH of 7.5 without the WHA(s) may have a pH in the range of 7.1 to 7.9, 7.2 to 7.8, 7.3 to 7.7, or 7.4 to 7.6, respectively, in the presence of such low concentrations of the WHA(s). However, this is not required, as some WHAs may advantageously contribute to achieving a desired pH for the composition (e.g. adapted to promote opening of hair scales and / or promote penetration of the hair) even at low concentrations, while other WHAs may have such a pH adjusting effect at the concentrations in which they are present.

[0105] The pH of the hair styling composition of the present invention can be adjusted to have any desired non-neutral pH, in particular to lift the hair scales and facilitate penetration of the monomers, but such mechanisms do not exclude the existence of additional methods of introducing the monomers into the fiber cortex. For example, monomers and agents necessary for their polymerization or for protection of the resulting polymer (or its effects) may still be sufficiently polar to diffuse through the hair scales, whether or not they are sufficiently open for direct transfer between the hair environment and its cortex.

[0106] Regardless of the form of the styling composition, and without being bound by theory, it is believed that the alkaline pH contributes to charging the surface of the hair fiber (due to chargeable groups, such as carboxyl groups, generally present on the fiber), in particular opening the scales of the hair cuticle, and thus allowing better penetration of monomers into the hair shaft. The alkaline pH also contributes to the charging of the hair styling composition, increasing the zeta potential difference (Δζ) between the hair and the composition, resulting in a higher gradient between the two and facilitating the migration of composition ingredients into the hair fiber for better contact.

[0107] In some embodiments, the hair styling composition (e.g., an oil-in-water emulsion) has a pH of at least 7, at least 8, at least 8.5, at least 9, at least 9.5, or at least 10. Typically, the pH of the composition does not exceed pH 11. In certain embodiments, the pH of the composition is 7-9, 7.5-9, 8-10.5, 9-10.5, or 9.5-10.5.

[0108] Such an alkaline pH of the hair styling composition can be achieved by dispersing or dissolving the oil phase in which the PBM is present in the aqueous phase at a suitable pH (e.g., to form an emulsion or single phase, respectively). The pH of the aqueous phase can be adjusted by using any suitable pH adjuster at any concentration adapted to maintain the desired pH. Such agents include bases such as ammonium hydroxide, sodium hydroxide, lithium hydroxide, or potassium hydroxide. The pH adjuster may also be an amine such as monoethanol-amine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, 2-amino-2-methyl-1-propanol, cocamide monoethanol-an, aminomethylpropanol, or oleylamine. Alternatively or additionally, other components of the hair styling composition that are basic in nature may provide or contribute to the alkaline pH of the composition (e.g., emulsion). For example, crosslinkers commercialized as "Dynasylan® AMEO" and "Dynasylan® SIVO 210" have such an effect in view of their amine groups.

[0109] Conversely, an acidic pH of 4.5 or less, 4 or less, or 3 or less can also contribute to the opening of hair scales. Typically, the pH of a hair styling composition having such an acidic pH is at least 1, at least 1.5, or at least 2, and generally 1-4, 1-3, 1-3.5, 2-4, or 2-3.5. Such an acidic pH can be achieved using an acid as a pH adjuster, which can be selected from acetic acid, perchloric acid, and sulfuric acid, to name a few. Alternatively, or in addition, other components of the hair styling composition that are acidic in nature may provide or contribute to the acidic pH of the composition (e.g., emulsion). For example, crosslinkers known as triethoxysilylpropylmaleic acid and trihydroxysilylethylphenylsulfonic acid have such an effect in terms of their respective acidic groups.

[0110] As illustrated above, many compounds present in a composition can contribute to any of its specific properties or functions.Whether they are dedicated to their purpose as their primary role or contribute essentially to achieving it, the properties desired for the composition are generally monitored in equilibrium.As an example, if it is desired that a hair styling composition according to the present teachings has a pH, polarity, charge, or any other property of interest within a certain range, such properties can be determined at any time after the composition is prepared 12 hours (even if similar values ​​can be obtained at the time the composition is prepared).

[0111] The aqueous phase in either the continuous phase or the oil-in-water emulsion in which the PBM is dissolved to produce a single-phase composition further comprises at least one water-soluble hygroscopic agent (WHA). Such hygroscopic agent is dissolved in the aqueous phase and is believed to penetrate into the hair fiber together with the components of the hair styling composition that allow polymerization, and is believed to settle in the interstices of the crosslinked PBM network formed in the hair fiber. When water is removed (e.g., during application of thermal energy), the hygroscopic agent crystallizes, so that the formed polymer network contains crystals of the hygroscopic agent entangled therein or forms separate crystal bodies. It is believed that the hygroscopic agent's crystallized state enhances its water absorption capacity and thus enhances its ability to sequester and remove any water molecules (e.g., from the ambient air humidity) that penetrate into the hair fiber, thereby allowing the styling of the hair to last longer. Conversely, the crystallized WHA can also function as an internal reservoir of water molecules that can also undergo desorption of water molecules under appropriate conditions, for example, in the method of restyling or de-styling hair fibers that have been pre-treated and styled with the composition.

[0112] Moisture absorbents suitable for the purposes of the present invention are soluble in water, with a solubility in pure deionized water at a pH of about 7.0 of more than 5 wt%, more typically more than 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, by weight of water. In some embodiments, the WHA is highly soluble, with a solubility of 15 wt% or more, 20 wt% or more, or 30 wt% or more by weight of deionized water. In some embodiments, the WHA has a similar solubility by weight of the aqueous environment to be treated at the pH of the liquid. By way of example, the WHA should have a solubility of more than 5 wt% by weight of the hair styling composition (in the case of a single aqueous phase) or in the aqueous phase of the composition (in the case of an emulsion), as well as by weight of pure water. Unless otherwise noted, all values ​​are measured at room temperature under atmospheric pressure.

[0113] In some embodiments, the WHA is highly soluble in water and can have a solubility of up to 150wt%, up to 125wt%, up to 100wt%, or up to 75wt% by weight of water. In other words, up to 150wt, up to 125wt, up to 100wt, or up to 75wt% of the WHA dissolves in 100wt of water. It is emphasized that the solubility of the WHA by weight of the liquid is not synonymous with the concentration of the WHA in the liquid containing the WHA. As an example, assuming that the WHA and water are the only components of the mixture, the concentration of the WHA with a solubility of up to 150wt% by weight of pure water can be up to 60wt% by weight of the aqueous mixture, and this relative concentration of the WHA will further decrease as other components (e.g., PBM) are added to form a complete hair styling composition. The solubility may be the same or slightly lower in an aqueous phase containing all water-miscible materials other than the WHA, which in some embodiments has a solubility of up to 140 wt%, up to 110 wt%, up to 80 wt%, or up to 50 wt%, based on the weight of the composition or its aqueous phase.

[0114] The hygroscopic agents used in the present compositions can be liquid at room temperature, but are advantageously solid to further enhance their persistence within the hair fiber. Thus, in some embodiments, at least one WHA has a melting temperature T m In certain embodiments, the T m is higher than body temperature or, under extreme conditions, higher than external temperature, since it is undesirable for the WHA to liquefy within the hair fibre in contact with the scalp and potentially leach out of the fibre. Thus, the WHA is preferably at a temperature of T m is 37° C. or higher, 40° C. or higher, 45° C. or higher, or 50° C. or higher. m is less than about 250°C, less than about 200°C, less than about 180°C, or less than about 160°C.

[0115] Additionally, the WHA(s) should have a boiling point T higher than the boiling point of water so that when the hair fiber is treated to remove water (e.g., when the hair is dried), the WHA will not evaporate easily. b In some embodiments, at least one WHA can be selected to have T b is 100° C. or more, 120° C. or more, or 140° C. or more. In some embodiments, the WHA has a T b is 300°C or less, 250°C or less, or 225°C or less. m , T b ) are typically provided by the manufacturer, but can be readily determined by standard techniques such as differential thermal analysis (DTA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), etc., as described in ASTM E794-06 or ASTM 3418.

[0116] For similar reasons (e.g., to increase the likelihood of the WHA remaining in the hair fiber for an extended period of time), the WHA(s) can be selected to have a vapor pressure lower than that of water (i.e., less than 2.3 kPa). In some embodiments, the WHA has a vapor pressure of 1.0 kPa or less, 0.5 kPa or less, 0.1 kPa or less, 10 Pascals (Pa) or less, or 1 Pa or less, measured at 25° C. In some embodiments, the WHA has a vapor pressure of 1 milliPascal (mPa) or more, 10 mPa or more, or 50 mPa or more, measured at 25° C. The vapor pressure of a material is typically provided by its manufacturer, but can be readily determined by standard methods, for example using DTA or DSC, as described, for example, in ASTM E1194, ASTM D2879, or ASTM E1782.

[0117] In order to give the moisture absorbent an advantage in the competition with other compounds for binding 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 between water molecules (in pure water). In some embodiments, at least one WHA has a hydrogen bond energy with water molecules 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 embodiments, at least one 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 bond energy of a material can be obtained from the literature or can be estimated by empirical or semi-empirical approaches, such as computer simulations known from density functional theory (DFT) calculations. Experimental studies showing the formation and relative strength of hydrogen bonds in various hydrogen-bonding complexes are generally based on spectroscopy such as infrared (IR), nuclear magnetic resonance (NMR), microwave, electronic and Raman spectroscopy, and crystallography. For example, the hydrogen bond energy between an amine group (as found in WHA) and water has been reported to be about 29 kJ / mol, while the hydrogen bond energy of a water molecule in pure water is about 21 kJ / mol.

[0118] It is desirable that the moisture absorbing agent does not substantially affect or modify the charge of the composition, and therefore non-ionic or non-electrolyte WHA is preferred.However, ionic moisture absorbing agents can be used to promote the transfer and retention of the composition on the surface of hair fiber, as long as they are present in an amount such that the zeta potential of the hair styling composition is sufficiently different from the zeta potential of hair.The effect of delta zeta potential on hair styling, particularly the relatively high absolute value that is expected to allow relatively large penetration of PBM and WHA, and relatively long-lasting styling effect, is described in more detail below.

[0119] It is further desired that the moisture absorbent used in the composition (as well as any other materials deemed appropriate) does not substantially adversely affect the stability of the dispersion, such as by not adversely affecting the size and / or size distribution of the emulsion droplets, which may lead to the collapse of the emulsion (e.g., phase separation). When the composition is an emulsion, it can have oil droplets that do not exceed a few micrometers (e.g., D90≦20 μm and / or D50≦10 μm, 5 μm, 2 μm, or 1 μm, and parameters such as D10, D50, and D90 can be measured by diffractive light scattering (DLS)).

[0120] In some embodiments, the water soluble moisture absorbent is selected from the group consisting of: amides (e.g., carboxamides, including aliphatic amides and amino acid amides); monosaccharides (e.g., glucose, fructose, galactose, or mannose); disaccharides (e.g., sucrose or lactose); and combinations thereof.

[0121] In one embodiment, WHA is a carboxamide having the general formula RC(=O)NR'R'', where R, R', and R'' each independently represent an organic group or a hydrogen atom. In some embodiments, R can include a second carboxamide group. For example, methanamide (also called formamide) and urea are carboxamides, where R is H or NH, respectively. 2 and R' and R'' are both hydrogen atoms. R, R', and R'' are generally relatively short molecular structures, such as short linear, branched, or cyclic, substituted or unsubstituted, saturated alkyls having 1 to 6 carbon atoms. 1 ~C 6 Carboxamides that are alkyl and where R'=R''=H include: a) ethanamide (also called acetamide) (R=CH 3 ), propanamide (R=CH 2 CH 3 ) and butanamide (R=CH 2 CH 2 CH 3 );b) Examples of short cyclic alkyls include cyclopropanecarboxamide, cyclobutanecarboxamide, cyclopentanecarboxamide, and cyclohexanecarboxamide; and c) Examples of diamides include ethanediamide (also known as oxamide), propanediamide (also known as malonamide), butanediamide, pentanediamide, and hexanediamide. Carboxamides with two or more amine groups, such as urea, can be related to amino acids, and such carboxamides are often referred to as amino acid amides. This group of WHA compounds includes alaninamide, asparagineamide, glutamineamide, glycineamide, and prolineamide. In a particular embodiment, the WHA is urea.

[0122] Single-phase compositions and oil-in-water emulsions generally differ from one another by the relative amounts of water and co-solvent that each may contain, and each type is discussed separately below. Note that the relative amounts of water and co-solvent suitable for a particular type of composition also depend on the monomers, cure accelerators, co-polymerization agents, WHAs, or other additives, and their respective amounts, so there may be overlap in the ranges of concentrations suitable for each type of composition.

[0123] In some embodiments, the concentration of water in the single-phase composition is at least 2 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, or at least 20 wt%, based on the weight of the single-phase composition. In some embodiments, the concentration of water is at most 80 wt%, at most 60 wt%, at most 40 wt%, at most 35 wt%, or at most 30 wt%, based on the weight of the single-phase composition. In certain embodiments, the concentration of water is 2-80 wt%, 2-60 wt%, 2-20 wt%, 2-15 wt%, 10-40 wt%, 10-30 wt%, or 15-40 wt%, based on the weight of the single-phase composition.

[0124] In some embodiments, the concentration of water in the oil-in-water emulsion is at least 40 wt%, at least 45 wt%, or at least 50 wt%, based on the weight of the oil-in-water emulsion. In some embodiments, the concentration of water is at most 70 wt%, at most 65 wt%, or at most 60 wt%, based on the weight of the oil-in-water emulsion. In certain embodiments, the concentration of water is 40-70 wt%, 40-65 wt%, or 45-65 wt%, based on the weight of the oil-in-water emulsion.

[0125] In some embodiments, the concentration of the water soluble hygroscopic agent in the oil-in-water emulsion is at least 10 wt%, at least 12.5 wt%, at least 15 wt%, at least 17.5 wt%, or at least 20 wt%, based on the weight of the oil-in-water emulsion. In some embodiments, 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%, based on the weight of the oil-in-water emulsion. In other embodiments, the concentration of the WHA in the oil-in-water emulsion is 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%.

[0126] Water does not have to be the only "liquid carrier" of the composition, and in some embodiments, the hair styling composition can further contain at least one co-solvent. The at least one co-solvent is a C 1 -based ester having at least one hydroxyl group. 1 ~C 10 Alcohols 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, benzyl alcohol, or dimethyl isosorbide; water-miscible ethers such as di(propylene glycol) methyl ether, diethylene glycol monoethyl ether, dioxane, dioxolane, or 1-methoxy-2-propanol; aprotic solvents such as ketones (methyl ethyl ketone, acetone, etc.), dimethyl sulfoxide, acetonitrile, n-methylpyrrolidone, dimethyl carbonate, dimethylformamide; esters such as benzoic acid C 12 ~ 15alkyl; and mineral or vegetable oils, such as isoparaffin fluids, olive oil, coconut oil, or sunflower oil. In a particular embodiment, the co-solvent is isopropyl alcohol. Without wishing to be bound by a particular theory, it is believed that the oil-based co-solvent (e.g., benzoic acid C 12~15 The alkyl group can also contribute to the hydrophobicity of the final composition.

[0127] As those skilled in the art can easily understand, some of these cosolvents can be mixed with the PBM of the oil phase, with the water phase, or with both, in the preparation of a different phase emulsion, or in the preparation of a single phase in which the oil phase is dissolved in the aqueous cosolvent phase. Thus, when referring to the total concentration of the cosolvents below, many situations are included: a) when a single cosolvent is used and mixed with either the PBM or the water phase; b) when a single cosolvent is used and mixed with both the PBM and the water phase; and c) when two or more cosolvents are used and mixed with at least one of the PBM and the water phase. Without wishing to be bound by a particular theory, it is believed that the cosolvent improves the surface tension of the oil phase, particularly to facilitate the penetration of the PBM, and / or increases the miscibility of the crosslinker, if any, in the PBM, and / or increases the miscibility of the PBM in the water phase to form a single-phase composition.

[0128] In some embodiments, the total concentration of the cosolvents in the single-phase composition is at least 20 wt%, at least 30 wt%, at least 40 wt%, or at least 50 wt%, based on the weight of the single-phase composition. The maximum dosage of the cosolvents may depend on the PBM selected and the presence of additional components. In any case, the concentration of the cosolvents is such that the composition is in the form of a single-phase composition. In some embodiments, the total concentration of these cosolvents is at most 80 wt%, at most 75 wt%, or at most 70 wt%, based on the weight of the single-phase composition. In certain embodiments, the total concentration of the cosolvents is 20-70 wt%, 30-70 wt%, or 35-65 wt%, based on the weight of the single-phase composition.

[0129] In some embodiments, the total concentration of the cosolvents in the oil-in-water emulsion is at least 1 wt%, at least 3 wt%, at least 5 wt%, or at least 7 wt%, based on the weight of the oil-in-water emulsion. The maximum dose of the cosolvents may depend on the PBM selected and the presence of additional ingredients. In any case, the concentration of the cosolvents is such that the composition is in the form of an emulsion. In some embodiments, the total concentration of the cosolvents is at most 20 wt%, at most 18 wt%, or at most 15 wt%, based on the weight of the oil-in-water emulsion. In certain embodiments, the total concentration of the cosolvents is 1-20 wt%, 5-18 wt%, or 7-15 wt%, based on the weight of the oil-in-water emulsion.

[0130] The single-phase composition and the oil-in-water emulsion can be prepared by any suitable method. For example, the composition of the present invention can be prepared by mixing a first mixture containing the PBM(s) and thus a predominant portion of the oil phase with a second liquid containing a predominant portion of the aqueous phase in which the WHA(s) will dissolve. Each of these separate sub-compositions forming the "PBM compartment" and the "aqueous compartment", respectively, containing any desired additives, are said to contain a predominant portion of either of the two phases, since it cannot be excluded that some of the compounds of the oil-in-water emulsion may actually partially migrate between the two phases. For example, considering the polymerizable sub-composition, the PBM may be prepared in the presence of a co-solvent (or any other component of the emulsion) that shows some miscibility with water, which may be slightly miscible with water and / or may partially merge with the aqueous phase when mixed predominantly with the aqueous sub-composition. When the two phases are mixed, if one dissolves in the other, a single-phase composition is obtained, not an emulsion.

[0131] When the oil-in-water emulsion is prepared by mixing a PBM compartment with an aqueous compartment containing a WHA, the amount of each component can be suitable to achieve the desired concentration in the final oil-in-water emulsion when the two compartments are mixed in a set ratio. By way of example, in some embodiments, the combined concentration of all PBMs (if more than one) in the PBM compartment is at least 2 wt%, at least 4 wt%, or at least 6 wt%, based on the weight of the PBM compartment. In some embodiments, the concentration of PBM is at most 40 wt%, at most 35 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 13 wt%, or at most 12 wt%, based on the weight of the PBM compartment. In certain embodiments, the concentration of PBM is 2-40 wt%, 2-35 wt%, 2-30 wt%, 2-25 wt%, 2-20 wt%, 2-15 wt%, 4-13 wt%, or 6-12 wt% based on the weight of the PBM compartment.

[0132] Since single-phase compositions and oil-in-water emulsions according to the present teachings can be prepared by any additional suitable method other than dissolving or emulsifying a mixture of a PBM compartment and an aqueous compartment containing a WHA, the concentration of PBM is alternatively provided by weight of the total / final composition (e.g., single-phase or emulsion).

[0133] In some embodiments, the total concentration of PBMs (if two or more) in the hair styling composition (e.g., oil-in-water emulsion) is at least 0.1 wt%, at least 0.15 wt%, at least 0.2 wt%, or at least 0.25 wt%, based on the total weight of the composition. In some embodiments, the concentration of PBMs is at most 5 wt%, at most 3 wt%, or at most 2 wt%, based on the weight of the hair styling composition. In certain embodiments, the concentration of PBMs is 0.1-5 wt%, 0.15-3 wt%, or 0.2-2 wt%, based on the weight of the hair styling composition.

[0134] In some embodiments, the PBM is maintained in an inert atmosphere, such as under argon or nitrogen, to reduce or eliminate environmental factors (e.g., oxygen) that can induce premature and undesirable polymerization.

[0135] In some embodiments, the total concentration of the crosslinking agent (if two or more) present in the hair styling composition is at most 5 wt%, at most 2.5 wt%, or at most 2 wt%, based on the total weight of the composition (e.g., oil-in-water emulsion). In some embodiments, the total concentration of the crosslinking agent is at least 0.001 wt%, at least 0.005 wt%, at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, or at least 0.2 wt%, based on the total weight of the composition. In certain embodiments, the crosslinking agent is present in a total concentration of 0.001-5 wt%, 0.005-5 wt%, 0.01-5 wt%, 0.05-5 wt%, 0.01-2.5 wt%, 0.05-2 wt%, 0.1-2.5 wt%, or 0.2-2 wt%, based on the total weight of the composition. When considering the weight per weight ratio of the PBM(s) and their crosslinkers, this ratio can be 1:15 to 10:1, 1:15 to 7.5:1, 1:15 to 5:1, 1:10 to 2.5:1, 1:10 to 2.5:1, or 1:5 to 5:1.

[0136] If it is desired for the composition to form a polymer network with a relatively low crosslink density to obtain a polymer backbone with thermoplastic behavior, a relatively low concentration of crosslinking agent can be used. In such cases, the crosslinking agent can be present in a total concentration of 0.001 wt% to 0.5 wt%, 0.05 wt% to 0.3 wt%, or 0.07 wt% to 0.2 wt%, based on the total weight of the composition. When considering the weight-per-weight ratio of the PBM(s) and their crosslinking agent, a ratio compatible with a relatively low crosslink density can be 10:1 to 2.5:1, or 7.5:1 to 2.5:1.

[0137] When the curing process involves thermal energy, the crosslinking agent is preferably selected to provide curing at a rate slow enough at elevated temperatures relative to ambient temperature and / or at room temperature to prevent or reduce natural curing during storage and / or application of the hair styling composition. The curing temperature of a suitable crosslinking agent need not be too high (e.g., 50°C to 60°C for hair fibers) so that use on live subjects is possible, and both the curing temperature and the curing rate of the crosslinking agent can be selected to provide curing under reasonable conditions.

[0138] In some embodiments, the total concentration of the cure accelerator (if more than one) is at most 50wt%, at most 45wt%, or at most 40wt%, at most 35wt%, at most 30wt%, at most 25wt%, at most 20wt%, at most 15wt%, at most 10wt%, or at most 5wt% based on the weight of the PBM(s), and optionally the cure accelerator is present at at least 0.01wt% of the PBM(s). Considering the amount of cure accelerator relative to the weight of the entire hair styling composition (e.g., oil-in-water emulsion), they are generally present at very low concentrations. In some embodiments, the total concentration of the cure accelerator is at most 5wt%, at most 3wt%, or at most 2wt% based on the weight of the hair styling composition, and optionally the cure accelerator is present at at least 0.001wt% of the hair styling composition.

[0139] When peroxides are used as cure accelerators for addition polymerization, the amount must be carefully considered in terms of their ability to bleach hair. Thus, the amount of peroxide must be sufficient to activate the polymerization, but low enough not to significantly bleach hair.

[0140] In some embodiments, the concentration of cure accelerator present in the hair styling composition (i.e., the combined concentration of crosslinker and cure accelerator, whether used in addition or condensation polymerization) is from 0.001 wt % to 15 wt %, from 0.001 wt % to 10 wt %, from 0.001 wt % to 5 wt %, from 0.05 wt % to 15 wt %, from 0.1 wt % to 10 wt %, or from 0.5 wt % to 5 wt %, based on the total hair styling composition.

[0141] In some embodiments, the single-phase composition or the oil-in-water emulsion may further comprise at least one additive adapted to enhance one or more properties of the hair styling composition. The additives may include, for example, auxiliary polymerization agents, emulsifiers, humectants, thickeners, charge control agents, or other ingredients conventionally included in hair styling compositions (e.g., fragrances).

[0142] In some embodiments, an auxiliary polymerization agent can be added to enhance and promote polymer formation. Such an auxiliary polymerization agent has at least one functional group that increases the concentration of any functional group available for crosslinking, either with the polymerizable group of the PBM or with the functional group(s) of the crosslinker or suitable curing accelerator. It is believed that the higher concentration of functional groups contained in the auxiliary polymerization agent contributes to a higher degree of crosslinking promotion. Considering the presence of at least one functional group, the auxiliary polymerization agent can be bound to the growing polymer network. Preferably, the density of functional groups of the auxiliary polymerization agent should be high enough to allow the use of an auxiliary polymerization agent with a molecular weight of less than 10,000 g / mol, less than 5,000 g / mol, or less than 3,000 g / mol, such a size does not hinder the ability to penetrate the hair shaft.

[0143] The functional groups contained in the auxiliary polymerization agent are hydroxyl group (-OH), carboxyl group (-COOH), amine group (-NH 2), or a carbonyl group (C=O). Suitable co-polymerization agents may also have functional groups such as anhydrides, isocyanates, and isothiocyanates, which can react, for example, with amine crosslinkers. Other suitable co-polymerization agents may have groups that can be further functionalized by other reactants present in the composition, such as double bonds, which can be cleaved (for example, by an amine crosslinker, or alternatively by a Michael addition reaction, or by a PBM that has been "activated" to contain further reactive radicals).

[0144] Exemplary co-polymerization agents may be selected from: shellac, rosin gum, alkyl or aryl substituted maleates and salicylates (e.g., dimethyl maleate, dibutyl maleate, and 2-ethylhexyl salicylate); oily diesters such as sebacic acid esters (e.g., bis(2-ethylhexyl) sebacate); fatty oils having an alkene chain of 16 or more carbon atoms, including terpenes and terpenoids (e.g., squalene and lycopene); fatty amines; (e.g., oleylamine); and non-conjugated unsaturated fatty acids such as arachidonic acid, linoleic acid, and linolenic acid; conjugated fatty acids such as retinoic acid, eleostearic acid, licanic acid, and punicic acid; and triglycerides of fatty acids containing conjugated or non-conjugated double bonds, such as pomegranate seed oil, chia seed oil, perilla seed oil, raspberry seed oil, and kiwi seed oil. Alkenes that may function as co-polymerization agents are distinguished from alkenes that may function as cross-linking agents by having more carbon atoms (e.g., 13 or more) and, in some cases, more double bonds per molecule (e.g., 3 or more). Additionally, co-polymerization agents having unsaturated alkene chains may be characterized by an iodine value of 100 g iodine per 100 g drug or more, with such value usually not exceeding 400.

[0145] Co-polymerization agents with thermoplastic behavior, such as shellac, can assist in the formation of polymer networks with thermoplastic behavior, while co-polymerization agents lacking thermoplastic behavior, such as fatty oils, can assist in the formation of polymer networks with relatively high crosslink density.

[0146] In some embodiments, the co-polymerizers used for the purposes of the present invention are hydrophobic and may also help protect the hair against the penetration of moisture, in addition to enhancing crosslinking within the hair fiber.

[0147] In certain embodiments, the copolymerizing agent is shellac, a natural bioadhesive resin harvested from insect secretions, which has many synthetic chemical equivalents. Generally, refined wax-free shellac has an average molecular weight of about 600-1,000 g / mol, and although its true structure is a mixture of various components and is subject to debate, it is known to contain repeating units of hydroxyl and carboxyl groups along with olefinic and aldehyde functionalities. Shellac can be provided with variable acid numbers up to 150 mg KOH / g, with the acid number typically ranging from 65-90 mg KOH / g, and the hydroxyl number typically ranging from 180-420 mg KOH / g. The acid number of shellac is usually provided by the manufacturer, and it can also be determined by conventional methods, such as acid-base titration, for example, by titrating a known amount of shellac with potassium hydroxide (KOH) base. For example, the acid number is expressed in milligrams of KOH per gram of shellac, following the procedure described in ASTM D664.

[0148] In some embodiments, the total concentration of the co-polymerization agents (if two or more) is from 0.01 wt % to 2 wt %, from 0.05 wt % to 2 wt %, from 0.1 wt % to 1.7 wt %, or from 0.1 wt % to 1.5 wt %, based on the weight of the hair styling composition.

[0149] When the hair styling composition is an oil-in-water emulsion, it may further contain an emulsifier to facilitate the formation of the emulsion and / or to prolong its stability. In some embodiments, the emulsifier is a non-ionic emulsifier, preferably having a hydrophile-lipophile balance (HLB) value of 2-20, 7-18, 10-18, 12-18, 12-17, 12-16, 12-15, or 13-16 on the Griffin scale. Suitable emulsifiers are water-soluble (e.g., having an HLB value of 8-20), such as polysorbates (often commercially available as Tweens), ester derivatives of sorbitan (often commercially available as Span), 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 of 2-8). It should be noted that some components of hair styling compositions selected for other functions can also function as emulsifiers. For example, linoleic acid, which is commonly used as a co-polymerizing agent, can also function as an emulsifier due to its polar head and fatty chain.

[0150] To facilitate the penetration of PBM into hair fibers, the composition must be able to spread adequately on the hair fiber to allow adequate contact. It is expected that the composition will adequately cover the hair fiber upon application, which will facilitate the penetration of monomers into the hair, likely through capillary action, to form a synthetic polymer that can constrain the desired shape. By adjusting the surface tension of the hair styling composition, measured in millinewtons per meter (mN / m), to be lower than the surface energy of the hair fiber, the proper wetting of the surface can theoretically be improved. Such properties can be determined according to standard methods, such as the procedure described in ASTM D1331-14, Method C.

[0151] Native hair fibers that have not been previously treated by any type of hair modification treatment generally have a surface energy of about 25-28 mN / m, while damaged hair generally has a higher surface energy, for example chemically bleached hair fibers have a surface energy in the range of 31-47 mN / m. Among the many differences between damaged and undamaged hair, the high presence of naturally occurring fatty acids in undamaged hair is believed to contribute to the relatively lower surface energy. Considering the above ranges, it can be assumed that adequate wetting will be observed in all hair types when carried out with a composition having a surface tension of less than 25 mN / m. It has been surprisingly found that hair styling compositions with too low a surface tension do not provide the expected results as far as monomer penetration is concerned. Counterintuitively, the inventors have found that compositions with a relatively higher surface tension than would be theoretically appropriate are more suitable for the purposes of the present invention. Without being bound by theory, it is believed that the absence of fatty acids within the hair shaft causes the surface energy experienced within the hair to be significantly higher than the surface energy measurable at the outer surface of the hair, necessitating the selection of a specific range of surface tension for compositions intended to penetrate the hair shaft.

[0152] In some embodiments, the compositions of the present invention have a surface tension of 25-60 mN / m, 25-55 mN / m, 25-50 mN / m, 25-45 mN / m, 25-40 mN / m, 25-35 mN / m, or 30-40 mN / m.

[0153] The compositions of the present invention suitable for natural hair are also suitable for previously treated hair fibers. However, in some embodiments, the styling composition may exhibit a surface tension suitable for adequately covering damaged hair, while not being fully satisfactory for natural hair fibers.

[0154] The wetting agent can be added to the composition at any suitable concentration that can reduce the surface tension to any of the suitable ranges described above. Examples of wetting agents can include silicone-based, fluorine-based, carbon-based, or amine alcohol-based. Silicone-based wetting agents can include silicone acrylates (e.g., SIU100 from Miwon Specialty Chemical Co., Ltd.). Fluorine-based wetting agents can include perfluorosulfonic acids (e.g., perfluorooctane sulfonic acid), or perfluorocarboxylic acids (e.g., perfluorooctanoic acid). Carbon-based wetting agents can include ethoxylated amines and / or fatty acid amides (e.g., cocamide diethanolamine), fatty alcohol ethoxylates (e.g., octaethylene glycol monododecyl ether), fatty acid esters of sorbitol (e.g., sorbitan monolaurate), polysorbates, and alkyl polyglucosides (e.g., lauryl glucoside). Amine functionalized silicones can also be used as wetting agents, such as amodimethicone or bisaminopropyl dimethicone, as well as alkanolamines, such as 2-amino-1-butanol and 2-amino-2-methyl-1-propanol. When wetting agents are added, they are typically present in the hair styling composition (e.g., oil-in-water emulsion) 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%, optionally 0.001-1.5 wt%, 0.01-1.4 wt%, or 0.1-1.3 wt%, based on the weight of the composition.

[0155] Alternatively, or in addition, some of the components present in the hair styling composition to perform different functions may contribute to the surface tension of the hair styling composition.For example, aminopropyltriethoxysilane (e.g., Dynasylan® AMEO), which is a crosslinking agent, can reduce the surface tension of the composition, while linoleic acid, which can be used as an auxiliary polymerization agent and emulsifier, can increase the surface tension of the composition.Therefore, the surface tension of the hair styling composition can be adjusted by selecting the appropriate concentration of such components.In addition to contributing to the type of hair styling composition that can be formed through its chemical formula and relative concentration, co-solvents can also contribute to the wetting ability of the composition on hair fibers.

[0156] In some embodiments, thickeners can be added to the oil-in-water emulsion or aqueous phase of the aqueous compartment, generally, to provide the desired viscosity. The viscosity needs to be low enough so that the composition can be easily applied to the hair to satisfactorily cover all individual hair fibers, but high enough to remain on the hair fiber for a sufficient time and prevent dripping. A relatively low viscosity also facilitates the penetration of the PBM into the hair by diffusion and / or capillary action. Exemplary thickeners include hyaluronic acid, poly(acrylamide-co-diallyl-dimethyl-ammonium chloride) copolymer (Polyquaternium 7, e.g., from Dow Chemicals), quaternized hydroxyethyl cellulose (Polyquaternium 10, e.g., from Dow Chemicals), hydroxypropyl methylcellulose, and the like. When added, thickeners are typically at a concentration of at least 0.1 wt%; at most 10 wt%; and optionally 0.5 wt% to 5 wt% by weight of the aqueous phase or single phase.

[0157] To facilitate migration and / or retention of the PBM to the surface of the hair fiber and then increase its penetration therein, there should preferably be a difference between the zeta potential of the composition and the hair. For example, the zeta potential (or zeta potential) of the hair styling composition at that pH is c) is the zeta potential (or ζ) of mammalian hair fibres at the same pH. h ) is preferably more negative or more positive than the zeta potential. In some cases, the components used in the composition can provide, in addition to other functions, sufficient charging of the composition to achieve such a gradient in zeta potential values. For example, pH adjusters, wetting agents and / or amine-based crosslinkers can contribute to the suitable charging of the oil-in-water emulsion. In some embodiments, agents dedicated to this effect, called charge adjusters, can be added to the composition. To illustrate, water-insoluble non-reactive amino silicone oils can be added to the oil phase of the emulsion to adjust the zeta potential.

[0158] In some embodiments, the zeta potential ζ of the composition c and the hair fiber ζ to be treated. h The difference between the zeta potential of c-h ), which has an absolute value of 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. c-h The absolute value of is in the range of 5-80mV, 10-80mV, 10-70mV, 10-60mV, 15-80mV, 15-70mV, 15-60mV, 20-80mV, 20-70mV, 20-60mV, 25-80mV, 25-70mV, 25-60mV, 30-80mV, 30-70mV, 30-60mV, 35-80mV, 35-70mV, or 35-60mV. Such values ​​are preferred for setting an initial charge gradient that operates towards the hair fiber, particularly for infusing the PBM(s) (e.g., as droplets) with the WHA(s). As can be appreciated, such a gradient decreases over time as the material of the composition initially accumulates on the outer hair surface, changing the zeta potential. This process is self-terminating and transfer of the composition to the hair will stop when the gradient becomes too low (e.g., when the delta zeta potential falls below 5 mV). Zeta potential can be measured by standard methods using any device suitable for measuring the charge of dispersed particles.

[0159] The composition may also contain any other additives conventionally used in cosmetic compositions, such as preservatives, antioxidants, bactericides, fungicides, chelating agents, vitamins and fragrances, or conventionally used in hair styling compositions, such as hair detangling agents and hair conditioning agents, the nature and concentrations of which need not be detailed further herein.

[0160] The composition may contain other optional additives conventional to the form in which the hair styling composition is to be applied, for example a propellant if the composition is to be sprayed, the nature and concentrations of which need not be detailed further herein.

[0161] Mixing and / or emulsification of the materials can be performed by any method known in the art. Although manual shaking is sufficient, a variety of devices can be used, such as vortexes, overhead stirrers, magnetic stirrers, ultrasonic dispersers, high shear homogenizers, sonicators, and planetary centrifugal mills, which typically result in a more uniform composition, e.g., a more uniform population of oil droplets in the aqueous phase of an oil-in-water emulsion.

[0162] In some embodiments, the hair styling composition can be prepared by mixing or emulsifying the contents of the PBM compartment and the aqueous compartment containing the WHA, with this combination occurring immediately after each portion is prepared. However, in another embodiment, the mixing of the two compartments can be withheld. In particular, when the composition contains PBM(s) and at least one hardening accelerator (e.g., crosslinker) that tend to separate into separate phases in the complete final composition, it may be desirable to allow prepolymerization of such materials in the same polymerizable compartment. In some embodiments, the prepolymerization step is performed on a single mixture of PBM(s) and hardening accelerator, and not on the entire contents of the PBM compartment if it contains additional materials that may adversely affect the process or simply slow it down. In other embodiments, the prepolymerization is performed on the PBM(s) alone, before combining with the hardening accelerator or any other components of the PBM compartment. Such prepolymerization can be referred to as "auto-prepolymerization". Without being bound by theory, when the PBM(s) contain unsaturated side chains, such as CNSL, such autoprepolymerization is believed to occur by cleavage of double bonds under appropriate conditions (e.g., elevated temperatures), thereby forming radicals that are available for polymerization with other CNSL molecules via addition polymerization.

[0163] Such prepolymerization, if necessary, with or without the presence of a cure accelerator, must have a sufficiently long time to prevent the monomer and cure accelerator from separating into different phases when mixed with the additives of the PBM compartment and / or with the contents of the aqueous compartment, to the extent that polymerization in the hair fiber after application of the mixed composition is significantly delayed. However, the prepolymerization must be short enough so that any oligomers that may be formed in this process (of the crosslinker itself or the monomer itself, or of the crosslinker and the monomer and other things) remain small enough to penetrate into the hair fiber after application of the composition. It is believed that the prepolymerization consumes the relevant building blocks (e.g., monomer and / or crosslinker) present in the compartment to be prepolymerized, resulting in the formation of oligomers (regardless of composition). This process can be monitored by the increase in viscosity of the prepolymerized mixture of monomer and cure accelerator over time. The prepolymerization step can be carried out at ambient conditions, such as room temperature, but can be further accelerated by any means suitable for inducing and / or enhancing polymerization, such as, for example, heating the mixture. The prepolymerization step can be carried out in an inert atmosphere, such as under argon or nitrogen, to reduce or remove environmental factors (e.g., oxygen) that may interfere with the prepolymerization reaction. The conditions of the prepolymerization, if carried out, may also depend on the type of PBM and the crosslinker selected. In some embodiments, the prepolymerization can be carried out at a temperature of 20°C to 60°C, 25°C to 60°C, 30°C to 60°C, or 40°C to 60°C, or at an elevated temperature, such as 100°C to 150°C or 150°C to 200°C, for 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. Typically, the duration of the prepolymerization will not exceed 24 hours, 18 hours, or 12 hours when carried out at a relatively mild temperature, but can be shortened when carried out at a relatively high temperature (e.g., 150°C to 200°C) requiring less than 8 hours, less than 5 hours, or less than 4 hours.After prepolymerization, additives can optionally be added to the prepolymerized compartment and / or the aqueous compartment can be combined therewith to form a hair styling composition.

[0164] A hair styling composition (e.g., an oil-in-water emulsion) can be easily applied after its preparation or within a period during which it remains suitably stable and effective. For example, in the case of an emulsion, the composition can be applied as long as the oil droplets are within the desired size range (e.g., a few micrometers or less, typically less than 10 μm), provided that the PBM is not fully polymerized in vitro. More generally, a hair styling composition can be used as long as a sufficient amount of PBM is available to at least partially penetrate and polymerize the hair fiber therein. In some embodiments, a single-phase composition or emulsion is applied to the hair fiber within at most 30 minutes, or within at most 20 minutes, within at most 10 minutes, or within at most 5 minutes of its dissolution or emulsification.

[0165] In some embodiments, the hair fiber can be pre-treated prior to application of the hair styling composition, either as a single phase composition or as an oil-in-water emulsion.

[0166] A typical pretreatment that can be carried out before applying the hair styling composition is a pre-washing treatment to cleanse the hair fibres, removing any residues that may be present on the hair, such as dirt or grease from hair products, by applying any suitable cleansing agent, such as sodium lauryl sulfate, and rinsing the hair fibres with excess water after this cleaning.

[0167] Another pre-treatment, which can be performed after washing or independently, is a pre-drying treatment to remove rinse water or residual moisture from the hair. This removal of water molecules from the hair fiber is generally achieved by heating the hair, which is believed to break hydrogen bonds that may have formed either on the surface of the hair cuticle and / or within the hair shaft.

[0168] As used herein, unless otherwise clear from the context or stated otherwise, the term "residual moisture" refers to the water present in relation to the hair fiber either on the outer surface of the scales of the hair cuticle, between and / or under the scales (i.e., in the cortex or medulla) from hair exposed to moisture (e.g., as a result of ambient humidity or wetting of the hair). Of course, complete removal of residual moisture is very difficult to achieve, since hair is constantly exposed to ambient humidity and humidity is almost never zero. Nevertheless, low levels of residual moisture are achievable or temporarily achievable by applying mainly thermal (i.e., heating) energy to the hair. Sufficient heat to achieve a slight level of residual moisture can be applied to the hair by any conventional method, for example, by using a hair dryer or a flat or curling iron for a sufficient time. Regardless of the method used to reduce the amount of water molecules in the hair, such a process can alternatively be called a drying treatment or drying process.

[0169] When considering hair with at least a wavy appearance, the hydrogen bonds are sufficiently broken by the drying pretreatment, which can be easily visually evaluated, since sufficient drying temporarily reduces the waves, and the hair fiber is completely flattened at the end of such a step, if desired. Alternatively, as in the case of straight hair, the duration of the drying pretreatment can be arbitrarily set as a function of the drying equipment used and the temperature that can be applied to the hair fiber. For example, a flat or curling iron that can be applied directly to the hair with a heat transfer temperature of about 200°C can sufficiently break the hydrogen bonds within a few minutes, while a conventional hair dryer may apply a relatively low temperature by heat transfer depending on the distance from the hair used, and a relatively long drying period will be required. Typically, the drying of the hair fiber can be performed by heating an area of ​​the hair fiber 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 at a time, and such a drying treatment can take up to 5 minutes for a tuft if the heating proceeds from one end of the tuft to the other.

[0170] In some embodiments, the residual moisture level after such drying treatment (if performed) and / or before application of the composition is at most 5 wt%, at most 4 wt%, at most 3 wt%, at most 2 wt%, or at most 1 wt% by weight of the hair fiber. Such amounts can be determined by standard methods, for example using thermogravimetric analysis or near infrared techniques such as photothermal transient emission radiometry.

[0171] Alternatively, or in addition, heating that may contribute inter alia to the cleavage of hydrogen bonds within the keratin polymers and / or materials in which the hair styling composition has penetrated the hair fiber is: a) heating optionally applied during application of the composition (e.g., the composition is heated before application); b) heating optionally applied during incubation of the composition on the hair fiber; and / or c) heating applied during styling of the hair fiber after application of the composition. Regardless of its effect on hydrogen bonds, heating accelerates the rate of diffusion of monomers / oligomers and / or hardening of the polymer, if any, within the hair fiber.

[0172] A third possible pretreatment (which can be carried out after washing and / or drying or independently) involves the application of a pretreatment composition intended to remain on the hair fibre during the performance of the hair styling method. The hair pretreatment composition can protect the hair fibre during the application of the hair styling composition, in particular during the application of heat, can facilitate the performance of the steps of the method and / or can enhance the properties of the hair styling composition.

[0173] Hair pretreatment compositions should not impair the effects sought by the compositions and methods of the present invention, such as not interfering with the opening of the hair cuticle, the transfer of the styling composition to the hair surface, the penetration of the styling composition into the hair shaft, the polymerization of the PBM(s) or the desired activity of the WHA(s), and any similar effects.

[0174] Generally, hair pretreatment compositions consist of oils that can be applied to the hair fibers to form a very thin oily layer on the surface of the fibers prior to treatment with the hair styling composition.

[0175] In some embodiments, the oil used in the pretreatment step or in the hair pretreatment composition has a solubility in water of 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, or 1 wt.% or less, by weight of water measured at a temperature of 25° C.

[0176] The factors that make a hair pretreatment composition suitable for the method of the present invention overlap some of the characteristics already described for hair styling compositions and will only be briefly discussed.

[0177] First, the hair pretreatment composition (which may also be called a pretreatment oil) must adequately wet the hair fiber. To do so, the pretreatment composition or the oil therein should have a surface tension lower than the surface energy of the hair fiber. In some embodiments, the pretreatment composition or oil has a surface tension of 35 mN / m or less, 30 mN / m or less, or 25 mN / m or less.

[0178] Second, if desired, the hair pretreatment composition or oil in the composition should be essentially non-volatile during the process in order to remain on the hair fiber and not evaporate during the application of energy. Thus, in some embodiments, the pretreatment oil has a vapor pressure of less than 40 Pa, less than 35 Pa, or less than 30 Pa. In other embodiments, the oil has a vapor pressure of more than 0.1 Pa, more than 0.2 Pa, or more than 0.5 Pa. In some embodiments, the pretreatment oil has a vapor pressure of 0.1 Pa to 40 Pa, 0.2 Pa to 35 Pa, or 0.5 Pa to 30 Pa. The vapor pressure of the oil is measured at a temperature of 25°C.

[0179] In order to facilitate coverage of the hair fiber with the desired hair pretreatment composition, the electrostatic attraction between the two can be promoted, and the hair pretreatment composition (e.g., oil pretreatment) preferably has a zeta potential (ζ h ) and the zeta potential (ζ o The pretreatment composition has a ζ o Also, the zeta potential (ζ) of the styling composition is important, particularly to allow attraction of the PBM to the oil pretreatment layer formed on the hair fiber. c ) between the pretreatment composition and the hair. Thus, in some embodiments, the delta zeta potential (Δζ o-h ) and the delta zeta potential (Δζ c-o ) is 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 (all absolute values). o-h and Δζ c-oThe absolute value of 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.

[0180] Since the material that preferentially penetrates the hair shaft is preferably one that participates in or promotes the in situ polymerization of PBM(s), it may be beneficial to select a hair pretreatment composition that is substantially incapable of penetrating hair.Thus, in some embodiments, the pretreatment oil has a hair penetration capacity measured as a weight gain of at most 5 wt%, at most 4 wt%, at most 3 wt%, at most 2 wt%, or at most 1 wt%, based on the weight of the hair fiber.Regardless of its ability to penetrate hair fibers, the hair pretreatment composition must not adversely affect the desired activity of the hair styling composition (e.g., must not interfere with its polymerization, as can be tested in vitro).

[0181] Hair pretreatment compositions may provide various beneficial effects, but in some embodiments of the present invention, one such benefit is provided by selecting a pretreatment oil that is incompatible with the hair styling composition in terms of miscibility. For example, the miscibility of the oil is, for example, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, or 1 wt% or less, based on the weight of the hair styling composition measured at a temperature of 25°C. In such a case, it is believed that the hair pretreatment composition forms a thin oily layer on the hair surface, onto which excess hydrophobic droplets of the hair styling composition may adhere. Thus, the thin layer of the pretreatment agent allows the penetration of the ingredients of the styling composition, while its presence facilitates the removal of the portion of the hair styling composition that did not penetrate into the hair fiber. The excess styling composition can be removed together with the layer of pretreatment oil, for example, by washing or wiping the hair. In such cases, the pre-treatment oil may improve the look, feel, and / or combability of the hair fibers at an earlier stage compared to hair fibers treated with the same hair styling composition in the absence of the pre-treatment oil.

[0182] In some embodiments, the pretreatment composition is an oil selected from silicone oils.

[0183] Whether or not any one of the aforementioned optional pretreatment steps has been previously performed, the hair styling composition (e.g., oil-in-water emulsion) is applied to the hair fiber and generally maintained on the hair for at least 5 minutes to allow the scales of the hair cuticle to swell and open, thus allowing at least a portion of the PBM, WHA and hardening accelerator (if present) to reach the hair shaft. To facilitate penetration into the cortex, the molecules involved in or promoting internal polymerization or protecting the resulting effect of the polymer (e.g., PBM, hardening accelerator, WHA, co-solvent) preferably have a molecular diameter of less than 2 nm, less than 1.8 nm, or less than 1.6 nm. The inventors believe that within the hair shaft, the monomers can bind to at least a portion of the hydrogen bonds of the hair fiber, thereby preventing the hair fiber from reforming to its previous natural state when exposed to water. The PBM may also, or instead, polymerize without binding to previously broken hydrogen bonds. Regardless of the mechanism of action, the polymer resulting from hardening of the monomers impregnated into the hair fiber can constrain the hair fiber into a new shape. It is believed that the curable composition of the present invention prevents or reduces the access of water (ambient water or water applied when wet) to the hair, thereby reducing or delaying the ability of hydrogen bonds to form again and delaying the ability of hair to return to its natural shape. The WHA can further contribute to water sequestration or other interactions that promote the desired effect of the polymer on styling. Regardless of the mechanism of action of the WHA on the hair styling method of the present invention, on the polymer, and on the duration of its effect on styling, the WHA is conveniently said to provide a protective or lengthening effect. For simplicity, the method is described in terms of disrupting the severing of hydrogen bonds and the severing of the bonds by binding to PBM or other components that may subsequently polymerize or interact with hair components, but this is not meant to exclude further reasons underlying the observed styling effect.

[0184] A sufficient time is provided to ensure that the monomers impregnate the hair fiber and, for example, bond with at least some of the broken hydrogen bonds in the hair fiber. In some embodiments, the composition can be left in contact with or applied to the hair fiber for 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 embodiments, the time that the composition remains applied to the hair fiber, or 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 certain embodiments, the composition is maintained on the hair fiber for a period of 5 minutes to 30 minutes, 10 minutes to 60 minutes, 30 minutes to 12 hours, 30 minutes to 5 hours, 40 minutes to 2 hours, or 50 minutes to 2 hours. It is noted that conventional hair straightening methods may require longer times and may require application for 3 to 4 hours, or even 6 to 8 hours.

[0185] The composition may be applied and maintained on the hair fibers at ambient temperature, although the process may alternatively be carried out at elevated temperatures of at least about 30° C., or at least about 40° C. In some embodiments, the temperature at which the composition may be maintained in contact with the hair fibers is up to about 60° C., up to about 55° C., or up to about 50° C. In certain embodiments, the liquid composition is maintained on the hair fibers at a temperature range of 15° C. to 23° C., 23° C. to 60° C., 25° C. to 55° C., or 25° C. to 50° C.

[0186] After said time, which allows at least a portion of the PBM and WHA of the composition to fully penetrate into the individual hair fibers, the monomers are then at least partially polymerized by the application of energy, optionally in the presence of a cure accelerator, thereby achieving at least a partial cure.

[0187] Upon polymerization of the PBM, the resulting polymer undergoes an increase in glass transition temperature (Tg), as can be more easily assessed in a liquid composition than in hair fibers. In some embodiments, upon full curing, the resulting PBP has a Tg of at least 50°C, at least 100°C, at least 150°C, or at least 200°C. Such a Tg allows the polymerized PBM to remain intact even when exposed to hot weather conditions, washing the hair with hot water (about 45°C), or in an elevated temperature environment, such as a sauna (about 70°C). The synthetic polymer formed in the hair fiber remains unaffected by such conditions or treatments due to its Tg, so the modified shape of the hair achieved using the compositions and methods of the present teachings remains intact.

[0188] In some embodiments, the energy that allows for at least partial curing of the composition (and therefore styling of the hair fiber) is thermal energy applied at a temperature of at least about 80°C, at least about 100°C, at least about 120°C, or at least about 140°C. In some embodiments, the heating temperature is up to 220°C, or up to 200°C. In certain embodiments, the temperature applied to achieve at least partial curing ranges from 80°C to 220°C, 100°C to 220°C, 120°C to 220°C, or 140°C to 200°C. It should be understood that the temperature provided by the heating device to at least partially cure the monomers is generally higher than the temperature sensed by the hair fiber. Given a long enough residence time (the period during which the hair segment is exposed to heat), the temperature of the hair fiber may eventually reach the heating temperature, but this is generally not the case, and the temperature of the hair fiber at which curing can take place is generally at a temperature of at least about 45°C, at least about 50°C, at least about 55°C, or at least about 60°C. To prevent irreversible damage to the hair fiber, the temperature of the hair fiber during the at least partial hardening step is desirably below 180° C., below 140° C., or below 100° C. The at least partial hardening can be performed while styling the hair into a desired shape, for example with a hair dryer, flat iron or curling iron, to modify the natural shape. This step can alternatively be called a styling step, since during this step the hair fiber is dynamically or statically mechanically restrained (for example pulled with a comb or brush, rolled with rollers or contacted with a styling iron) to modify the shape.

[0189] At such temperatures, the time required for at least partial curing is generally short. Typically, areas of individual hair fibers that experience temperatures of 100° C. or higher can result in localized partial polymerization of the PBM within seconds, while hair fibers that reach temperatures as low as about 50° C. may require up to several minutes (e.g., 5 minutes). The time that the hair is heated, and thus needs to experience a particular temperature suitable for curing, can depend on the shape of the hair being modified and the new shape being formed. Relatively mild modifications may require less time than relatively more dramatic shape changes.

[0190] The period of time that the hair fiber should be at the appropriate temperature can be independently tested in vitro by exposing the oil phase of the subject composition, dissolved or emulsified, to the temperature intended for hair treatment and measuring the time it takes for the liquid phase to start to solidify (i.e., harden). When considering a mammalian subject, the amount of time allocated for the partial hardening step (in other words, styling the hair itself) will depend, among other things, on the type of hair, the density and length of the scalp hair, and the device used to deliver heat and its extent. Thus, at the level of the entire scalp of hair, partial hardening may take several minutes, but generally less than an hour. Such considerations apply to any other treatment of hair fibers, and the time periods provided herein generally refer to periods appropriate for any amount of hair fiber that can be treated simultaneously. When the entire scalp of hair is treated in stages by repeating the same treatment on different strands of hair fiber, the period of treatment for the entire scalp can be the sum of the periods according to the actual number of individual repetitions of the simultaneous treatment. For example, if simultaneous treatment of the first strand of hair fibre requires 5 minutes and the entire hair scalp consists of four strands, treatment will be completed in approximately 20 minutes.

[0191] Prior to at least partial curing, optionally, excess liquid composition is removed from the outer surface of the hair fiber by rinsing the hair fiber with a rinsing liquid, thus preventing the formation of a thick coating on the surface of the hair fiber, which would cause the hair to feel sticky and rough. The removal of such coating can be further promoted by applying a suitable pre-treatment composition, such as an oil pre-treatment, as mentioned above. Rinsed hair fibers may also have improved thermal conductivity, accelerating partial curing.

[0192] Alternatively, or in addition, after application of the hair styling composition and its incubation on the hair fiber, and optionally after rinsing, but before hair styling, it is possible to apply a second composition consisting of a cure accelerator to the hair fiber impregnated with PBM. The composition that can be used in this optional step can be called a curable composition. It contains the same cure accelerator selected from the crosslinking agent and cure accelerator previously described for the hair styling composition, and generally, the curable composition consists of a cure accelerator. In contrast to the hair styling composition, the cure accelerator (e.g., cure accelerator) can be present in the curable composition in an excess amount (e.g., 5 wt%) that allows the application of the cure composition to the hair fiber to be relatively short (e.g., 5 minutes to 15 minutes, or less). The curable composition can further serve to rinse the hair fiber in addition to or instead of the rinse.

[0193] After at least partial curing sufficient to achieve the desired modified shape, the hair fiber can optionally be subjected to further curing by application of further energy, preferably heat, to ensure further curing of the composition. Further energy can be applied by using a styling device as described above, for example a hair dryer or a styling iron. In some embodiments, further curing can be carried out at a temperature as described for the at least partial curing of the third step, generally for a time significantly longer than for partial curing. For example, if the hair fiber is treated with a composition that allows at least partial curing at a given temperature in a specific styling device within 20 minutes (established by the fiber throughout the scalp showing the desired modified shape), any additional heating step favoring further curing will be carried out under at least the same conditions for at least 40 minutes. Although partial curing is achieved during the modification of the fiber shape, the step referred to herein as further curing is applied when the hair fiber is in the desired modified shape, so that it is no longer necessary to simultaneously mechanically restrain the fiber to conform to the desired shape. Further curing is expected to increase the degree of polymerization of the PBM within the hair fiber, but is not expected to result in complete curing (eg, after which polymerization no longer occurs).

[0194] In some embodiments, after heat curing (e.g., achieved during the styling step and optional further curing), the hair fiber can be kept without washing to reduce exposure to water, allowing the curing to proceed further, if applicable. The period during which washing of the hair fiber can be avoided can depend on the type of hair, the composition applied thereto, the procedure used to modify the natural shape, the temperature, the relative humidity, the desired modified shape, and the desired duration of said modification. In general, assuming that the hair fiber is maintained at room temperature with a relative humidity of about 40-60 RH%, washing of the hair may be performed at least 18 hours after the end of at least partial curing (e.g., styling including mechanical restraint) or any further curing step (e.g., heating without mechanical restraint). In some cases, washing can be postponed for at least 24 hours, at least 36 hours, or at least 48 hours. Typically, washing of hair styled according to the present method is performed within at most one week of styling. Hair styled according to the present invention is not limited to the use of a specific shampoo to avoid impairing the styling effect, as is often required in conventional methods, and can be washed with any shampoo. However, regular shampoos can be improved by including set accelerators.

[0195] Advantageously, hair treated with the hair styling composition of the present invention and the method according thereto is not only free from current specific care, but the teachings of the present invention can also be suitable for hair fibers that have previously undergone other hair treatments (e.g., bleaching, coloring, styling, etc.). Such conventional treatments generally damage the hair, for example by imposing physical and / or chemical structural changes that may hinder subsequent hair treatments, such as styling by conventional methods (e.g., organic or Japanese). For example, bleached hair may not be effectively straightened by the Japanese method, since the bleaching chemicals affect the hair components required for this method. In contrast, the compositions of the present invention allow hair fibers to be effectively styled, regardless of previous hair treatments that they may have undergone.

[0196] Figures 1A and 1B show FIB-SEM images of hair fibers washed with tap water containing 5% sodium lauryl sulfate to remove residues on the hair, allowing better visualization of the cuticular scales of a reference untreated hair fiber. Figure 1A shows scanning electron microscopy (SEM) and focused ion beam (FIB) images of overlapping cuticular scales 11 performed on a cross section of a hair fiber using a Zeiss Crossbeam340 microscope. The cross section was performed by bombarding the sample with ionized gallium at 30 kV and 100 pA at an angle of 54° from the SEM column, and the images were taken using the SEM column and in-lens detector at a magnification of x20K, a voltage of 1.20 kV, and a working distance of 5 mm. FIG. 1B is another FIB-SEM image of the same hair fiber, but with a working distance of 4.9 mm and a voltage of 10 kV (cuticular scales are not visible at this voltage).

[0197] Figures 2A and 2B show FIB-SEM images taken as described above of a hair fibre treated with an oil-in-water emulsion of the invention (specifically emulsion PU6 prepared as described in Example 3) immediately after styling the hair fibre as described in step 4 of Example 5, i.e. before step 5 of washing the hair fibre. The images were taken at two different voltages, a lower one to enhance the visibility of the cuticle and its contours, and a higher one to enhance the visibility of the composition. The images were taken at the same cross section and therefore can be "overlaid" on each other to combine the information collected at each voltage. Figure 2A was taken at a voltage of 1.20 kV and a working distance of 5 mm, and shows that the cuticles 11 are layered on top of each other, separated by a dark line 21 that may represent the cuticle-cuticle cell membrane complex (CMC). At this voltage, the hardened hair styling composition is not visible. To better illustrate the hair structure, a schematic diagram of Figure 2A is shown in Figure 2A'. Figure 2B is an image of the same hair fibre, but taken at a voltage of 10 kV and a working distance of 4.9 mm, which fades the outline of the hair cuticle but makes the cured composition visible as a light layer 22, indicating that it has penetrated through several layers of the hair cuticle into the hair fibre. Figure 2B' is a schematic depiction of Figure 2B, where the cured composition is shown as sparsely scattered white areas within the hair fibre (itself shown as a shaded area).

[0198] The method of the present invention provides durable hair styling that maintains hair fibers in a desired shape even after the hair is exposed to moisture, whether from atmospheric humidity or after wetting or washing the hair. The styling shape is not affected in a significantly detectable manner even after 5 or more shampoo washes, and hair styling can be maintained for a long period of time. As demonstrated in the examples, in some embodiments, the hair styling composition and method according to the present teachings provide a lasting modification of hair shape, as evidenced by the ability of treated hair to withstand 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.

[0199] Figures 3A and 3B are FIB-SEM images of hair fibres treated by application of emulsion PU6, straightened and then washed with 16 wash cycles. The straightening and washing procedures are described in Examples 4 and 5, respectively. The images were taken as described above. Figure 3A shows a cross section taken at a voltage of 1.20 kV and a working distance of 4.7 mm, while Figure 3B shows the same cross section of a styled hair fibre, the image taken at a voltage of 10 kV and a working distance of 4.6 mm. Figures 3A and 3B show the presence of hardened composition within the hair fibre, even after 16 washes.

[0200] While it cannot be excluded that some of this "wash resistance" is due to a diffuse coating remaining on the outer surface of the fiber, the inventor speculates that such an outer coating tends to wear off relatively quickly with washing, and that the ability to style hair according to the present teachings may be primarily due to the internal polymerization of the PBM. This fugitive diffuse coating is relatively thin, usually not exceeding an initial thickness of 1 μm, and often less than 0.5 μm thick. As such, it is noted that this distinguishes hair fibers treated according to the present teachings against traditional styling methods with a continuous outer coating of a few microns that constrains the fiber in a desired shape. Without wishing to be bound by theory, it is believed that this temporary thin coating of the hair fiber temporarily protects the inner shaft so that the monomers that have penetrated inside further promote hardening and strengthen polymerization, thereby extending the durability of the hair styling. As exemplified below, hair styling according to the present method remains free of the temporary coating. Avoidance of this coating may be facilitated by providing the hair fiber with an oil pretreatment.

[0201] As used herein, a composition that provides a modified shape that can withstand 5-9 shampooing washes can be said to have a short-term styling effect. A composition that provides wash resistance for 10-49 shampooing cycles can be said to provide semi-permanent styling, while a composition that provides wash resistance for more than 50 shampooings can be said to provide permanent styling.

[0202] Methods that rely on such peripheral contraction structures to persistently maintain the shape of straightened hair have often proven detrimental to the health and natural appearance of the hair, and thus the rapid elimination of continuous outer coverage (which is not critical to the present long-lasting styling effect) would be advantageous.

[0203] Figure 4A shows a tress of naturally untreated curly black hair in which the kinks in the hair fiber (e.g., valleys 42 and peaks 44) are clearly detectable. A similar hair sample treated with a hair styling composition described in the present invention as PU6 and straightened with a flat iron is shown for comparison in Figure 4B. As can be seen, the treated hair fiber has a dramatically reduced number of kinks compared to the untreated reference.

[0204] While alternatives are typically harmful to hair, and often to health, the compositions and methods of the present invention are particularly beneficial for long-lasting hair styling, and can also or alternatively be used for short-term hair styling, with hair fibers returning to their natural original shape after 2-4 shampoo washes.

[0205] Figure 5 shows the results of a DSC study showing that conventional hair straightening methods are damaging to hair, and illustrates the expected effects of a non-toxic hair styling method, such as that expected for the hair styling composition of the present invention. As can be seen, the curve of the hair fiber sample that would appear when treated with the composition of the present invention can be comparable to that of the untreated natural hair sample, indicating no significant structural changes, i.e., no damage to the hair. On the other hand, the DSC curves of the commercially available hair straighteners (organic and Japanese) are significantly altered from the natural hair curve, indicating the expected structural changes when using such a dramatic hair styling method. The DSC study is further detailed in Example 11 below.

[0206] Advantageously, hair fibers treated with a composition according to the present teachings are expected to exhibit at least one endothermic temperature within 4°C, within 3°C, within 2°C, or within 1°C of a similar untreated fiber, as measured by thermal analysis.

[0207] The non-damaging effect of the inventive composition on hair fibers treated with the inventive composition can be confirmed or alternatively established by tensile tests in which various mechanical parameters can be compared between treated and untreated hair fibers, as described in Example 12 below. Fibers styled with conventional organic hair straightening are expected to exhibit inferior mechanical properties compared to untreated fibers, whereas fibers treated according to the present invention may behave similarly or better than untreated fibers with similar properties. Without wishing to be bound by a particular theory, it is believed that such improved properties, or at least the lack of significant degradation, are due to the presence of the polymerized form of PBM inside the hair fiber.

[0208] One mechanical parameter that hair fibers treated according to the invention are expected to perform at least as well as untreated hair relates to the pressure (or force per cross-sectional area) required to break the hair, or the breaking stress, measured at the break point of the strain-stress curve. A second mechanical parameter is the hair toughness, which estimates the amount of energy that the hair can absorb before breaking (i.e. the area under the strain-stress curve). Elastic modulus is another mechanical parameter that indicates the resistance of the hair fiber to elastic modification, and fibers treated according to the method of the invention are expected to perform at least as well as untreated hair.

[0209] In some embodiments, hair fibers treated with a composition according to the present teachings exhibit at least one of the following, as measured by tensile property analysis: i) a stress at break that is at least 5%, at least 10%, at least 20%, or at least 25% greater than the stress at break of a similar untreated fiber; and ii) At least 95%, at least 100%, at least 105%, at least 110%, at least 115%, or at least 120% of the toughness of similar untreated hair fibers.

[0210] The method of the present invention is suitable for any desired hairstyle and shape, such as straightening, curling, or producing intermediate shapes, where the hair grows into a shape that is less wavy than its natural unaltered shape.

[0211] Advantageously, the composition of the present invention allows restyling without the need for application of a new composition. Thus, after going through the above-mentioned embodiment of the method that functions to modify the shape of the hair fiber from its natural shape to a first modified shape, the hair fiber can be reformed into a second modified shape. This can be achieved by subjecting the hair fiber to a temperature above the Tg or softening temperature of the polymer formed during the first shaping, and is therefore sometimes referred to as "at least partially softening". During and / or after such at least partially softening step, the hair fiber is formed into the desired second shape. The temperature can then be reduced below the Tg or softening temperature while maintaining the hair in the desired shape, allowing the polymer to regain a suitable restraining structure to hold the second shape. Alternatively, the temperature can be actively reduced, such as by applying cold air to the hair. The second modified shape can be the same as the first modified shape or different. While this innovative restyling method has been described with respect to softening the polymer previously infiltrated within the fiber, it is believed that the heat applied to achieve this softening may further function to lower the moisture content. As explained above, it is believed that the elimination of residual moisture in turn affects hydrogen bonding, enhancing the effectiveness of the reformed polymer when softening ceases.

[0212] Advantageously, the composition of the present invention allows for "de-styling" if desired, which means that hair fibers treated according to the present invention can regain their original shape without waiting for the effect of styling to disappear over time or for the naturally shaped hair fibers to regrow. This can be achieved by subjecting the previously styled hair fibers to a temperature above the Tg or softening temperature of the polymer in the presence of water for a time sufficient for the temperature to soften the polymer and for the water to penetrate the hair fibers. Without wishing to be bound by theory, it is believed that such a de-styling treatment may result in the softening of the polymer, thus breaking to some extent the bonds that the polymer would have formed with parts of the hair fibers that are prone to form hydrogen bonds. The presence of water during the de-styling treatment allows such molecules to penetrate the hair, thereby allowing at least some of the hydrogen bonds that naturally occur in untreated hair to be reformed. Depending on the extent of reformation of the original hydrogen bonds of the hair fiber and the form the polymer can assume when cooled back down to a lower temperature that no longer supports softening, destyling can be partial or complete, and the hair can accordingly return slightly or more closely to its original shape. Since the destyling process is believed to only affect the shape of the polymer remaining within the hair shaft, after destyling, if desired, the hair fiber can be subjected to further styling treatments as described above for restyling.

[0213] The Tg or softening temperature of a synthetic polymer in a hair fiber can be evaluated experimentally, for example, in vitro. A sample of hair to be restyled or destyled can be taken from the scalp of the hair to be treated in such a way and placed in the intended restyling / destyle liquid (e.g., water). At this stage, the sample hair fiber has a specific modified shape. The temperature can be gradually increased and the ability to relax the shape due to the temperature can be monitored. The temperature at which the hair fiber loses the modified shape and returns to its natural shape is deemed suitable for at least partial softening of the polymer. The suitable temperature also depends on the incubation time of the sample. Alternatively, the Tg of a phenolic polymer (PBP) formed by polymerizing a phenolic monomer (PBM) in vitro according to the method described above can be determined by standard thermal analysis methods, for example, DSC as described in ASTM E1356. In some embodiments, the Tg or softening temperature of the polymer is at least 40°C, at least 50°C, or at least 60°C, and such softening temperature generally does not exceed 80°C. The time for which the hair fiber should be exposed to such temperatures to achieve restyling or destyling can be determined as well. Typically, such treatment lasts for at least 5 minutes, at least 10 minutes, at least 20 minutes, at least 30 minutes, at least 40 minutes, at least 50 minutes, or at least 60 minutes, and generally does not exceed 4 hours or 3 hours, with higher temperatures requiring shorter softening times. Hair styling compositions can be sold with instructions regarding the temperature and time required for restyling or destyling, if desired.

[0214] Advantageously, the compositions and methods of the present invention are suitable for styling growing hair. The synthetic polymer formed by the initial application of the hair styling composition is expected to be located at the site of the hair fiber available on the scalp at the time of application of the monomer. With the passage of time and growth of the hair, such sites are found to be more and more distant from the scalp, and the newly grown hair adjacent to the scalp lacks such an internal styling skeleton. It is believed that the hair styling composition applied at a later time after such hair growth will likely act primarily on the newly grown sites, with the previously treated sites already being "occupied" by the preformed synthetic polymer and crystallized WHA. However, as explained, the existing polymers can functionally merge with the polymers that will be newly formed at the new sites to allow for restyling or de-styling of the hair fiber, providing "styling continuity" along the entire fiber of the existing and newly grown.

[0215] The present invention further provides a liquid composition for styling mammalian hair fibres, the liquid composition comprising: At least one PBM, as described herein; At least one WHA as described herein; Water, and one or more co-solvents; A curable single-phase composition comprising: The liquid composition has a pH adapted to promote penetration of at least a portion of the PBM(s) and WHA(s) into the hair fiber.

[0216] The present invention further provides a liquid composition for styling mammalian hair fibers, the liquid composition being a hardenable oil-in-water emulsion comprising: an oil phase containing at least one PBM as described herein; and an aqueous phase containing water and at least one WHA as described herein, wherein the water and / or aqueous phase is at a pH adapted to promote penetration of at least a portion of the PBM(s) and WHA(s) into the hair fiber; Each of the oil and aqueous phases optionally further comprises one or more co-solvents; and The oil phase is dispersed in the water phase.

[0217] In some embodiments, the single-phase composition or the oil-in-water emulsion optionally further contains at least one cure accelerator selected from crosslinkers and cure accelerators, as described above and in further detail herein.

[0218] In some embodiments, the liquid hair styling composition (e.g., an oil-in-water emulsion) optionally further comprises at least one additive selected from the group comprising emulsifiers, humectants, thickeners, auxiliary polymerization agents, and charge control agents, as described above and in further detail herein.

[0219] Advantageously, the hair styling composition according to the present teachings does not contain known carcinogenic compounds.For example, in some embodiments, the hair styling composition contains acceptable trace amounts of such compounds, which can be less than 0.5 wt% formaldehyde, less than 0.2 wt% formaldehyde, less than 0.1 wt. formaldehyde, or even less than the acceptable standard levels of less than 0.05 wt% formaldehyde, less than 0.01 wt% formaldehyde, less than 0.005 wt% formaldehyde, less than 0.001 wt% formaldehyde, or no formaldehyde at all, depending on the jurisdiction, by weight of the composition. The same limiting concentrations apply to products that may generate or act as formaldehyde (e.g., glyoxylic acid and its derivatives, or other formaldehyde liberators) and to products that may generate or act as glutaraldehyde (e.g., 2-alkoxy-3,4-dihydropyrans). These hazardous compounds include their respective precursors or substituted forms (also called formaldehyde generating compounds or formaldehyde releasing agents), such as quaternium-15 (including, for example, Dowicil™ 200; Dowicil™ 75; Dowicil™ 100; Dowco™ 184; and Dowicide™ Q, available from Dow Chemical Company); imidazolidinyl urea (such as Germall™ 115, available from Ashland); diazolidinyl urea (such as Germall™ II); bromonitropropanediol (Bronopol); polyoxymethylene urea; 1,2-dimethylol-5,6-dimethyl (DMDM) hydantoin (sold as Glydant); tris(hydroxymethyl)nitromethane (Tris Nitro); tris(N-hydroxyethyl)hexahydrotriazine (Grotan® BK); and sodium hydroxymethylglycinate, which may be referred to herein individually and collectively as small reactive aldehydes (SRAs).

[0220] As will be appreciated by those skilled in the art of organic chemistry, the SRA molecule need not itself be an aldehyde, but may be further chemical families, so long as it is capable of forming (e.g., by hydrolysis, decomposition, reaction, etc.) harmful aldehydes, such as formaldehyde and glutaraldehyde. Such formation may be triggered by conditions common in hair styling, such as the application of heat. Some such precursors may be fully converted to formaldehyde or glutaraldehyde, and one molecule of SRA may generate one or more molecules of formaldehyde under ideal conditions, optionally via intermediate products, but this may be an extreme case, and other precursors may only be partially converted. Heximinium salts are an example of the latter.

[0221] In any case, assuming that the SRA compound is other than formaldehyde or glutaraldehyde, their weight in the composition will exceed the final weight of formaldehyde or glutaraldehyde that can be formed thereby.In certain embodiments, the hair styling composition contains less than 0.5wt% SRA, less than 0.2wt% SRA, less than 0.1wt% SRA, less than 0.05wt% SRA, less than 0.01wt% SRA, less than 0.005wt% SRA, less than 0.001wt% SRA, or no SRA, based on the weight of the composition.As will be understood, a hair styling composition is considered to be essentially free of SRA molecules if it contains or generates undetectable levels of formaldehyde during the hair styling method (e.g., upon heating the composition).

[0222] Since formaldehyde reacts with hair proteins, the substantial absence of formaldehyde in the hair styling composition corresponds to the absence of its reaction products in treated hair fibers.The reaction products of formaldehyde depend on the amino acid with which it reacts, for example, reaction with cysteine ​​produces thiazolidines and hemithioacetals, reaction with homocysteine ​​produces thiazinanes and hemithioacetals, reaction with threonine produces oxozolidines, and reaction with homoserine produces 1,3-oxazinanes.These reaction products can be detected in hair fibers by standard methods such as NMR.

[0223] Thus, mammalian hair fibers styled by the method or with the composition of the present invention can be characterized as containing less than 0.2 wt%, less than 0.1 wt%, less than 0.05 wt%, less than 0.01 wt%, less than 0.005 wt%, less than 0.001 wt%, or substantially devoid of reaction products between formaldehyde and amino acids. In some embodiments, mammalian hair fibers treated according to the present teachings contain undetectable levels of at least one of thiazolidine, hemithioacetal, thiazinane, oxozolidine, and 1,3-oxazinane, as can be measured by NMR. Since cysteine ​​can account for up to 18% of the amino acid repeats in normal human keratin protein, the absence of thiazolidine and / or hemithioacetal in hair fibers can be the most important marker corresponding to the absence of formaldehyde and formaldehyde-forming products in the composition previously used to treat the hair.

[0224] In some embodiments, the hair styling composition is substantially devoid of amino acids, peptides and / or proteins. The proteins absent from the composition may be naturally occurring proteins such as keratin and collagen, or may be synthetic and / or modified (e.g., hydrolyzed) forms thereof, and the peptides absent may be smaller fragments of such proteins. For simplicity, such peptides may be named according to the larger proteins they may be a part of, for example, considering the proteins most frequently used in hair treatment, they may be referred to as keratin-related peptides or collagen-related peptides.

[0225] The compositions according to the invention are considered to be substantially devoid of amino acids, peptides or proteins, particularly keratin, collagen and their related peptides, when they constitute less than 1 wt% of the composition, preferably less than 0.5 wt%, less than 0.1 wt%, or less than 0.05 wt% of each of them by weight of the hair styling composition. In some embodiments, such substances are accordingly substantially absent from the composition (e.g., about 0 wt%). The presence or absence of such biomolecules can be determined by standard methods, including, for example, by matrix-assisted laser desorption / ionization (MALDI) and related techniques, including by time-of-flight mass spectrometry (MALDI-TOF).

[0226] Thus, mammalian hair fibres styled by the method or with the composition of the present invention may additionally or alternatively be characterized as being substantially devoid of peptides and proteins other than those naturally formed. In contrast to hair fibres treated in conventional manner with naturally occurring proteins or related peptide fragments thereof, hair fibres styled by the method of the present invention may be characterized as being substantially devoid of peptides of proteins naturally occurring in the hair fibre.

[0227] The compositions according to the invention and mammalian hair fibres styled therewith may additionally or alternatively be characterised by the presence of a WHA in the composition or within the hair fibre, which may be determined by any method appropriate for the WHA in question.

[0228] When attempting to detect a substance within hair fibers, the hair fibers are usually thoroughly washed and rinsed (e.g., at least 10 times) with a detergent that does not contain the substance under evaluation, to ensure that any levels detected after extraction originate only from the inside of the hair fiber. By way of example, if the substance to be detected is a WHA and the substance used in the hair styling composition or method of the present invention is urea, the detergent used to wash the hair fibers does not contain urea, and after sufficient extraction (e.g., in a suitable liquid such as water, preferably at an elevated temperature such as 70° C., for up to 12 hours), the presence of urea in the extract obtained from the treated hair fiber sample can be detected by electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD), or standard laboratory methods commonly used for pharmaceutical purposes.

[0229] Identification of the hair styling compositions of the present invention can also be achieved by detection of characteristic functional groups, such as phenols, in the essential components of the composition or in extracts from the hair styled fibers, which functional groups can be detected by any method known in the art, such as Fourier transform infrared spectroscopy (FTIR).

[0230] In summary, mammalian hair fibers containing therein at least partially cured PBM of the present invention forming a synthetic polymer within the fiber can be characterized by at least one of the following features: i) having less than 0.2 wt. % of reaction products of formaldehyde and amino acids based on the weight of the hair fiber, said reaction products being selected from the group including thiazolidines, hemithioacetals, thiazinanes, oxozolidines, and 1,3-oxazinanthiazolidines; ii) exhibiting at least one endothermic temperature within 4°C, within 3°C, within 2°C, or within 1°C of untreated hair fiber as measured by thermal analysis such as DSC; iii) having a stress at break that is at least 5%, at least 10%, at least 20%, or at least 25% greater than the stress at break of a similar untreated hair fiber as measured by tensile analysis; iv) having a toughness as measured by tensile analysis that is at least 95%, at least 100%, at least 105%, at least 110%, at least 115%, or at least 120% of that of a similar untreated hair fiber; v) less than 0.2 wt%, less than 0.1 wt%, less than 0.05 wt%, less than 0.01 wt%, less than 0.005 wt%, or less than 0.001 wt% small reactive aldehydes (SRAs) selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals by weight of the hair fiber; and vi) exhibiting a signal indicative of the presence of a WHA, such as an electrochemical impedance spectroscopy (EIS) signal indicative of the presence of urea.

[0231] In one embodiment, the mammalian hair fibre satisfies at least the characteristics i) listed above); at least the characteristics ii) listed above); at least the characteristics iii) listed above); at least the characteristics iv) listed above); at least the characteristics v) listed above); or at least the characteristics vi) listed above. In one embodiment, the mammalian hair fibre satisfies at least the characteristics i) and ii) listed above); at least the characteristics i) and iii) listed above); at least the characteristics i) and iv) listed above); at least the characteristics i) and v) listed above); at least the characteristics i) and v) listed above); at least the characteristics iii) and iv) listed above); at least the characteristics i), iii) and iv) listed above); at least the characteristics i), ii), iii), iv) and v) listed above; or at least the characteristics i), ii), iii), iv), v) and vi) listed above.

[0232] The present invention also provides a kit for styling a mammalian hair fibre, the kit comprising: I. a first compartment containing at least one PBM; and II. At least one WHA with: 1) Water; 2) co-solvents; and 3) pH adjusters; and a second compartment containing at least one of Including, the contents of the second compartment being a liquid having a pH selected to enhance penetration of at least a portion of the monomer into the hair fiber; Mixing of the contents of these compartments produces a hair styling composition (eg, a single phase or oil-in-water emulsion) as described above and further detailed herein.

[0233] In some embodiments, the components of the kit are packaged and maintained in various compartments under an inert environment, preferably under an inert gas, such as argon or nitrogen, and / or any other suitable conditions that prevent or reduce adverse reactions during storage of the kit that may reduce the efficacy of the composition. For example, the kit should be stored at a temperature that does not induce polymerization, such as below 30°C, below 27°C, or below 25°C.

[0234] In some embodiments, at least one PBM is prepolymerized prior to being placed in the first compartment of the kit.

[0235] The kit may further comprise at least one curing accelerator, which is a condensation curing crosslinker or an addition curing crosslinker. The curing accelerator may also be a curing accelerator as described above, used to accelerate polymerization. The curing accelerator (which may be a crosslinker or a curing accelerator) may be placed in the first or second compartment depending on its reactivity with any one of the components of these compartments. For example, a polyamine-based crosslinker may be included in the first compartment, since it does not react with PBM at room temperature. Alternatively, if the curing accelerator tends to react spontaneously with any component, it may be placed in another additional compartment. A reactive silane crosslinker is such an example, and would be placed separately in the kit, since if it were placed in the same compartment as the PBM, it would react even at room temperature.

[0236] The kit may optionally further comprise at least one of the following, as detailed above: co-solvent, emulsifier, wetting agent, thickener, auxiliary polymerization agent, and charge control agent, which may be contained in any one of the above compartments or in another additional compartment. When considering the arrangement of such additives, it is preferable to arrange the oil-soluble components in a compartment containing more oil-based components (e.g., the first compartment) and the water-soluble components in a compartment containing more aqueous components (e.g., the second compartment).

[0237] The kit typically includes a leaflet directing the end user on how to mix the various compartments, the order of which may depend on the nature and / or contents of the components in each compartment. In general, the suggested mixing and application method is one that allows for the preparation of an effective and safe composition to be applied within a time appropriate for its efficacy and intended use. For example, if the kit includes a third compartment containing a silane derivative as a cure accelerator, the leaflet may indicate to mix the cure accelerator with the PBM first, and then add the contents of the aqueous compartment. Conversely, if a cure accelerator is present but is not a silane derivative, it may be included in the first compartment, obviating the need for a separate third compartment.

[0238] In some embodiments, the ingredients of the various compartments are mixed as may be indicated in such leaflets before applying the final hair styling composition to the hair fibers. In such cases, the resulting composition may be used immediately before application to the hair fibers or may be left unapplied for up to 3 hours, up to 2.5 hours, up to 2 hours, up to 1.5 hours or up to 1 hour before application to the hair fibers.

[0239] Similarly, the timing and duration of application of the oil-in-water emulsion can be suggested as a function of the desired styling durability, for example, if short-term styling is desired, the composition can be applied relatively later and / or for a shorter period of time than if a longer-lasting styling is desired. EXAMPLES

[0240] Working Example material The materials used in the following examples are listed in Table 1 below. Reported properties were obtained or estimated from product data sheets provided by the respective suppliers. All materials were purchased at the highest purity available unless otherwise noted. N / A indicates information not available. [Table 1] JPEG2024531373000008.jpg163153

[0241] In the following examples, for brevity, materials may be referred to by the acronyms shown in the table above, e.g., "AMEO" refers to "Dynasylan® AMEO" and "IPA" refers to "Isopropyl Alcohol."

[0242] Device Confocal laser microscope: Lext 5000 (Olympus, Japan) Differential scanning calorimeter: DSC Q2000 (TA Instruments, USA) Flat Iron: Babyliss® I-Pro 235 Intense protect Gas chromatograph GC-MS: GCD G1800A (HP, USA) Hair dryer: Itamar superturbo Parlux 4600 (Parlux®, Italy) oven: Drying oven, TZ-150L (Zhengzhou Brother Furnace Co., China) Muffle furnace: 30 / 1300 (Snoll, Germany) Potentiostat: VSP modular 5-channel potentiostat (BioLogic, France) Sonicator: DC-1500H (MRC Lab, Israel) Stirring hotplate: C-MAG HS 7 Control (IKA, Germany) Tensile testing machine: MTT157 (Dia-Stron, UK) Vortex mixer: Vortex-Genie 2 (Scientific Industries, USA) Zeta potential: Malvern Zetasizer NanoS (Malvern Instruments Ltd., UK)

[0243] Example 1: Preparation of stock solutions I. PS / DBM Stock Solution 5 g of phenyl salicylate (PS) and 5 g of dibutyl maleate (DBM) were placed in a 20 ml cup and heated in a hair dryer for 30 seconds until completely dissolved. The resulting PS / DBM stock solution (1:1 by weight) was mixed with 4 Å molecular sieves to reduce the reaction of the stock solution with environmental humidity and kept for at least 3 days to ensure that residual moisture was reduced and preferably removed before further use of the stock solution.

[0244] II. PS / DBM / POSS (EP0409) stock solution 0.05 g of Glycidyl POSS® Cage Mixture EP0409 was placed in a 20 ml cup and mixed with 1.95 g of the PS / DBM stock solution prepared above at room temperature with stirring to obtain a homogenous solution containing 2.5 wt % POSS® EP0409, 48.75 wt % PS, and 48.75 wt % DBM.

[0245] III. PS / DBM / POSS (MA0735) stock solution 0.1 g of Glycidyl POSS® Cage Mixture MA0735 was placed in a 20 ml cup and mixed with 1.9 g of the previously prepared PS / DBM stock at room temperature with stirring to give a homogenous solution containing 5 wt % POSS® MA0735, 47.5 wt % PS, and 47.5 wt % DBM.

[0246] IV. Shellac Stock Solution 2 g of shellac and 8 g of oleylamine were placed in a 20 ml cup. The cup was placed on a hot plate equipped with a magnetic stirrer and the mixture was stirred and held at 160° C. for 40 minutes to obtain a homogenous stock solution of 20 wt % shellac (this will be referred to as the "20% shellac stock solution"). Another shellac stock solution was similarly prepared by mixing 3 g of shellac with 6 g of oleylamine, which contained 33.3 wt % shellac and will be referred to as the "33.3% shellac stock solution".

[0247] V. Al(OBu) 3 Stock solution In a 20 ml cup, add 8 g of aluminum tri-sec-butoxide (Al(OBu) 3 ) was combined with 2 g of 2-butanol at room temperature with stirring for about 5 minutes to give a homogeneous solution.

[0248] VI. PS / DBM / POSS(MA0735) / BPO stock solution In a 20 ml cup, 0.05 g of Glycidyl POSS® Cage Mixture MA0735 and 0.05 g of benzoyl peroxide (BPO) were placed and mixed with 1.9 g of the PS / DBM stock solution prepared above while stirring at room temperature to obtain a homogenous solution.

[0249] These stock solutions prepared in this example were once dried over molecular sieves and then used to prepare oil-in-water emulsions as described in the following examples.

[0250] Example 2: Oil-in-water emulsion containing PBM and WHA PBM Compartment In a 20 ml vial, 1 g of PS / DBM stock solution was combined with 1 g of AMEO and 0.5 g of 20% shellac stock, and the contents of the vial were mixed on a vortex for approximately 10 seconds after the addition of each component. The resulting mixture was transferred to a 20 ml cup equipped with a magnetic stirrer and stirred at room temperature for approximately 80 minutes to allow for prepolymerization of the PBM phase.

[0251] Next, 0.4 g of the prepolymerized PBM phase was placed in a separate 20 ml cup and combined with 0.4 g of IPA and mixed by vortexing to obtain the PBM mixture (also referred to as the PBM compartment).

[0252] The ability of a hair styling composition according to the present teachings to be suitably curable can be evaluated in vitro at this early stage based on the identity of its components, their concentrations and relative proportions. Samples of the prepolymerized PBM phase were allowed to self-level on a microscope slide in contact with a hot plate at 160° C. Mixtures capable of forming a continuous dry coating within 2-3 minutes were considered suitable candidates for further study, and this method allowed for the screening of a large number of compositions prior to testing on hair fibers.

[0253] Aqueous Compartment: An aqueous solution containing urea as a water-soluble moisture absorbent was prepared: 16 g of a 40% aqueous urea solution with a pH of 10 (adjusted separately with ammonium hydroxide) was placed in a 100 ml plastic cup, 2 g of IPA was added, and the resulting aqueous mixture (also referred to as the aqueous compartment) was mixed manually for approximately 10 seconds.

[0254] Oil-in-water emulsions: The contents of the vial containing the PBM mixture was added to the cup containing the aqueous mixture and mixed vigorously by hand for approximately 10 seconds until an emulsion (a "milky" appearance) was obtained. This emulsion is referred to as "PBM-Urea 1," or "PU1." A comparative oil-in-water emulsion without urea ("PBM-No Urea 1," or PNU1) was prepared similarly to PU1, except that 16 g of the 40% aqueous urea solution was replaced with 16 g of water that had been adjusted to pH 10.

[0255] Other oil-in-water emulsions were similarly prepared containing different ingredients, excipients and dosages in each of the two compartments: PU2 containing POSS® EP0409, which was prepared by substituting the PS / DBM / POSS (EP0409) stock solution prepared in Example 1 for the PS / DBM stock solution described above; PU3 containing POSS® MA0735, which was prepared by substituting the PS / DBM / POSS (MA0735) stock solution prepared in Example 1 for the PS / DBM stock solution above; and PU4 containing POSS® MA0735 and benzoyl peroxide. This was prepared by substituting the PS / DBM / POSS((MA0735) / BPO stock solution prepared in Example 1 for the PS / DBM above. The benzoyl peroxide serves to promote activation of the acrylate groups of the POSS® MA0735 crosslinker.

[0256] These compositions are reported in Table 2. The values ​​reported in the table correspond to the concentration of each component in wt% relative to the total weight of the emulsion, except for the value for the prepolymerized PBM phase, which corresponds to the weight percent of that component in that particular mixture. The values ​​are rounded up to the nearest two decimal places, so they may not add up exactly to 100 wt%.

[0257] [Table 2]

[0258] The presence of aldehydes, particularly formaldehyde, can be confirmed in the composition by gas chromatography-mass spectrometry (GC-MS) following standard methods (NIOSH 2539 for aldehydes in general, and NIOSH 2541 for formaldehyde in particular). A sample of the PU1 composition was held at 220°C for 1 hour, which allows for at least partial curing of the PBM in addition to vaporization of the volatile components of the sample, and tested for the presence or formation of formaldehyde. The concentration measured with a detector (Hewlett-Packard GCD, model G1800A) was found to be less than 1 ppm (i.e., 0.0001 wt% or less), confirming that the hair styling composition is substantially free of such SRAs.

[0259] Example 3: Oil-in-water emulsion containing PBM, WHA and cure accelerator Oil-in-water emulsions PU5-PU14 were prepared as described in Example 2, using 20% ​​or 33.3% shellac stock solution and Al(OBu) as a cure accelerator. 3 and were used, which were added to the PBM phase for prepolymerization of PBM.

[0260] Comparative oil-in-water emulsions based on PU5 and PU6 were prepared in the absence of urea as previously done for PNU1 and are designated PNU5 and PNU6.

[0261] These compositions are reported in Tables 3A and 3B. The values ​​reported in the tables correspond to the concentration of each component in wt % based on the total weight of the emulsion, except for the value for the prepolymerized PBM phase, which corresponds to the weight percent of that component in that particular mixture.

[0262] [Table 3A] [Table 3B] JPEG2024531373000012.jpg53153

[0263] Notably, compositions PU12, PU13, and PU14 lack a dedicated crosslinker (such as AMEO, which is included in the other compositions of this example) and contain the cure accelerator Al(OBu) 3 is also believed to function as a crosslinker in these compositions.

[0264] Compositions with relatively low amounts of crosslinker or cure accelerator, when they also act as crosslinkers, are believed to form polymers that behave thermoplastically. To confirm the thermoplastic nature of the compositions, two drops (approximately 0.05 g) of each of PU12, PU13, and PU14 were pipetted onto a glass slide and the second slide was pressed against the first slide to spread and form a thin layer of uniform thickness. The second slide was removed and the glass slides holding the layers of each composition were placed on a hot plate heated to a temperature of 160° C. for 5 minutes. This caused the compositions to become tacky to the touch. The slides were then removed from the hot plate and the compositions were allowed to cool to room temperature and solidify. This process was repeated by heating the slides to a temperature of 60-70° C., which caused the compositions to become tacky again and solidify again when removed from the hot plate and cooled. This behavior is consistent with a thermoplastic composition and is believed to indicate the formation of a polymer network with a low crosslink density.

[0265] The preparation of compositions PU12 and PU13 was repeated, varying the pH of the deionized water in the aqueous compartment from 7.5 to 10 to evaluate which pH could provide the optimal respective charging of the hair fibers and the emulsion droplets. For this purpose, the aqueous compartment was prepared as described in Example 2, with the difference that urea was combined with water at neutral pH and the resulting solution was kept overnight at room temperature to allow the pH to reach equilibrium. Ammonium hydroxide was then added to adjust the desired pH (pH values ​​7.5, 8.0, 8.5, 9.0 and 10.0).

[0266] Example 4: Hair electrostatic charge dependence on pH of PBM-WHA compositions The effect of pH on the zeta potential of the PBM-WHA composition was examined. Samples of composition PU13 with pH values ​​of 7, 8, and 9 were prepared as described in Example 3, and the zeta potential of each sample was measured.

[0267] Table 4 shows the composition PU13(ζ PU13 The table shows the measured zeta potentials of natural hair (ζ h ), and the absolute value of the zeta potential difference between the composition and the hair (△ζ PU13-h ) are also shown.

[0268] [Table 4]

[0269] As can be seen from the table above, all pH values ​​tested were found to be suitable to promote sufficient zeta potential difference between the styling composition and natural hair fibers to enable delivery of the composition to hair. Since bleached hair is known to have more negative binding sites than natural hair, its zeta potential is expected to be more negative compared to natural hair, which would result in a further increase in the delta zeta potential exhibited by the present composition. Therefore, a pH in the range of at least 7.0-9.0 is expected to enable a suitable charge for delivery of PU13 to either natural or bleached hair.

[0270] Example 5: Hair straightening using PBM-WHA composition The hair tresses used to test the hair straightening ability of the compositions of the present invention containing at least a PBM in combination (or not) with a WHA were curly black hair of Brazilian origin (approximately 30 cm long). Each tress was held together at one end with epoxy adhesive and weighed approximately 0.6-1.3 g including the glued tip. The hair used was either natural hair (without any pretreatment), bleached hair, or colored hair.

[0271] Bleaching was performed according to the bleach product package instructions using one of the following: A - blue anti-orange bleach powder ("Blu Bleach decolor", Elgon, Italy) and 9% oxygen cream (Afrodita Cosmetics, Israel) combined in a 1:2 w / w ratio; B - Blue anti-orange bleach powder ("Blu Bleach decolor", Elgon, Italy) and 12% oxygen cream (Professionnel Oxydant Cream, L'Oreal, France) combined in a 1:2 w / w ratio; or C - 4 wt% ammonium hydroxide solution (to mimic products with lower ammonium concentration) and 9% oxygen cream (Afrodita Cosmetics, Israel) combined in a 1:2 w / w ratio.

[0272] Colouring was performed using "Kolston naturals" colour cream (Wella, Switzerland) according to the manufacturer's instructions.

[0273] Curly hair tresses (either natural, bleached, or colored) were washed with tap water containing 5% sodium lauryl sulfate at a temperature of 38-40°C to remove any material adhering to the hair (e.g., dirt or oil), rinsed with excess tap water, and blow-dried or hung to dry at room temperature for at least 1 hour, allowing the tresses to regain their natural shape.

[0274] The basic treatment and straightening procedure applied to clean hair samples is shown diagrammatically in Figure 6, which shows a simplified diagram of the various steps, which are described further below. For simplicity, in this example, the composition or method may be referred to as "straightening", a term that generally denotes the "complete flattening" of the hair fiber, although the term is intended to encompass any significant shape alteration in which the hair is stretched into a less wavy shape than its natural shape.

[0275] procedure: 1. Application of the composition (as depicted in step S-01 of FIG. 6): A hair tress was immersed in a 100 ml plastic cup containing approximately 15-20 g of a hair styling composition (e.g., an oil-in-water emulsion) such as those prepared in Examples 2-3. 2. Incubation of the compositions (as depicted in step S-02 of FIG. 6): The cups containing the hair tress samples immersed in the various compositions were maintained at room temperature for 1 hour, unless otherwise stated, to allow, inter alia, the PBM and WHA to at least partially penetrate into the hair fibers. 3. Rinsing of the hair fibers (as depicted in step S-03 of FIG. 6): The hair tresses thus treated were thoroughly rinsed to remove excess composition from the surface of the hair fibers. Unless otherwise noted, the hair fibers were rinsed with tap water at about 38-40° C. for 10-20 seconds and dried with a hair dryer for 2-3 minutes. 4. Styling the Hair Fiber (as depicted in step S-04 of FIG. 6): The rinsed and dried treated hair tresses were then straightened using a flat iron at a temperature of 220° C. for approximately 2-3 minutes (approximately 30-50 passes) depending on the length of the tress, until the tress was completely dry and had the desired modified shape. This step allows for at least partial curing of the PBM(s). 5. Washing of hair fibers (as depicted in step S-05 of Figure 6): The styled hair strands were then washed by rubbing a standard shampoo on the hair fibers with fingers for about 30 seconds, completely covering the hair from tip to tip and ensuring intimate contact with the hair. The shampooed hair strands were then rinsed with tap water at about 38-40°C, similarly "massaged" with hair conditioner for about 30 seconds, and rinsed again with tap water at the same temperature. The rinsed hair strands were thoroughly dried with a hair dryer. Unless otherwise noted, the standard shampoo was Shea Natural Keratin Shampoo from Saryna Key, Israel, and the hair conditioner was TRESemme's Pro Collection, Biotin+Repair7 from Unilever, USA.

[0276] As will be readily understood, the steps of the procedure described above are exemplary and may be performed under different conditions. The hair styling procedure may also include further steps. Such optional step S-00 (shown in dashed outline in FIG. 6) includes pre-treatment of the hair fiber before applying the composition of step 1, where the hair fiber can be washed and / or residual water can be removed from the hair bundle, for example, using a flat iron to pass over the hair bundle several times at high temperature, such as 200° C.; and / or a pre-treatment composition (e.g., oil) can be applied.

[0277] Another optional step involves further curing the polymerizable styling composition once at least partially cured within the hair fiber. This step can include subjecting the straightened and dried hair strand after styling step 4 or washing step 5 to additional heat using a hair dryer to promote further curing of the PBM already at least partially polymerized in the hair fiber in the previous step. The hair sample can be, for example, held on a brush and the hair dryer moved over the hair strand for a short distance about 15 times, blowing air at a temperature of 150-220°C, so that the hair fiber experiences an elevated temperature of up to 220°C for a few seconds.

[0278] Alternatively, or in addition, a curable composition containing an excess of a curing accelerator may be applied for a short time, for example by rinsing with a dedicated solution containing such material. Similarly, before styling the hair fiber (S-04), the hair may be treated with a formulation that protects the hair from damage that may result from the temperatures applied during styling (described below). Such heat protection formulations may include or consist of oils that have a relatively high smoke point at temperatures higher than those applied for styling. For this purpose, silicone oils may be used. Alternatively, the styling composition may include an agent that provides such heat protection, for example, a suitable lubricant (e.g., silicone oil) may be added to the PBM, the oil being immiscible with the PBM to form an oil-in-water emulsion that allows it to dissolve to protect the PBM during styling, so that the PBM remains sufficiently active to polymerize. In general, a suitable immiscible oil has a density lower than that of the PBM, so that it migrates when the emulsion dissociates with heat. Such a composition is exemplified by two versions of PU7 (each using a different type of silicone oil) prepared in Example 3.

[0279] Example 6: Durability of hair straightening Hair tresses treated with the compositions of the present invention described in Example 5 were subjected to a series of washes beginning 48 hours after wash step 5. In each wash cycle, the hair tresses were washed with shampoo and conditioner as described in wash step 5 of Example 5. Wash cycles were performed up to five times per day, usually at least one hour apart.

[0280] The number of washes that the hair strands remain "straightened" after washing, including any type of modified shape initially obtained at the end of the straightening procedure of Example 5, is an indication of the durability of the hair styling provided by the present compositions and methods. This number can also be referred to as the "wash resistance" obtained by a particular composition under the conditions applied and tested. Wash resistance can be qualitatively and visually assessed by a trained operator, with the results indicating the number of wash cycles until a change in shape becomes visually detectable. Alternatively, wash resistance can be quantified, for example, by measuring the length of hair samples after a styling treatment and after a desired amount of wash cycles, and / or by counting the number of deviations from straight hair (e.g., peaks and dips) on 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 "kinks" of the hair fiber can be obtained by counting the number of amplitudes (minimum and maximum) found on the fiber. The number of kinks can be normalized by the length of the hair, and the straightening efficiency can be calculated by dividing the normalized number of kinks after the considered treatment by the normalized number of kinks before treatment (a reference value). The straightening efficiency can be expressed as a percentage relative to a reference. A hair fiber is "wash resistant" as long as the measurements (e.g., length, number of kinks, straightening efficiency) before wash and at the considered wash cycle are similar (e.g., within 10% of each other) or as long as no visual changes can be detected by a trained operator. Similarly, such methods can be used to evaluate the effectiveness of hair styling compositions.

[0281] Tables 5A and 5B show the wash resistance of the compositions of Examples 2-3 applied to hair tresses treated and straightened as described in Example 5. Results were evaluated qualitatively by trained operators. Table 5A shows the maximum wash resistance tested on natural hair treated with various compositions (formulated at various pH). The values ​​reported for PU7 apply to both compositions containing Silwax® B116 and those containing Silwax® H416.

[0282] [Table 5A]

[0283] As can be seen from the above table, all PU1-PU13 compositions containing a water soluble moisture absorbent (in this example the WHA is urea) provided wash resistance of 6 cycles or more, reaching wash resistance of 90 cycles or more, thereby supporting at least partial penetration of the PBM into the hair fiber and polymerization therein. These conclusions regarding at least partial penetration of the hair styling composition into the hair fiber are further supported by the FIB-SEM analysis reported above with reference to Figures 2A, 2B and 3B.

[0284] In the tables, the symbol ≧ before the reported number of wash cycles indicates that the experiment was stopped at this stage, and therefore the wash resistance provided by these compositions may be greater or even significantly greater than the reported value.

[0285] In comparison, hair fibers treated with compositions lacking urea (i.e., PNU1, PNU5, and PNU6) resulted in hair straightening for up to 5 washes. Thus, in this example, the presence of WHA improved wash resistance by at least 5 times over that of a similar composition without WHA. In the case of PU1 compared to PNU1, the effect of WHA was even more dramatic, increasing wash resistance by more than 20 times. This result is quite surprising, since, as explained above, WHA is relatively water-soluble and would be expected to be washed out very quickly. It is believed that WHA penetrates into the hair fiber and forms a resilient water trap there, and / or a hardening polymer and / or an interaction with hair components.

[0286] The effectiveness of some hair styling compositions was also tested on previously treated hair, i.e., bleached or colored hair, and wash resistance results are reported in Table 5B as a weighted average of replicate experiments.

[0287] [Table 5B]

[0288] Hair fibers that had been previously treated by bleaching or coloring survived a weighted average of at least 7 washes and reached a weighted average of as many as 23 wash cycles, demonstrating that the hair styling compositions of the present invention are effective even on damaged hair.

[0289] Thus, as demonstrated in Example 4, a pH of 7-9 was found to be adequate to obtain a satisfactory zeta potential, but the compositions tested demonstrated efficacy and durability on both natural and damaged hair (bleached or colored hair) over a broader pH range of 5 to 10. As will be appreciated, factors other than the pH of a hair styling composition may affect its efficacy, as assessed herein by the resistance of the styling effect to repeated washings.

[0290] In a second series of experiments, the hair styling procedure was modified to include steps intended to protect the hair fibres from subsequent heat straightening and / or ensure that the hair fibres remain separate after application of the hair styling composition, incubation with the hair and rinsing. For this purpose, a fluorinated silicone lubricant (Fluorosil® J15, Siltech) was applied to the dry hair obtained at the end of step 3, before the ironing in step 4. This was done on hair fibres treated with PU6 in step 2. Interestingly, the hair samples treated with the unmodified procedure achieved a wash resistance of 25 cycles, while the hair samples that benefited from an additional pretreatment of the hair samples with a lubricant managed to maintain the styled shape for up to 39 wash cycles. These results support the beneficial effect of such further steps when included in the hair styling method.

[0291] Example 7: Pretreatment of hair with oil Although styling of hair fibers as described in Example 5 gave satisfactory results (as evidenced by the resulting wash resistance as described in Example 6), the procedure can be modified by including an oil pretreatment step.

[0292] Selecting the right oil Lack of penetration: The penetration of candidate oils into hair can be assessed as follows: a group of hair fibers not treated with the composition of the present invention is weighed and placed in a cup containing the test oil for a sufficient time to allow penetration into the hair. The hair fibers are then removed from the oil, wiped clean, and weighed again. Any increase in the weight of the hair compared to the weight before immersion in the oil can be attributed to the oil penetrating the fibers. Oils with a weight increase of less than 5% are considered suitable for further screening as pre-treatment oils.

[0293] Lack of polymerization inhibition: The inhibitory activity of a candidate oil can be evaluated by applying a thin layer of the test oil on a glass slide, followed by a layer of the curable styling composition according to the present teachings, to test its compatibility with the proposed pretreatment oil. The glass slide is then subjected to the application of energy at an appropriate temperature for a sufficient time to induce complete curing of the styling composition (e.g., placed in a hot plate or oven). The slide with the cured styling agent layer is cooled. The cured layer is then peeled off the slide, and the residual oil applied underneath on the slide is wiped off. If the side of the cured composition that was in contact with the oil remains sticky, this indicates that the curing was not complete, in which case the test oil is considered to have an inhibitory effect on the proper polymerization of the hair styling composition. Conversely, if neither the side that was previously in contact with the oil nor the side that was in contact with air is sticky, the test oil is considered to be suitable for further screening as a pretreatment oil.

[0294] Lack of miscibility: The miscibility of the candidate oils with the styling composition to be applied to the oils was tested as follows: 0.05g of the test oil was added to 0.95g of the hair styling composition under investigation and mixed thoroughly on a vortex for 10 seconds to allow the mixture to phase separate. Oils found to be immiscible with the styling composition were deemed suitable as pre-treatment oils for the later application of said composition.

[0295] Silquat® J2-2B, Silamine® C-300, Silwax® J1016, Silube® CO Di-10, and Silube® TMP D219 were found to be incompatible with the PU5 composition, and Silube® TMP D219 was further found to be incompatible with PU6.

[0296] Pretreatment with selected oils Natural hair fibres were pre-treated with each of the selected oils prior to the first step of the procedure described in Example 5, in which the hair styling composition was applied.

[0297] 20 g of IPA and 0.2 g of pretreatment oil were mixed manually in a 100 ml plastic cup. Hair tresses, previously washed with sodium lauryl sulfate, rinsed and dried as described in Example 5, were immersed in the various oil / IPA mixtures and kept at room temperature for 5 minutes. The tresses were then rinsed with tap water and blow-dried for several minutes until completely dry.

[0298] The hair tresses pretreated with the PU5 or PU6 compositions prepared in Example 3 were then styled according to the procedure described in Example 5, and the durability of the styling treatment was tested as described in Example 6.

[0299] The pre-treatment oils and styling compositions used in combination are shown in Table 5 along with the wash durability results.

[0300] [Table 5]

[0301] The oil pretreatment tested in this study allowed the compositions tested to be used for styling, as assessed by trained operators, while improving the feel and combability of all tested tresses. Hair fibers styled with PU6 were analyzed by FIB-SEM microscopy to evaluate the effect of Silube® TMP D219 on the fugitive coating that may initially form on the outer surface of treated hair fibers. Hair fibers not pretreated with oil showed a fugitive coating of up to 1 μm after only two washes (which were subsequently washed off), while hair fibers pretreated with oil showed no detectable fugitive coating on their outer surface after the same number of washes.

[0302] Example 8: Detection of urea in hair fibers As will be readily understood by those skilled in the art, the presence of ingredients as disclosed herein for the present compositions can be detected in the composition by any standard method adapted to identify the ingredient of interest (e.g., PBM, WHA, cure accelerator, etc.) and using any suitable equipment adapted for such analysis. However, this example is directed to the detection of ingredients of the composition that successfully penetrate the hair fiber after application of the hair styling composition. In particular, since the compositions of the present invention contain PBM and WHA, this study is particularly directed to the detection of urea (i.e., WHA).

[0303] The detection of urea in extracts obtained from hair samples treated with the composition of the present invention was carried out by electrochemical impedance spectroscopy (EIS) using an interdigitated gold electrode. The interdigitated electrode was coated with nickel cobalt oxide (NiCo), an electrocatalyst that promotes the electrooxidation of urea. 2 O 4 ), resulting in the formation of conductive species and an increase in the conductivity of the solution. Using such a technique, minute amounts of urea can be detected.

[0304] Nico 2 O 4 Synthesis of Nickel cobaltate was prepared by mixing 1.300 g of cobalt chloride, 1.185 g of nickel chloride hexahydrate, 2.000 g of urea, and 75 mL of distilled water in a 150 ml glass cup and stirring for 30 minutes using a magnetic stirrer until a homogenous solution was obtained. The cup containing the growth solution was sealed with aluminum foil and kept in a preheated drying oven at a temperature of 95 °C for 5 hours. The precipitate formed was filtered from the growth solution, washed with distilled water, and dried by keeping it at room temperature overnight. The obtained dried powder was calcined in a muffle oven at a temperature of 500 °C for 3 hours.

[0305] Nico 2 O 4 Fabrication of coated interdigitated electrodes 4mg of calcined NiCo 2 O 4 The powder and 1 ml of isopropyl alcohol were placed in a 20 ml glass vial and sonicated for 15 minutes. 0.5 ml of 5% Nafion™ solution was added and mixed with a vortex mixer to obtain a suspension.

[0306] Interdigitated gold electrodes (Eltek, Israel) were prepared by the drop-casting method as follows: 2 O 4 -Nafion™ solution: 4 drops of the solution (approximately 100 μl) were placed on the interdigitated portion of the electrode and the electrode was kept at room temperature for 3 hours to allow the liquid to evaporate, thereby forming a NiCo 2 O 4 A dry coating of Nafion™ was formed.

[0307] Preparation of hair fiber extract samples Two hair tresses (each tress from a different source) were treated with composition PU12 according to Example 5 and washed 12 times with a urea-free detergent to remove external traces of this substance.

[0308] Ten hair fibers from each tress were placed into two 20 ml vials each containing 2 g of distilled water, and the vials were placed in a 70°C oven with constant shaking at 200 RPM. After 12 hours, the vials were removed from the oven and allowed to cool to room temperature. Each hair sample was filtered and the resulting extract was transferred for impedance analysis.

[0309] A reference extract sample was similarly prepared using hair fibers that had not been treated with the PBM-urea composition but simply washed and rinsed 12 times with tap water containing 5% sodium lauryl sulfate.

[0310] Electrochemical impedance measurements The detection of urea in the extract was carried out by the following oxidation reaction (NiCo 2 O 4 This was based on electrochemical impedance measurements of the solution, according to the reaction whereby conductive ions are formed, catalyzed by an electrocatalyst: [ka]

[0311] The produced ions contribute to an impedance change in the solution that is proportional to their concentration, and thus indicates the concentration of urea in the test solution.

[0312] Electrochemical impedance measurements were performed at room temperature using a potentiostat with frequency response analysis (FRA) (combined with EC-Lab® software) in potentiostatic mode, with a frequency range of 100 kHz to 1 Hz and a constant potential: either 0 mV or 850 mV urea oxidation potential (as in previous measurements). A conventional assembly of a two-electrode setup was used, where the working electrode cable was connected to a NiCo 2 O 4 A NiCo2O4 coated interdigital electrode was connected to one side of the interdigital electrode, and a counter electrode and a reference electrode were attached together to the other side of the interdigital electrode. The NiCo2O4 coated interdigital electrode was manually cleaned before each scan by washing with water and then dried with a compressed air blower.

[0313] Impedance measurements were performed for each of the two test samples. First, a potentiostatic step was performed, applying each selected potential to the electrodes for 10 seconds (a potential of 850 mV was applied to initiate the oxidation reaction, and a potential of 0 mV was applied as a reference).

[0314] Resistance values ​​(R) were calculated for each extract by Zfit data processing and then converted to conductivity (C = 1 / R). The calculated conductivity values ​​were used to determine the relative conductivity change (ΔC / C), where ΔC is the difference between the conductivity at 850 mV and the conductivity at 0 mV divided by the conductivity at 0 mV. The change in conductivity was then divided by the mass of the sample (m) to obtain a normalized value. The detection limit of this method was approximately 0.001 mg, as measured according to an untreated standard sample. -1 It was.

[0315] The impedance of the two extract samples was measured, and the (ΔC / C) / m value was calculated, which was an average of 0.024 mg -1 , indicating the presence of urea in the extract. Since the extraction of the hair fiber contents was performed after 12 washing cycles, it is believed that the urea detected in the extract actually comes from composition PU12 that has penetrated the hair fiber.

[0316] In a comparative experiment, ten hair fibres were immersed in 20ml of a 40% urea solution for 1 hour. The fibres were then removed from the urea solution and washed 12 times as described above. Extract samples were obtained from the washed fibres and impedance measurements were performed as described above.

[0317] After 12 washes of hair fibers exposed to high concentrations of urea, the (△C / C) / m value obtained was 0.002 mg -1 and 0.001 mg obtained in the absence of urea. -1The results were close to the baseline of 0.01, indicating that most of the urea present in and on the hair fiber was washed out. This value is lower than that obtained for hair treated with composition PU12, suggesting that the hair styling composition according to the present teachings not only penetrated the hair fiber as supported by the presence of urea, but also limited or reduced the washing out of urea from the hair (which occurs more freely in the absence of the polymeric styling composition, as shown in the comparative experiment).

[0318] Example 9: Re-styling of hair treated with a composition containing PBM-WHA Hair samples treated with compositions as prepared in Examples 2-3, which show sufficient wash resistance as tested in Example 6 (e.g., by surviving at least 10 wash cycles or other set number of cycles to confirm the formation of PBPs in the fiber), can be subjected to a restyling treatment, such as hair fiber straightening, as described in step 4 of Example 5. This heat treatment is expected to soften the formed polymer sufficiently to reshape the shape of the hair fiber in order to restyle the hair fiber. The restyling can be the same shape provided by the original styling treatment or any other second modified shape that can be applied to the fiber. After the application of heat, the hair sample is cooled back to room temperature, allowing the polymer to regain its hard / unsoftened structure. The hair sample thus restyling can be subjected to a wash cycle as described in Example 6 to evaluate the resistance of the reformed polymer and the continued protective effect of the WHA.

[0319] Example 10: Destyling of hair treated with a composition containing PBM-WHA Hair samples treated with compositions as prepared in Examples 2-3 that exhibit sufficient wash resistance as tested in Example 6 (e.g., by enduring at least 10 wash cycles or other set number of cycles to ensure PBPs are formed within the fibers) and are still in a styled (straightened) configuration can be subjected to a destyling treatment that allows the hair to regain its original (unaltered, e.g., curly) shape.

[0320] The styled hair sample can be immersed in a 100 ml plastic cup containing about 15 g of destyling solution, which is an ammonium solution at pH 10.5. The cup is then placed on a digital orbital shaker and shaken at 60° C. for 1 hour. The appearance of the hair sample thus "destyled" is compared to that of a natural, untreated hair sample to evaluate the effectiveness of the destyling treatment. The inventors speculate that the destyling treatment does not remove the synthetic polymers incorporated within the hair fiber, as previously described, as evidenced by the ability to further restyle the hair sample.

[0321] Example 11: Differential Scanning Calorimetry (DSC) Studies Keratin hair fibers exhibit characteristic endothermic peaks in many thermal analysis methods, each peak indicating a chemical change occurring near a different temperature. Hair samples treated according to Examples 5 and 6 can be analyzed by DSC to evaluate the effect of the compositions of Examples 2-3 on the physicochemical properties of the hair fiber and compared to an untreated reference of the same hair type.

[0322] The reference and treated hair samples were cut into small pieces (approximately 2 mm long) with ordinary scissors. For each measurement, approximately 5 mg of hair piece was placed in a 70 μl DSC platinum crucible. The crucible was left open during the measurement.

[0323] The sample was placed in a differential scanning calorimeter and subjected to DSC measurements, specifically, the sample was heated to 400°C at a rate of 10°C / min under nitrogen while data was collected and stored.

[0324] The stored data is plotted to obtain a DSC curve for each hair sample and the endothermic value is extracted. If the modified hair fiber and the natural hair fiber exhibit at least one essentially similar endothermic temperature, the composition that achieved this modification is considered to be non-hazardous. The endothermic temperatures of two materials or hair fibers can be considered to be essentially similar if they are within 4°C, 3°C, 2°C, or 1°C of each other.

[0325] Figure 5 shows the results of a DSC study that shows how a non-damaging hair styling method as proposed by the present invention can keep hair intact in contrast to conventional methods. As can be seen, the curve of the hair fiber sample treated with the hypothesized non-harmful composition of the present invention is comparable to that of the untreated natural hair sample, indicating no significant structural changes. The solid line at the bottom of the plot represents the curve of the untreated black hair fiber. Two endotherms were observed at 234.5°C and 250°C, which are characteristic temperatures of hair fibers. The first endotherm around 234.5°C is believed to indicate melting of α-keratin in the fiber, while the second endotherm around 250°C is believed to indicate decomposition of keratin and cleavage of disulfide bonds.

[0326] In contrast, the DSC curves of the commercial hair straightening methods (organic and Japanese) actually tested against the untreated reference show considerable changes from the curve of the natural hair sample, indicating the structural changes that would be expected when using such a drastic hair styling method.

[0327] Such measurements may alternatively be obtained from other thermal analysis methods, such as thermomechanical analysis (TMA) or dynamic mechanical analysis (DMA).

[0328] Example 12: Mechanical properties of hair fibres Hair samples treated according to Examples 4 and 5 were analyzed by tensile testing to evaluate the effect of compositions of the present invention (such as those prepared in Examples 2-3) on the mechanical properties of hair fibers and compared to an untreated reference of the same hair type.

[0329] Ten hair fibers were taken from each of the reference sample and the PU6-treated hair sample and kept under the same conditions (e.g., temperature 25°C, humidity 45% RH (relative humidity)) for three days for standardization. The hair fibers were then cut to a length of 30 mm and a representative cross section was measured by confocal laser microscope, taking into account both the maximum and minimum radius of a typical elliptical hair fiber. Tensile parameters, elongation at break, breaking stress, toughness and elastic modulus were measured by a tensile tester for the tested hair fibers (100% extension limit, extension rate of 20 mm / min, gauge force of 2 g, break detection limit of 5 g and maximum force of 2000 g). The average results of the 10 fibers of the treated hair sample were compared with those of the reference sample.

[0330] Hair fibers straightened with PU6 have comparable elongation at break, stress at break, and toughness to untreated hair fibers, with the average results being slightly higher without statistical significance. Only in modulus, samples treated with the composition were found to be higher than untreated samples. These results were observed in sets of hair fibers obtained from two different sources. For comparison, hair fibers treated with organic straightening (known to be damaging, as shown in the DSC examples) were found to be generally inferior to the untreated reference, and thus to hair fibers treated with the method of the present invention. For example, hair samples straightened with the method of the present invention showed 10% higher toughness than untreated hair, while hair samples straightened with organic technology showed 30% lower toughness. Similarly, hair samples straightened with the method of the present invention showed 6% higher stress at break than untreated hair, while in contrast, hair samples straightened with organic technology showed 12% lower toughness. Regardless of the statistical significance of the results, it can be said with confidence that the methods and compositions of the present invention at least do not damage, and may even improve, the hair fiber.

[0331] Although these observations were made with a single sample treated with the compositions and methods of the present invention, it is believed that they illustrate trends that may be applicable to other compositions.

[0332] In general, the breaking stress of the treated hair fibers is expected to be at least 5%, at least 10%, at least 20%, at least 25% higher than the breaking stress of a similar untreated fiber. Furthermore, the treated hair fibers are expected to have a toughness of at least 95%, at least 100%, at least 105%, at least 110%, at least 115%, or at least 120% of that of a similar untreated hair fiber. The modulus of elasticity of treated and untreated samples is expected to be at least comparable, since negative controls such as organic straightening do not affect this particular parameter.

[0333] Example 13: Field Testing of Hair Styling Compositions The hair styling compositions according to the present teachings can be tested on human volunteers with hair lengths of at least 25 cm or more. The volunteers have wavy to curly hair, and the hair is either naturally uncolored or colored with a conventional color formulation. The hair of the study group styled with a particular composition can include at least six people and form different subgroups. All volunteers participate in the testing procedure with clean, dry hair, and each volunteer is assigned a baseline value for unstretched hair length, number of peaks and valleys along a representative core and hair fiber, and similar parameters for testing the effectiveness of the sample composition as described previously.

[0334] This test is similar in principle to the in vitro procedure described in Examples 4 and 5, with the following modifications. First, the thickener is formulated to have sufficient viscosity to retain the composition on the hair during the incubation period. Second, since the hair is not immersed in a beaker, the thickened composition can be applied with a brush to individual groups of hair fibers one at a time, and each core of the hair fiber is then wrapped in aluminum foil that is folded around the already coated hair fiber until the entire scalp hair is coated with the hair styling composition to be tested. After application, the hair styling sample is allowed to remain on the hair fiber for the incubation period (e.g., 1 hour at room temperature). The hair is then rinsed thoroughly with tap water at about 35-40°C and dried with a hair dryer for 2-3 minutes. Next, the volunteers' hair is preconditioned with a protective lubricant (e.g., silicone oil) and then straightened using a flat iron at a temperature of 220°C for approximately 2-3 minutes (approximately 30-50 passes) for each core of the hair until the hair is completely dry and has the desired corrected shape. The straightened hair fibers are washed with shampoo and conditioner and dried. At this stage the hair is defined as "styled". The styled hair of each volunteer is analyzed again to determine new values ​​for the length of the hair, the number of peaks and valleys along a representative core and fiber, which have been changed from the untreated baseline. These parameters are measured and recorded at predetermined time points along the study.

[0335] Once the hair has been "styled" as detailed above, the volunteers wash the hair at the prescribed times every two days, and the appearance of the washed hair and the parameters that give more quantitative changes are again measured and recorded. Compositions that provide a stable modified shape for at least 10 wash cycles (22 days) are considered successful.

[0336] It is understood that certain features of the disclosure that are described for clarity in the context of separate embodiments can also be provided in combination in a single embodiment. Conversely, various features of the disclosure that are described for brevity in the context of a single embodiment can also be provided separately or in any suitable subcombination or in any other described embodiment of the disclosure, as appropriate. Certain features described in the context of various embodiments are not considered essential features of those embodiments, unless the embodiment does not function without those elements.

[0337] Although the present disclosure has been described with respect to various specific embodiments presented therein for illustrative purposes only, such specifically disclosed embodiments should not be considered as limiting. Based on the applicant's disclosure herein, many other alternatives, modifications, and variations of such embodiments will occur to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications, and variations, and to be bound only to those changes that are within the spirit and scope of the present disclosure and within the scope of their meaning and equivalence.

[0338] In the specification and claims of this disclosure, the verbs "comprise," "include," and "have," and each of their conjugations, are used to indicate that the object or objects of the verb are not necessarily an exhaustive list of features, members, steps, components, elements, or moieties of the subject or subjects of the verb, such that the compositions of the present teachings also consist essentially of or consist of the recited components, and the methods of the present teachings also consist essentially of or consist of the recited process steps.

[0339] As used herein, the singular forms "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 in some embodiments may mean A and B.

[0340] Unless otherwise noted, the use of the word "and / or" between the last two elements of a list of alternatives for selection indicates that one or more of the listed alternatives are eligible and can be selected.

[0341] Unless otherwise stated, when outer boundaries of ranges for features of embodiments of the present technology are set forth in the disclosure, it should be understood that in that embodiment, possible values ​​of the feature can include the set forth outer boundaries, as well as values ​​between the set forth outer boundaries.

[0342] As used herein, unless otherwise stated, adjectives such as "substantially," "approximately," and "about" modifying the condition or relationship characteristics of one or more features of an embodiment of the present technology are defined as conditions or characteristics within the tolerances allowed for operation of the embodiment in its intended use, or within the expected variation from the measurements made and / or the measurement equipment used. When the terms "about" and "approximately" precede a numerical value, they are intended to indicate only + / -15%, or + / -10%, or even + / -5%, as the case may be, to indicate the exact value. Furthermore, unless otherwise stated, the terms (e.g., numbers) used in this disclosure should be interpreted as having a tolerance that may deviate from the exact meaning of the associated term without such adjectives, but that allows the present invention or its relevant portions to operate and function as described and as understood by one of ordinary skill in the art.

[0343] While the present disclosure has been described in terms of specific embodiments and generally associated methods, modifications and permutations of the embodiments and methods will be apparent to those skilled in the art, and it is to be understood that the present disclosure is not limited by the specific embodiments described herein.

[0344] Certain marks referenced herein may be common law trademarks or registered trademarks of third parties. Use of these marks is exemplary and is not to be construed as descriptive or to limit the scope of the present disclosure solely to the material associated with those marks.

Claims

1. 1. A method of styling mammalian hair fibers having a natural shape, said method comprising: a) applying a hair styling composition to individual hair fibers, wherein the hair styling composition comprises at least one energy-curable water-insoluble phenolic monomer (PBM) having an average molecular weight of 10,000 g / mol or less, at least one polar water-soluble hygroscopic agent (WHA), and water; b) leaving the hair styling composition in contact with the hair fiber for at least 5 minutes to ensure at least partial penetration of the PBM(s) and WHA(s) into the hair fiber; and c) applying energy to at least partially cure at least a portion of the PBM within the hair fiber, wherein said curing occurs while the hair fiber is at a temperature of at least 50°C, resulting in a treated hair fiber; Including, wherein the hair styling composition contains less than 0.1 wt. % of a small reactive aldehyde (SRA), the SRA being selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals.

2. At least one energy-curable, water-insoluble PBM has the general formula I: 【Chemical Formula 1】 where: i) R １ , R ２ , R ３ , and R ５ are each independently a hydrogen atom, a hydroxyl, or a linear, branched, or cyclic, substituted or unsubstituted C １ ~C ２０ Alkyl, C １ ~C ６ Alkoxy, C １ ~C ６ Allyl, C １ ~C ８ Aromatic esters, or C １ ~C ８ is a non-aromatic ester; and ii) R ４ is a hydrogen atom, a hydroxyl, or a saturated or unsaturated C Ｘ H Ｙ alkyl, where X is an integer less than or equal to 15, and Y is equal to 2X+1-n, where n is selected from 0, 2, 4, and 6; The method of claim 1.

3. The or each water-soluble moisture absorbent has the following structural characteristics: i) WHA is a non-electrolyte; ii) the WHA has a hydrogen bond energy with water of at least 21 kJ / mol; iii) the WHA has a hydrogen bond energy with water of at most 40 kJ / mol; iv) the WHA has a hydrogen bond energy with water of 21 kJ / mol to 40 kJ / mol; v) the WHA has a solubility in water of 5 wt % or more, based on the weight of water, measured at a temperature of 25°C; vi) the WHA has a solubility in water of 150 wt % or less, based on the weight of water, measured at a temperature of 25°C; vii) the WHA has a solubility in water in the range of 5 wt % to 150 wt %, based on the weight of water, measured at a temperature of 25°C; viii) the WHA has a solubility in the hair styling composition or its aqueous phase, measured at a temperature of 25°C, of 5 wt% or more, based on the weight of the composition or its aqueous phase; ix) the WHA has a solubility in the hair styling composition or its aqueous phase of 140 wt % or less, based on the weight of the composition or its aqueous phase, measured at a temperature of 25°C; x) the WHA has a solubility in the hair styling composition or its aqueous phase in the range of 5 wt % to 140 wt %, based on the weight of the composition or its aqueous phase, measured at a temperature of 25°C; xi) WHA is the melting temperature (T ｍ ) is 25°C or higher; xii) WHA is the melting temperature (T ｍ ) is 200°C or less; xiii) WHA is the melting temperature (T ｍ ) is in the range of 25°C to 200°C; xiv) WHA is the boiling temperature (T ｂ ) is 100°C or higher; xv) WHA is the boiling temperature (T ｂ ) is 300°C or less; xvi) WHA is the boiling temperature (T ｂ ) is in the range of 100°C to 300°C; xvii) the WHA has a vapor pressure of 2.3 kPa or less, measured at 25°C; and xviii) the WHA has a vapor pressure of 1 mPa or more, measured at 25°C; 3. The method according to claim 1, characterized in that at least one, at least two or at least three of:

4. The hair styling composition is an oil-in-water emulsion, wherein at least one energy-curable water-insoluble PBM is present in the oil phase of the emulsion and at least one WHA is present in the water phase of the emulsion, and the hair styling composition comprises: I) a cure accelerator selected from a crosslinker and a cure accelerator, wherein the or each cure accelerator is adapted to be in the same phase as the PBM within the hair fiber and is present in a total concentration of from 0.001 wt % to 5 wt %, from 0.005 wt % to 5 wt %, based on the weight of the hair styling composition; II) a co-polymerization agent comprising at least one functional group capable of cross-polymerizing with at least one of the PBM and the cure accelerator, wherein, if present, the or each co-polymerization agent functional group is selected from hydroxyl, carboxyl, amine, anhydride, isocyanate, isothiocyanate, and double bond; and III) co-solvents, wherein the or each co-solvent is present in an amount sufficient to form an oil-in-water emulsion, and wherein at least one co-solvent is adapted to be in the same phase as the PBM within the hair fiber; and further comprising at least one of 3. The method of claim 1 or 2, wherein the hair styling composition has a pH that allows at least a portion of the PBM(s) and WHA(s) to penetrate into the hair fiber, said pH being in a range other than the isoelectric point of the hair.

5. The following steps: I) before applying the hair styling composition to the hair fiber: A—prepolymerizing the at least one PBM, and, if present, the at least one cure accelerator, and / or the at least one co-polymerization agent before mixing with water, and / or B—pre-treating the hair fiber by at least one of: a) washing the hair fiber; b) drying the hair fiber; and c) applying a pre-treatment composition to the hair fiber; and / or II) after step b), at least one of: [I] removing excess hair styling composition from the hair fiber surface by rinsing the fibers with a rinse solution before applying energy that results in at least partial curing, and [II] applying a curing composition comprising a cure accelerator to the hair fibers; and / or III) maintaining the hair fiber in a desired modified shape during step c), which modified shape is different from the natural shape; and / or IV) after step c), at least one of [III] washing the fibers with a washing liquid and [IV] conditioning the fibers with a conditioning liquid; The method of claim 1 or 2, further comprising one or more of:

6. 3. The method of claim 1 or 2, wherein the treated fiber and the untreated fiber exhibit at least one endothermic temperature within 4°C, within 3°C, within 2°C, or within 1°C of each other as measured by thermal analysis.

7. 1. A hair styling composition for modifying the shape of mammalian hair fibers, the composition comprising: a) at least one energy-curable water-insoluble phenolic monomer (PBM) having an average molecular weight of 10,000 g / mol or less; b) at least one polar, water-soluble hygroscopic agent (WHA); and c) water; wherein the hair styling composition has the following characteristics: a- the hair styling composition contains less than 0.1 wt% of small reactive aldehydes (SRAs), the SRAs being selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals; b- the hair styling composition contains less than 1 wt% amino acids; c- the hair styling composition contains less than 1 wt% peptides; and d- the hair styling composition contains less than 1 wt% protein; The hair styling composition further characterized by one or more of:

8. At least one energy-curable, water-insoluble PBM has the general formula I: 【Chemistry 3】 where: i) R １ , R ２ , R ３ , and R ５ are each independently a hydrogen atom, a hydroxyl, or a linear, branched, or cyclic, substituted or unsubstituted C １ ~C ２０ Alkyl, C １ ~C ６ Alkoxy, C １ ~C ６ Allyl, C １ ~C ８ Aromatic esters, or C １ ~C ８ is a non-aromatic ester; and ii) R ４ is a hydrogen atom, a hydroxyl, or a saturated or unsaturated C Ｘ H Ｙ alkyl, where X is an integer less than or equal to 15, and Y is equal to 2X+1-n, where n is selected from 0, 2, 4, and 6; The hair styling composition of claim 7.

9. At least one of R 1 , R 2 , and R 3 is a carboxylic acid ester, and the PBM, or each PBM, has: A) a carboxylate substituent selected from R １ and the PBM is selected from the group comprising 2-hydroxybenzoic acid derivatives; B) the carboxylate substituent is R ２ wherein the PBM is selected from the group comprising 3-hydroxybenzoic acid derivatives; or C) wherein the carboxylate substituent is R ３ wherein the PBM is selected from the group comprising 4-hydroxybenzoic acid derivatives; 9. The hair styling composition of claim 8, wherein the hydroxybenzoic acid ring of the PBM is either unsubstituted or further substituted with one or more hydroxyl groups, and / or the carboxylate substituent is either unsubstituted or further substituted with a hydroxyl or amine group.

10. The or each water-soluble moisture absorbent has the following structural characteristics: i) WHA is a non-electrolyte; ii) the WHA has a hydrogen bond energy with water of at least 21 kJ / mol; iii) the WHA has a hydrogen bond energy with water of at most 40 kJ / mol; iv) the WHA has a hydrogen bond energy with water in the range of 21 kJ / mol to 40 kJ / mol; v) the WHA has a solubility in water of 5 wt % or more, based on the weight of water, measured at a temperature of 25°C; vi) the WHA has a solubility in water of not more than 150 wt %, based on the weight of water, measured at a temperature of 25°C; vii) the WHA has a solubility in water in the range of 5 wt % to 150 wt %, based on the weight of water, measured at a temperature of 25°C; viii) the WHA has a solubility in the hair styling composition or its aqueous phase of 5 wt % or more, based on the weight of the composition or its aqueous phase, measured at a temperature of 25°C; ix) the WHA has a solubility in the hair styling composition or its aqueous phase of 140 wt % or less, based on the weight of the composition or its aqueous phase, measured at a temperature of 25°C; x) the WHA has a solubility in the hair styling composition or its aqueous phase in the range of 5 wt % to 140 wt %, based on the weight of the composition or its aqueous phase, measured at a temperature of 25°C; xi) WHA is the melting temperature (T ｍ ) is 25°C or higher; xii) WHA is the melting temperature (T ｍ ) is 200°C or less; xiii) WHA is the melting temperature (T ｍ ) is in the range of 25°C to 200°C; xiv) WHA is the boiling temperature (T ｂ ) is 100°C or higher; xv) WHA is the boiling temperature (T ｂ ) is 300°C or less; xvi) WHA is the boiling temperature (T ｂ ) is in the range of 100°C to 300°C; xvii) the WHA has a vapor pressure of 2.3 kPa or less, measured at 25°C; and xviii) the WHA has a vapor pressure of 1 mPa or more, measured at 25°C; 10. The hair styling composition of any one of claims 7 to 9, characterized by at least one, at least two, or at least three of:

11. 10. The hair styling composition of any one of claims 7 to 9, wherein each of the at least one WHA is selected from the group consisting of carboxamides, monosaccharides, and disaccharides.

12. A hair styling composition as claimed in claim 11, wherein the or each WHA is 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 radical having not more than 6 carbon atoms, or a hydrogen atom, the organic radical of R with or without a second carboxamide group, said carboxamide being selected from the group consisting of urea, methanamide, ethanamide, propanamide, butanamide, cyclopropanecarboxamide, cyclobutanecarboxamide, cyclopentanecarboxamide; cyclohexanecarboxamide; ethanediamide, propanediamide, butanediamide, pentanediamide, hexanediamide; alaninamide, asparagineamide, glutaminamide, glycinamide, and prolinamide.

13. The hair styling composition is an oil-in-water emulsion, wherein at least one energy-curable water-insoluble PBM is present in the oil phase of the emulsion and at least one WHA is present in the water phase of the emulsion, comprising: A - the total concentration of the at least one energy-curable water-insoluble PBM is at least 0.1 wt. % and / or at most 5 wt. % based on the weight of the hair styling composition; and / or B - the total concentration of the at least one WHA is at least 10 wt. % and / or at most 50 wt. % based on the weight of the hair styling composition; A hair styling composition according to any one of claims 7 to 9.

14. The hair styling composition comprises: I) a cure accelerator selected from a crosslinker and a cure accelerator, wherein the or each cure accelerator is adapted to be in the same phase as the PBM within the hair fiber, and wherein the total concentration of the at least one cure accelerator is at least 0.001 wt. % and / or at most 5 wt. % based on the weight of the hair styling composition; II) a co-polymerization agent comprising at least one functional group capable of cross-polymerizing with at least one of the PBM and, if present, the cure accelerator, wherein the functional group is selected from: hydroxyl, carboxyl, amine, anhydride, isocyanate, isothiocyanate, and double bond, and wherein the concentration of the co-polymerization agent is from 0.01 wt % to 2 wt % based on the weight of the hair styling composition; III) C having at least one hydroxyl group １ ~C １０ a cosolvent selected from the group consisting of alcohols, water-miscible ethers, aprotic solvents, esters, and mineral or vegetable oils; and IV) an additive selected from the group comprising emulsifiers, wetting agents, thickeners and charge control agents; The hair styling composition of any one of claims 7 to 9, further comprising at least one of:

15. When present, the or each accelerator is: a) a crosslinker selected from reactive silanes having at least two silanol groups and a molecular weight of at most 1,000 g / mol, mixtures of reactive silanes and aminosilanes, polybasic acids, polyols, polyamines, mono- and diglycidyl, diisocyanate, allyl compounds, polyphenols, acrylates, silsesquioxanes having attached organic glycidyl or methacrylate groups, and linear, branched or cyclic alkene compounds containing up to 15 carbon atoms and containing enough double bonds to form at least two radicals upon opening of the double bond; or b) a curing accelerator suitable for at least one of condensation polymerization and addition polymerization, such as a metal complex, a metal soap, a metal salen, and an organic peroxide; the curing accelerator selected from 15. The hair styling composition of claim 14, wherein

16. The hair styling composition comprises: a) a glass transition temperature (T ｇ ); and / or b) a pH different from the isoelectric point of the mammalian hair fiber to be styled, to allow at least partial penetration of the PBM(s) and WHA(s) into the hair fiber; The hair styling composition of any one of claims 7 to 9, having

17. 1. A kit for styling mammalian hair fibers, said kit comprising: i) a first compartment containing at least one energy-curable water-insoluble phenolic monomer (PBM) having an average molecular weight of 10,000 g / mol or less; and ii) at least one polar water-soluble moisture absorbent (WHA), and i) water; and ii) pH adjusters; a second compartment containing at least one of: Including, wherein the contents of the second compartment are a liquid having a pH selected to increase penetration of at least a portion of the PBM into the hair fiber; and wherein at least one of the PBM(s) in the first compartment and at least one of the WHA(s) in the second compartment are a PBM or WHA of a hair styling composition according to any one of claims 7 to 16, respectively, and mixing the contents of the two compartments produces an oil-in-water emulsion; The kit further comprises at least one of: a) a cure accelerator selected from a crosslinker and a cure accelerator; b) a co-polymerization agent; and c) a co-solvent.

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