Compositions, kits and methods for styling hair fibers

Abstract

The present disclosure relates to a method for styling mammalian hair fibers, including adding volume, straightening, relaxing, curling, or applying any other desired modification to the shape of the hair. The method involves applying a hair styling composition containing at least one hair-penetrating phenolic monomer to the hair, allowing the monomer to penetrate into the hair, and curing the monomer to form an internal polymer that can overcome the tendency of the hair to return to its natural shape. If the curing is performed while the hair is in a state where it has been modified to a desired shape, the resulting polymer can maintain the modified shape. Also disclosed are suitable compositions and kits for preparing the same.

Description

[Technical Field]

[0001] Related Applications This application claims Paris Convention priority of UK Application No. 2006573.6 filed May 4, 2020, and UK Application No. 2010599.5 filed July 9, 2020. The entire disclosures of all of the foregoing applications are incorporated herein by reference for all purposes as if fully set forth herein.

[0002] Technical Field SUMMARY The present disclosure relates to compositions, kits, and methods for styling keratinous fibers, such as mammalian hair. [Background technology]

[0003] 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 the central hair shaft, which is composed of the cortex and medulla. This cuticle layer is made up of overlapping, scale-like cells that stack together like roof shingles. The physical appearance and shape of a hair fiber are determined by the various interactions between keratin chains within the fiber, and the amino acid composition of keratin determines the types of interactions possible. While cysteine ​​side chains allow for the formation of disulfide bonds, 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 within the fiber, their proportion along the fiber, and their capacity due to the fiber's configuration determine the occurrence of these interactions and the appearance of hair composed of a fiber or multiple such fibers.

[0004] 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).

[0005] One such procedure, called "Japanese straightening," uses reducing agents, such as mercaptans or sulfites, to selectively cleave disulfide bonds, thereby mechanically relaxing the keratin, after which the free sulfhydryl groups are reoxidized and the disulfide bonds are rebonded 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 compression to permanently conform the hair to the desired shape, whether straight or wavy.

[0006] Another procedure for permanent styling of hair involves the use of stronger reducing agents, such as strong alkalis with a pH above 11.0, which cleave disulfide bonds in a less selective manner that interferes with possible rearrangement of disulfide bonds as the alkalis penetrate deeper into the pH-induced swollen hair.

[0007] Other procedures, known as "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; most straighteners contain 2-10% of these chemicals. Examples of formaldehyde-generating agents, also known as 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 hair fibers and act as crosslinkers, thereby prolonging the life of the new hair form and shape. Formaldehyde and glutaraldehyde are known carcinogens and can cause eye and nose irritation and allergic reactions to the skin, eyes, and lungs. As a result, they have been deemed hazardous by the Occupational Safety and Health Administration (OSHA), which requires hair styling product manufacturers to limit their use to 0.2 wt% or less, and even 0.1 wt% or less in some jurisdictions. OSHA has tested several keratin treatments and found that even when products are marketed as "formaldehyde-free" or do not include formaldehyde in their ingredient lists, many contain formaldehyde in solution or release formaldehyde when heated, raising public doubts about the safety claims of "non-formaldehyde" keratin straightening products. It has been reported that in such products, formaldehyde may simply be replaced by formaldehyde-generating agents. While such products penetrate the hair fiber below the cuticle to some extent, they are believed to work primarily through a superficial coating, and this external protective sheath is the basis for the smoothing and gloss benefits achieved by this method. However, this is a temporary effect as the coating strips moisture from the hair, leaving it brittle, dry and dull as the protective keratin-containing film thins.

[0008] Some permanent or semi-permanent straightening methods require the use of specialized shampoos to maintain the effect over 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 you want to further modify the hair color, hair style, or return to a natural style, which usually requires a new permanent treatment that further damages the hair or waiting for hair regrowth.

[0009] 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. Exposing hair to heat (e.g., a flat iron or hair dryer can remove moisture from hair) can disrupt these hydrogen bonds, allowing them to recombine upon drying or cooling, allowing for temporary hair styling. While these methods do not use chemicals that damage hair, their effects are only temporary due to the sensitivity of the fibers formed in this way to water, such as the relative humidity of the environment. Summary of the Invention [Problem to be solved by the invention]

[0010] The classification of hair styling methods as permanent, semi-permanent, or temporary usually depends on the number of shampoos required for the hair to regain its natural shape. Permanent methods can be harsh enough to require new hair fiber growth, and although some non-temporary styling may reverse itself, such methods can themselves be damaging.

[0011] Therefore, there is a need for a hair styling method that reduces hair damage and the need for harmful reagents, while advantageously providing long-lasting hair style and shape. [Means for solving the problem]

[0012] 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 drawbacks 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 (straightening) or relaxing the hair if it is wavy, curly, or coiled; or conversely, curling the hair if it is relatively straighter than desired; thus optionally increasing or decreasing the natural tendency of the hair fiber to be curly.

[0013] Advantageously, the curable compositions and methods of the present teachings enable temporary or permanent hair styling without severing disulfide bonds within the hair fiber or permanently altering its molecular structure. Thus, if a hair fiber has a certain number of sulfur bonds in its native (unmodified) configuration prior to styling according to the present teachings, the fiber styled to have a modified configuration will exhibit essentially the same number of sulfur bonds. Alternatively, the harmlessness of the present compositions and methods can be assessed by modified hair fibers exhibiting essentially the same physicochemical structure as native hair fibers. For example, in some embodiments, the mechanical properties of the hair fiber are not impaired by the present compositions and methods, and in certain embodiments, some properties may even be improved. The fact that the chemical structure of the hair fiber is not adversely affected can be demonstrated, for example, by thermal analysis, in which modified (treated) and native (untreated) hair fibers may exhibit at least one essentially similar endothermic temperature (as determined by various methods, e.g., 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 fiber and the untreated fiber serving as the reference are measured by the same thermal analysis method, with DSC being preferred. [Brief explanation of the drawings]

[0014] [Figure 1AB] Figure 1A shows an image taken by focused ion beam milling combined with scanning electron microscopy (FIB-SEM) showing the cross section of a reference untreated hair fiber. Figure 1B is a schematic representation of the SEM image shown in Figure 1A. [Figure 2AB] Figure 2A is a FIB-SEM image showing the cross section of a hair fiber treated with a CNSL oil-in-water emulsion according to one embodiment of the present invention, and Figure 2B is a schematic representation of the FIB-SEM image of Figure 2A. [Figure 3AB] Figure 3A is an SEM image of a top view of a hair fiber treated with a control solution, and Figure 3B is an SEM image of a top view of a hair fiber treated with a CNSL oil-in-water emulsion according to one embodiment of the present invention. [Figure 4] FIG. 4 is an image taken by FIB-SEM showing the cross section of a hair fiber treated with a CNSL oil-in-water emulsion according to one embodiment of the present invention, before any washing cycle of the hair. [Figure 5AB] Figure 5A is an image taken by FIB-SEM showing the cross section of a hair fiber treated with the same CNSL oil-in-water emulsion as shown in Figure 4 after 49 washes, taken at a voltage of 1.20 kV. Figure 5B is an image taken by FIB-SEM showing the cross section of a hair fiber treated with CNSL oil-in-water emulsion as shown in Figure 5A after 49 hair wash cycles, but taken at a voltage of 10 kV. [Figure 6A] FIG. 6A shows a photograph of an untreated curly black hair fiber compared to a similar curly black hair fiber treated with a CNSL oil-in-water emulsion according to one embodiment of the present invention (FIG. 6B). [Figure 6B] FIG. 6A shows a photograph of an untreated curly black hair fiber compared to a similar curly black hair fiber treated with a CNSL oil-in-water emulsion according to one embodiment of the present invention (FIG. 6B). [Figure 7]FIG. 7 shows a series of Differential Scanning Calorimetry (DSC) plots of the thermal analysis of hair samples, including a reference untreated hair sample, two hair samples treated by a commercial method, and one hair sample treated with a CNSL oil-in-water emulsion according to one embodiment of the present invention. [Figure 8] FIG. 8 is a simplified schematic diagram of a hair styling method according to one embodiment of the present teachings. [Figure 9AB] FIG. 9A shows the breaking stress of hair fibers as a function of treatment, shown as a percentage of untreated hair; and FIG. 9B shows the tenacity of hair fibers as a function of treatment, shown as a percentage of untreated hair. DETAILED DESCRIPTION OF THE INVENTION

[0015] Mechanical properties such as tensile strength of hair fibres can be assessed using conventional methods, and it has been found that the tensile strength of hair fibres treated by the method of the present invention is not reduced (e.g. the modulus of elasticity of treated and untreated fibres is similar), and some parameters such as the breaking stress and toughness of the hair fibre may even be increased.

[0016] 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 its native shape to a desired modified shape, the method comprising: a) applying to individual hair fibers a hair styling composition that covers the hair fibers, said hair styling composition comprising at least one hair fiber-penetrating monomer (HPM) and optionally one or more curing facilitators miscible therewith; b) leaving the composition in contact with the hair fiber for a time sufficient to ensure at least partial penetration of the HPM(s) into the hair fiber; and c) applying energy to the hair fiber to at least partially cure at least a portion of the HPM that has penetrated into the hair fiber, wherein said partial curing optionally occurs while the hair fiber is in the desired modified shape.

[0017] In a second aspect of the present invention, there is provided a method of styling mammalian hair fibres by modifying the shape of the fibre from its native shape to a desired modified shape, the method comprising: a) applying to individual hair fibers a hair styling composition that covers the hair fibers, said hair styling composition comprising at least one phenol-based monomer (PBM) and optionally one or more curing accelerators miscible therewith; b) leaving the hair styling composition in contact with the hair fiber for a time sufficient to ensure at least partial penetration of the PBM(s) into the hair fiber; and c) applying energy to the hair fiber to at least partially cure at least a portion of the PBM that has infiltrated within the hair fiber, wherein said partial curing optionally occurs while the hair fiber is in the desired modified shape.

[0018] In some embodiments of the first and second aspects, the hair styling composition contains less than 0.2 wt. % small reactive aldehyde (SRA), the SRA being selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals.

[0019] In some embodiments, prior to step a) applying a hair styling composition comprising an HPM or PBM, the hair fiber is dried at a temperature and for a time sufficient to ensure severing of at least a portion of the hydrogen bonds in the hair fiber.

[0020] As will be explained in more detail in the context of restyling and destyling, the actual styling step that imparts a modified shape to hair fibers treated by the method of the present invention does not necessarily occur simultaneously with the curing of the monomers, which gradually form polymers that can overcome the tendency of the hair fiber to return to its previous (e.g., unmodified / native / unmodified) shape. Once the polymers are formed within the hair fiber, their shape can be modified later as desired. This treatment method can be considered a styling method regardless of the timeline of modifying the overall shape of the fiber, and can also be considered a styling effect regardless of the degree of detectability of the change, simply because the formation of polymers within the fiber can impart volume.

[0021] In some embodiments, the energy applied to at least partially cure at least a portion of the energy-curable monomers (HPM or PBM) 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 applied energy is more generally electromagnetic (EM), which may include, for example, ultraviolet (UV) radiation in addition to the IR radiation mentioned above. Some HPMs are primarily or solely curable by thermal energy (heat), while others are primarily or solely curable by electromagnetic energy. The former are sometimes referred to as thermosetting monomers, and the latter are sometimes referred to as EM-curable monomers. In some embodiments, HPMs may be curable by both mechanisms, in which case they may be referred to as hybrid-curable monomers.

[0022] In some embodiments of the first and second aspects, 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.

[0023] In a third 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 while at a temperature below its softening temperature, and wherein 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 fiber is in a second modified hair shape of the desired restyling, the second modified hair shape being the same as or different from the first shape.

[0024] 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.

[0025] 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.

[0026] In a fourth aspect of the present invention, there is provided a method of destyling hair fibres having an altered hair shape achieved by the styling method or hair styling composition as further detailed herein, namely a method of destyling hair fibres comprising therein a synthetic polymer having a softening temperature, said synthetic polymer being capable of imparting shape to the hair fibre whilst at a temperature below its softening temperature, said destyling method comprising: a) applying energy to a hair fiber having a first shape, wherein said application of energy is for a time sufficient to soften a 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; b) 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 c) ceasing the application of said energy and water while the hair fiber is devoid of artificial restraint, so as to allow the polymer to resume its unsoftened shape while the hair fiber is in its native, unaltered shape.

[0027] In some embodiments, fibers with their native, 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.

[0028] The ability to restyling or de-styling hair previously treated with the methods and compositions of the present invention (i.e., hair fibers containing therein polymers synthesized in situ by crosslinking PBM) is advantageous and unexpected in the art, where conventional methods typically require the application of an appropriate composition to further alter the hair shape.

[0029] In a fifth aspect of the present invention, there is provided a hair styling composition for modifying the shape of mammalian hair fibres, the hair styling composition comprising: A - A single-phase composition, said single phase comprising at least one hair fibre penetrating monomer (HPM), water having a pH selected to enhance penetration of said HPM(s) into the hair fibre, and a co-solvent, said single phase optionally further comprising one or more set accelerators miscible therewith; and B- An oil-in-water emulsion, said emulsion consisting of: a) an oil phase containing at least one hair fiber penetrating monomer (HPM); and b) an aqueous phase having a pH selected to enhance the penetration of said monomer into the hair fiber; is selected from The hair styling compositions are further described herein and in the accompanying claims.

[0030] In a sixth aspect of the present invention, there is provided a hair styling composition for modifying the shape of mammalian hair fibres, the hair styling composition comprising: A - A single-phase composition, said single phase comprising at least one phenolic monomer (PBM), water having a pH selected to increase the penetration of said monomer into the hair fiber, and a co-solvent, said single phase optionally further comprising one or more cure accelerators miscible therewith; and B - an oil-in-water emulsion, said emulsion consisting of a) an oil phase comprising at least one phenolic monomer (PBM) and optionally one or more set accelerators miscible therewith, and b) an aqueous phase having a pH selected to increase the penetration of the monomers into the hair fiber; is selected from The hair styling compositions are further described herein and in the accompanying claims.

[0031] In some embodiments of the fifth and sixth aspects, the hair styling composition contains less than 0.2 wt. % small reactive aldehyde (SRA), the SRA being selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals.

[0032] In some embodiments of the fifth and sixth aspects, the hair styling composition further comprises 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, the functional group being chosen from: hydroxyl, carboxyl, amine, anhydride, isocyanate, isothiocyanate, and double bond.

[0033] In some embodiments of the fifth and sixth aspects, the hair styling composition further comprises at least one additive selected from the group comprising emulsifiers, humectants, thickeners, and charge control agents.

[0034] In a seventh 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 hair fiber penetrating monomer (HPM); and i. Water with a pH selected to enhance penetration of the HPM into the hair fiber; or ii. at least one pH adjuster; A second compartment containing either Including, The compartments are mixed to produce the hair styling composition as a single phase composition or an oil-in-water emulsion, as further described herein and claimed in the appended claims.

[0035] In an eighth 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 phenolic monomer (PBM); and i. water at a pH selected to increase penetration of the monomer into the hair fiber; or ii. at least one pH adjuster; A second compartment containing either Including, The compartments are mixed to produce the hair styling composition as a single phase composition or an oil-in-water emulsion, as further described herein and claimed in the appended claims.

[0036] In some embodiments of the seventh and eighth aspects, at least one HPM or PBM of the first compartment is prepolymerized prior to being placed in the kit.

[0037] 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 a desired storage temperature (e.g., not exceeding room temperature). In some embodiments of the seventh and eighth aspects, with or without prepolymerization of the HPM / PBM, the first compartment is 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.

[0038] In some embodiments of the seventh and eighth aspects, 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 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 cure and / or addition cure) and a cure accelerator is further included in the hair styling composition, kit, or method. In some embodiments, the present compositions and methods may include two or more types of crosslinkers that enable both addition cure and condensation cure of the prepolymer in combination. Such a cure accelerator can be placed in the first or second compartment if it does not spontaneously react (e.g., at room temperature) with any one of the components in the first or second compartment, respectively. Alternatively, the cure accelerator can be placed in a separate, additional compartment so that it is 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] In some embodiments of the seventh and eighth aspects, the first compartment of the kit further comprises at least one co-polymerization agent.

[0041] In some embodiments, the kit further comprises at least one co-solvent, which may be contained in the first, second, or another additional compartment.

[0042] In some embodiments of the seventh and eighth aspects, the kit further comprises at least one additive selected from the group comprising an emulsifier, a humectant, a thickener, and a charge control agent. 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.

[0043] In certain embodiments, a kit for styling mammalian hair fibers is provided, the kit comprising: a) a first compartment comprising at least one PBM and at least one co-polymerization agent; b) a second compartment containing water and at least one co-solvent having a pH in the range of 5 to 11; and c) a third compartment containing one or more cross-linking agents compatible with condensation curing of the PBM; Including, The kit optionally comprises: (a) at least one crosslinker compatible with addition curing of the PBM; (b) cure accelerators; (c) cosolvent; (d) an emulsifier; and (e) thickeners; and further comprising at least one of Any of (a)-(c) may each be independently disposed in a first, second or other additional compartment(s), and any of (d) and (e) may each be independently disposed in a second or other additional compartment(s).

[0044] In one embodiment, the kit further comprises at least component (a) listed above. In one embodiment, the kit further comprises at least component (b) listed above. In one embodiment, the kit further comprises at least component (c) listed above. In one embodiment, the kit further comprises at least component (d) listed above. In one embodiment, the kit further comprises at least component (e) listed above.

[0045] In one embodiment, the kit further comprises at least components (a) and (b) listed above. In one embodiment, the kit further comprises at least components (a) and (c) listed above. In one embodiment, the kit further comprises at least components (a) and (d) listed above. In one embodiment, the kit further comprises at least components (a) and (e) listed above. In one embodiment, the kit further comprises at least components (a), (b), (c), (d), and (e) listed above.

[0046] In a ninth aspect of the present invention, there is provided a mammalian hair fibre having a shape other than its native shape, said hair fibre comprising therein an at least partially cured hair fibre-penetrating monomer (HPM), hair fibre-penetrating oligomer (HPO) or hair fibre-penetrating polymer (HPP); the HPM, HPO or HPP corresponding to the components of the hair styling composition as further detailed herein and at least partially cured versions of said components.

[0047] In a tenth aspect of the present invention, there is provided a mammalian hair fibre having a shape other than its native shape, said hair fibre comprising therein at least partially cured phenolic monomer (PBM), phenol-based oligomer (PBO), or phenol-based polymer (PBP); the PBM, PBO, or PBP corresponding to the components of the hair styling composition as further detailed herein and at least partially cured versions of said components.

[0048] Additional objects, features, and advantages of the present disclosure will be set forth in the detailed description that follows, and in part will become readily apparent to those skilled in the art from this specification or may be learned by practice of the present disclosure as set forth in this specification and claims, as well as the accompanying drawings. Various features and sub-combinations of the embodiments of the present disclosure may be employed without reference to other features and sub-combinations.

[0049] 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, in which like reference numerals or characters indicate corresponding or similar components. This description, together with the drawings, will make apparent to those skilled in the art how some embodiments of the present disclosure may be implemented. The drawings are for illustrative discussion purposes and do not attempt to show structural details of the embodiments in more detail than is necessary for a fundamental understanding of the present disclosure. For clarity and convenience of illustration, some of the features shown in the drawings have not necessarily been drawn to scale.

[0050] Detailed Description The present disclosure relates to compositions for styling hair fibers, and more particularly to curable compositions comprising at least one hair fiber-penetrating monomer (HPM) or phenolic monomer (PBM) capable of undergoing polymerization by any suitable reaction to produce a polymer (e.g., a polymer). As used herein, the term monomer is not meant to include only a single repeating molecule, but may also include short oligomers, so long as the repeat number results in a molecular weight of 10,000 g / mol, 5,000 g / mol, or 3,000 g / mol or less, as deemed appropriate for the molecule's ability to penetrate the hair fiber. Hair styling compositions allow for the delivery of energy-curable monomers, along with any compounds necessary for proper polymerization, to the interior of the hair fiber, where such compounds are in situ miscible with the monomers. The compounds that are miscible with the monomers and promote their curing may be cure accelerators and / or cosolvents. Such compounds 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 selected from single-phase compositions and oil-in-water emulsions, both of which generally have a pH adapted to promote penetration of the monomer. The promoting pH can act by promoting a) sufficient opening of the hair scales and / or b) sufficient charging of the hair fiber and hair styling composition (e.g., as measured by zeta potential); 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 between pH 9 and pH 11. In other words, the pH is determined to be favorable for penetration into the hair fiber as long as it is outside the isoelectric point of the hair, and may vary slightly between 3.5 to 5, 4 to 5, or 3.5 to 4, depending on the hair fiber and its health.

[0051] Methods for preparing and using the same, and kits containing such compositions and enabling such styling, are also described.

[0052] The principles, applications, and embodiments of the teachings herein may be better understood with reference to the accompanying specification and figures. Upon perusal of the description and figures presented herein, one skilled in the art will be able to practice the present disclosure without undue effort or experimentation.

[0053] Before describing at least one embodiment in detail, it should be understood that the present disclosure is not necessarily limited in its application to the details of structure and configuration of the components and / or methods set forth herein. The present disclosure is capable of other embodiments or of being practiced or carried out in various ways. The terms and phrases used herein are for purposes of description and should not be considered limiting. For example, while many references are made to hair to describe the benefits of the present invention, it should be clear that the teachings of the present invention equally apply to wigs, hair extensions, or eyelashes, to name a few options. Thus, providing a durable hairstyle may refer to hair, wigs, or hair extensions attached to a human subject, and the term may further refer to eyelashes, including, by way of example, providing a durable eyelash shape.

[0054] It will be understood that both the foregoing general description and the following detailed description, including materials, methods, and examples, are merely exemplary of the present disclosure and are intended to provide an overview or framework for understanding the nature and character of the present disclosure as claimed, and are not intended to be necessarily limiting.

[0055] In one aspect of the present invention, a method is provided for styling mammalian hair fibers by modifying the shape of the mammalian hair fiber.

[0056] In the first step of the method of the present invention, a liquid hair styling composition is applied to individual hair fibers, the liquid composition being a single-phase composition or oil-in-water emulsion comprising water and: i) at least one hair fiber-penetrating monomer (HPM) or phenolic monomer (PBM). When the hair styling composition is provided as a single phase, a suitable cosolvent is provided in an amount sufficient to ensure miscibility of the monomer with the water portion of the liquid, and the aqueous medium containing the cosolvent is further compatible with the miscibility of any other materials desired for polymerization of the monomer (e.g., optional cure accelerators and / or copolymerization agents) or for the composition's form and applicability (e.g., emulsifiers, humectants, thickeners, etc.). When the hair styling composition is provided as a two-phase emulsion, a cosolvent, if present at all, is provided to ensure miscibility of at least the monomer with any cure accelerator, the monomer being present in the oil phase of the emulsion.

[0057] Before detailing specific compounds suitable for the methods and compositions of the present invention, it should be emphasized that, in addition to the aforementioned ability of the monomers (and any agents accelerating their polymerization) to penetrate into hair fibers and be miscible with each other after and / or until curing is set to proceed, these materials must generally be compatible with styling compositions and their methods of preparation and use. By "compatible," we mean that the monomer, cure accelerator, co-polymerization agent, cosolvent, or other compatible component of the composition does not adversely affect the effectiveness of any other compound or the ability to prepare or use the final composition. "Compatibility" can be chemical, physical, or both, and can depend on relative amounts. For example, a cure accelerator is considered compatible if it has functional groups compatible with cross-linking between monomers and / or otherwise accelerating the process. A cosolvent is considered compatible if it has a sufficiently slow rate of change so that polymerization proceeds while the related 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 is subjected during preparation or use of the composition for hair styling. Although not required, all materials can be liquid at room temperature (about 23°C) for ease of preparation and use, or, if solid, can be easily miscible with the liquid components of the composition. Furthermore, 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 relative to the appropriate heating temperature to selectively promote its dissolution without causing the thermosetting monomer to cure faster than normal or otherwise affecting its polymerization ability. If desired, a plasticizer can be included to keep the hair styling composition, particularly the monomers and other curable components intended to penetrate hair fibers, liquid at room temperature.

[0058] Returning to the premise that such compounds are usually able to penetrate into hair fibers after the hair scales have properly opened, without wishing to be bound by any particular theory, it is believed that smaller molecules can migrate into fibers more easily than larger molecules. Although the physical size of the molecule may depend on additional factors (such as a particular structure and "compactness," or lack thereof), the molecular weight of the compound can help estimate its ability to penetrate fibers. In some embodiments, materials for polymerization within hair fibers (e.g., monomers and crosslinkers), or materials for facilitating such polymerization (e.g., co-polymerization agents, cosolvents, and cure accelerators) have an average molecular weight 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.

[0059] In one embodiment, at least one HPM is a PBM. In one such embodiment, at least one PBM is of general formula I: [ka] During the ceremony, R1, R2, R3 and R5 each independently represent a hydrogen atom, a hydroxyl, a linear, cyclic or branched, substituted or unsubstituted C1 to C 20 alkyl, C1-C6 alkoxy, C1-C6 aryl, C1-C8 phenyl ester, or C1-C8 glycol ester; and R4 is a hydrogen atom, a hydroxyl, or a saturated or unsaturated C X H Y alkyl, 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.

[0060] In some embodiments, R1, R2, R3, and R5 are each independently a hydrogen atom, hydroxyl, methyl, 2-propenyl, phenylacetate, ethylene glycol monoacetate, or methoxy. In other embodiments, R4 is a hydrogen atom, hydroxyl, or C 15 H 31-n alkyl, and n is selected from 0, 2, 4 and 6.

[0061] In embodiments, if the composition comprises at least one PBM of general formula I, where R4 is hydroxyl and R1, R2, R3 and R5 are all hydrogen atoms, and the monomer, i.e., benzene-1,3-diol, is also known as resorcinol, then the composition may further need to comprise at least a second HPM or PBM of general formula I, a second HPM or PBM other than resorcinol, and optionally a cure accelerator.

[0062] In certain embodiments, at least one PBM is selected from any of the following Formulae II-V: [ka]

[0063] C of PBM 15 H 31-n The side chains are hydrocarbon (alkyl) substituents with varying degrees of unsaturation, i.e., they can be saturated (n=0), monoene (n=2), diene (n=4), and triene (n=6) hydrocarbon side chains.

[0064] In some embodiments, the compound of general formula II constituting at least one of the PBMs of the present composition is a cardanol derivative, which can be selected from the group consisting of 3-pentadecylphenol (n=0), 3-[pentadeca-8-enyl]phenol (n=2), 3-[pentadeca-8,11-dienyl]phenol (n=4), 3-[pentadeca-8,11,14-trienyl]phenol (n=6), and conformers thereof.

[0065] In another embodiment, the compound of general formula III constituting at least one of the PBMs of the present composition is a cardol derivative, which can 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.

[0066] In yet another embodiment, the compound of general formula IV constituting at least one of the PBMs of the present composition is a 2-methyl cardol derivative, which can 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.

[0067] In certain embodiments, at least one PBM of the composition is cashew nut shell liquid (CNSL) or a component thereof.

[0068] CNSL is produced 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. CNSL components are phenolic compounds of the general formulas II-IV shown above, in which the R4 side chain has varying 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, as depicted below. [ka]

[0069] 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 between 60 and 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 (general 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.

[0070] The saturated and unsaturated derivatives of each of the CNSL components can be present in varying 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 methods such as molecular distillation, thin layer chromatography (TLC) / gas liquid chromatography (GLC), and TLC-mass spectrometry.

[0071] The hydroxyl groups (-OH) of PBM, along with varying degrees of unsaturation when the R4 side chain is other than a hydroxyl group or a saturated hydrocarbon, make PBM a highly polymerizable material capable of undergoing a variety of polymerization reactions (e.g., by condensation or addition). Without wishing to be bound by theory, it is believed that PBM can be polymerized by condensation of its hydroxyl groups with other condensation-polymerizable groups, while suitable R4 side chain unsaturation can, under appropriate conditions, be the basis for addition polymerization.

[0072] In some embodiments, to accelerate polymerization, hair styling compositions (e.g., single-phase or oil-in-water emulsions) compatible with the hair styling method of the present invention further comprise, in addition to at least one HPM or PBM, ii) at least one curing facilitator selected from crosslinkers and curing accelerators. A crosslinker refers to a compound that actively participates in the curing process and becomes incorporated into the resulting polymer network, while a curing accelerator can merely catalyze or activate curing (e.g., by lowering the polymerization temperature or increasing its rate). The curing accelerator should preferably be oil-miscible so that it is in phase with the oily monomers when polymerized within the hair fiber. Note that if a curing accelerator is used after applying the hair styling composition to the hair, the curing accelerator used in such a process can be water-soluble, provided that the accelerator is aqueous.

[0073] In some embodiments, the crosslinker can react with the monomer via a condensation cure mechanism and is referred to as a "condensation-cure crosslinker." In other embodiments, the crosslinker can react with the monomer via an addition cure mechanism and is referred to as an "addition-cure crosslinker." In some embodiments, the same cure accelerator can act as both a crosslinker and a cure accelerator. Regardless of the type of crosslinkable monomer and cure accelerator that 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 imply that the monomers need to be artificial (not naturally occurring), but rather that the resulting polymer is synthesized in situ and is not natively present within the hair fiber. Simply put, the exogenous polymer "locks" the hair fiber into the desired shape, allowing the fiber to overcome its natural forces or otherwise assume or regain its natural shape.

[0074] In some embodiments, crosslinkers suitable for the hair styling compositions and methods of the present invention have two or more crosslinkable functional groups, advantageously three or more crosslinkable functional groups, which can increase the density of the three-dimensional network formed.

[0075] 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 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 (reaction products thereof, optionally combined with a dialkyl maleate, such as dimethyl maleate, diethyl maleate, or dibutyl maleate, to produce an active crosslinker capable of reacting with the monomers of the present 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(cyclohexyl isocyanate); 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.

[0076] As will be readily understood by those skilled in the art of crosslinker-promoted polymerization, such compounds are generally present in an amount corresponding 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 result in an excess of crosslinker, especially if some of the crosslinkable groups of the monomers and increasingly oligomers are inhibited as curing proceeds to form more complex polymers. Nevertheless, in some embodiments, it may be desirable to include more than simply a stoichiometric concentration of such cure accelerators, especially when the crosslinkers, in addition to their ability to react with the monomers, can also react with each other.

[0077] Advantageously, although not necessarily, crosslinkers may further serve to modify the pH of the composition, promoting the opening of the cuticle scales of the hair fiber to which the composition containing them is applied, allowing the HPM or PBM, or a portion thereof, to penetrate into the hair shaft.

[0078] Without wishing to be bound by any particular theory, it is believed that the HPM or PBM according to the present teachings are sufficiently small molecules (e.g., having a molecular weight of 10,000 g / mol or less) to at least partially penetrate the fiber trunk, where they can subsequently polymerize upon application of energy (e.g., heat or electromagnetic radiation suitable for inducing polymerization of the monomers). The penetration of the HPM or PBM into the hair fiber can be observed and monitored by microscopic techniques, such as FIB-SEM (e.g., FIG. 2A , discussed further below). If polymerization occurs while the hair fiber is in the desired modified shape, the resulting hair fiber-penetrating oligomer (HPO) and hair fiber-penetrating polymer (HPP), or, if the HPM is a PBM, phenolic oligomer (PBO) and phenolic polymer (PBP), can maintain the hair fiber in the modified shape or delay the ability of the fiber to resume its native (unmodified) shape. Such processes are described in more detail in a later section.

[0079] Returning to the composition that can be applied to individual fibers as the first step of the hair styling method of the present invention, the crosslinker linkers, if present, can undergo at least partial hydrolysis, e.g., with water, before combination with the HPM or PBM, regardless of any additional benefits they may provide. Alternatively, a hydrolysis accelerator can be used to induce hydrolysis after combination of the crosslinker with the HPM or PBM. Suitable accelerators for such hydrolysis can be acids having (or providing) a pH between 4 and 6, such as salicylic acid, lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, malic acid, tartaric acid, azelaic acid, or propionic acid. The hydrolysis accelerator can be present in the composition applied to the hair fibers and / or can be applied to the hair fibers later. In either case, partial hydrolysis of the appropriate crosslinker is expected to enhance the activity of the crosslinker and promote condensation, which leads to polymerization of the HPM or PBM.

[0080] In some embodiments, cure accelerators suitable for hair styling compositions comprising PBMs, and methods of the present invention using same, are suitable for condensation polymerization and can be selected from, for example, metal complexes (e.g., having the metals Co, Mn, Ce, Fe, Al, Zn, Zr, Se, or Cu) including metal carboxylates such as acetylacetonates or naphthenates; metal soaps such as aluminum stearate, magnesium stearate; metal salen complexes such as complexes of N,N'-bis(salicylidene)ethylenediamine with Fe or Mn; strong acids such as p-toluenesulfonic acid, sulfuric acid, phosphoric acid, sulfosuccinic acid, and the like; and strong bases such as NaOH, KOH, NH4OH, and the like.

[0081] In some embodiments, the PBM of the present invention can further contain at least one addition-curable group, such as a conjugated or non-conjugated double bond, allowing the monomer to undergo both condensation polymerization via the hydroxyl groups of the PBM and addition polymerization. For example, if the PBM is CNSL, its non-conjugated unsaturated alkyl side chain at the R4 position allows such polymerization by addition curing under appropriate conditions. Such conditions include the addition of a cure accelerator to the composition to open the double bond in the side chain to form a radical and initiate addition polymerization. Cure accelerators suitable 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.

[0082] Alternatively, if 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 may 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 specialized cure accelerator.

[0083] 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 H14 O) and farnesene (C 15 H 24 The crosslinker may contain at least one double bond at the end of the alkene chain, such as a short fatty oil or a short monoterpene (e.g., 1,5-hexadiene or 1,5-hexadiene-3,4-diol), or at least one double bond at the end of the alkene chain. Therefore, short alkene crosslinkers with double bonds at both ends of the alkene chain (e.g., 1,5-hexadiene or 1,5-hexadiene-3,4-diol) are also suitable.

[0084] 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 another crosslinker optionally donates only one radical upon double bond opening.

[0085] Polymerization of PBM upon addition curing, either alone or in combination with additional components of the hair styling compositions of the present invention, can be monitored by standard methods. For 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 interior portion of hair fibers using 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 materials extracted from the hair fiber after penetration and curing. Materials, including synthetic internal polymers, can be extracted from the hair fiber by diffusion (e.g., immersion in IPA at 40-60°C for 2 hours) and concentrated to obtain a sample compatible with the test method. Iodine value can be measured by standard methods, such as those described in ASTM D-1959.

[0086] While compositions and methods according to the present teachings can be applied and practiced on isolated hair fibers (e.g., on fur or wigs), they are generally intended for use on the hair of live mammalian subjects, particularly the human scalp. Accordingly, while numerous crosslinkers, cure accelerators, or other agents and additives, as detailed below, can be used in compositions capable of satisfactorily modifying the shape of hair fibers, all such ingredients, as well as HPMs or PBMs, are preferably cosmetically acceptable. An ingredient, composition, or formulation made therefrom is considered "cosmetically acceptable" if it is suitable for use in contact with keratin fibers, particularly human hair, without excessive toxicity, instability, allergic reactivity, etc. Some ingredients may be "cosmetically acceptable" when present at relatively low concentrations, in accordance with relevant regulations.

[0087] When the desired hair styling composition is a single-phase composition, it is achieved when the HPM or PBM is dissolved in a continuous aqueous phase containing a suitable cosolvent. When the desired hair styling composition is an oil-in-water emulsion, it is achieved when the HPM or PBM is emulsified and dispersed as oil droplets in a continuous aqueous phase that can optionally further contain a suitable cosolvent. The cure accelerator, if present, must be miscible with the monomers while in the hair fiber, regardless of the phase in which they may be delivered to the hair cortex.

[0088] 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 the composition containing the HPM or PBM, b) providing a suitable solubility (or 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) can also enable such an effect. Selecting a non-neutral pH relative to others may depend on the chemical nature of the monomers and cure accelerators; some may inherently contribute to an acidic or basic pH, or may favor one pH over the other.

[0089] The pH of the hair styling compositions of the present invention can be adjusted to have any desired non-neutral pH, particularly to lift the hair scales and promote penetration of the monomer, but such mechanisms do not exclude the existence of additional methods of introducing the monomer into the fiber cortex. For example, the monomers and agents required for their polymerization may be sufficiently polar to diffuse through the hair scales, whether or not they are sufficiently open for direct movement between the hair environment and its cortex.

[0090] As previously described and further detailed herein, HPM or PBM is essentially oily, i.e., substantially immiscible in water, and therefore resides in the oil phase of an oil-in-water emulsion in the absence of an appropriate amount of a suitable cosolvent. In some embodiments, the solubility of the residue of HPM or PBM (or any material considered water-insoluble) is 5 wt% or less, 1 wt% or less, or 0.5 wt% or less, based on the weight of the aqueous environment in which it is treated at the liquid's pH. Solubility can be assessed with the naked eye, and a soluble composition (e.g., a single-phase composition) is generally clear (not cloudy) at room temperature (about 23°C). Alternatively, this condition can be quantified by measuring the refractive index of the solution and comparing it to a calibration curve using a known amount of HPM or PBM in water. However, in the presence of an appropriate amount of a suitable cosolvent (e.g., greater than 30 wt%), a single-phase composition can alternatively be formed.

[0091] Regardless of the form of the styling composition, and without being bound by theory, an alkaline pH is believed to contribute, among other things, to the opening of the cuticle scales by charging the surface of the hair fiber (typically due to chargeable groups, e.g., carboxyl groups, present on the fiber), allowing better penetration of monomers into the hair shaft. 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 9, or at least 10. Generally, the pH of the composition does not exceed pH 11. In certain embodiments, the pH of the composition is between 8 and 10.5, between 9 and 10.5, or between 9.5 and 10.5.

[0092] Such an alkaline pH of the hair styling composition can be achieved by dispersing or dissolving the oil phase in which the HPM or PBM is present in an aqueous phase of appropriate 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 monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, 2-amino-2-methyl-1-propanol, cocamide monoethanolamine, aminomethylpropanol, or oleylamine. Alternatively, or in addition, 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, the crosslinkers commercialized as "Dynasylan® AMEO" and "Dynasylan® SIVO 210" have such an effect in view of their amine groups.

[0093] 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, hair styling compositions having such an acidic pH have a pH of at least 1, at least 1.5, or at least 2, and generally range from 1 to 4, 1 to 3, 1 to 3.5, 2 to 4, or 2 to 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 triethoxysilylpropyl maleic acid and trihydroxysilylethylphenyl sulfonic acid have such an effect in terms of their respective acidic groups.

[0094] Single-phase compositions and oil-in-water emulsions generally differ from one another by the relative amounts of water and co-solvents that each may contain, and each type is discussed separately below. It should be noted 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, or other additives, and their respective amounts, so there may be overlap in the ranges of concentrations suitable for each type of composition.

[0095] 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 between 2 and 80 wt%, between 2 and 60 wt%, between 2 and 20 wt%, between 2 and 15 wt%, between 10 and 40 wt%, between 10 and 30 wt%, or between 15 and 40 wt%, based on the weight of the single-phase composition.

[0096] In some embodiments, the concentration of water in the oil-in-water emulsion is at least 60 wt%, at least 65 wt%, or at least 70 wt%, based on the weight of the oil-in-water emulsion. In some embodiments, the concentration of water is at most 90 wt%, at most 87 wt%, or at most 85 wt%, based on the weight of the oil-in-water emulsion. In certain embodiments, the concentration of water is between 60-90 wt%, between 60-87 wt%, between 65-87 wt%, or between 70-85 wt%, based on the weight of the oil-in-water emulsion.

[0097] Water need not be the only "liquid carrier" of the composition, and in some embodiments, the hair styling composition may further contain at least one co-solvent. The at least one co-solvent may be a C1-C hydroxyl group-containing copolymer. 10Alcohols, 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 (e.g., methyl ethyl ketone, acetone), dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone, dimethyl carbonate, or dimethylformide; benzoic acid C 12 ~ 15 Alkyl or esters such as dibutyl maleate; and mineral or vegetable oils such as isoparaffin liquid, olive oil, coconut oil, or sunflower oil. In certain embodiments, the co-solvent is isopropyl alcohol. Without wishing to be bound by any particular theory, oily co-solvents (e.g., C 12~15 Alkyl benzoates) can also contribute to the hydrophobicity of the final composition.

[0098] As those skilled in the art will readily understand, some of these cosolvents can be mixed indiscriminately with the HPM or PBM in the oil phase, with the aqueous phase, or partially with both, during the preparation of a phase-distinguishable emulsion, or during 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 these cosolvents below, several situations are encompassed: a) a single cosolvent is used and is mixed with either the HPM or PBM or the aqueous phase; b) a single cosolvent is used and is mixed with both the HPM or PBM and the aqueous phase; or c) two or more cosolvents are used and are mixed with at least one HPM or PBM and the aqueous phase. Without being bound by any particular theory, it is believed that the cosolvent improves the surface tension of the oil phase, facilitating penetration of the HPM or PBM and / or increasing miscibility crosslinking within the HPM or PBM, if present, and / or enhancing the miscibility of the HPM or PBM in the aqueous phase to form a single-phase composition.

[0099] In some embodiments, the total concentration of these 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 amount of cosolvent may depend on the HPM or 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 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 between 20 and 70 wt%, between 30 and 70 wt%, or between 35 and 65 wt%, based on the weight of the single-phase composition.

[0100] In some embodiments, the total concentration of these cosolvents in the oil-in-water emulsion is at least 1 wt%, at least 5 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, or at least 13 wt%, based on the weight of the oil-in-water emulsion. The maximum amount of cosolvent may depend on the HPM or PBM selected, as well as the presence of additional ingredients. In any event, 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 40 wt%, at most 35 wt%, or at most 30 wt%, based on the weight of the oil-in-water emulsion. In certain embodiments, the total concentration of the cosolvents is between 1 and 40 wt%, between 5 and 40 wt%, between 10 and 40 wt%, between 12 and 35 wt%, or between 13 and 30 wt%, based on the weight of the oil-in-water emulsion.

[0101] Single-phase compositions and oil-in-water emulsions can be prepared by any suitable method. For example, the compositions of the present invention can be prepared by mixing a first mixture containing HPM(s) or PBM(s), thus containing a predominant oil phase, with a second liquid containing a predominant aqueous phase. These separate subcompositions, forming the "HPM compartment" or "PBM compartment" and the "aqueous compartment," each containing any desired additives, are each referred to as containing the predominant portion of one 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 a polymerizable subcomposition, the HPM or PBM may be substantially immiscible with water and / or may be prepared in the presence of a cosolvent (or any other component of the emulsion) that exhibits some miscibility with water and can partially merge with the aqueous phase when mixed with the predominant aqueous subcomposition. When the two phases are mixed, a single-phase composition is obtained, rather than an emulsion, when one dissolves in the other.

[0102] When an oil-in-water emulsion is prepared by mixing an HPM or PBM compartment with an aqueous compartment, each can contain an amount of each component appropriate to achieve the desired concentration of the final oil-in-water emulsion upon mixing the two compartments in a set ratio. By way of example, in some embodiments, the total concentration of all HPMs or PBMs (if more than one) in an HPM or PBM compartment is at least 2 wt%, at least 5 wt%, at least 9 wt%, at least 13 wt%, or at least 15 wt%, based on the weight of the HPM or PBM compartment. In some embodiments, the concentration of HPM or PBM is at most 50 wt%, at most 40 wt%, at most 37 wt%, at most 35 wt%, at most 33 wt%, or at most 32 wt%, based on the weight of the HPM or PBM compartment. In certain embodiments, the concentration of HPM or PBM is between 2 and 50 wt%, between 2 and 40 wt%, between 5 and 35 wt%, between 5 and 33 wt%, between 9 and 33 wt%, or between 9 and 32 wt%, based on the weight of the HPM or PBM compartment.

[0103] Because 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 an HPM or PBM compartment and an aqueous compartment, the concentration of HPM or PBM is alternatively provided by weight of the total / final composition (e.g., single-phase or emulsion).

[0104] In some embodiments, the combined concentration of HPM or PBM (if two or more) in the hair styling composition (e.g., an oil-in-water emulsion) is at least 0.1 wt%, at least 0.25 wt%, at least 0.5 wt%, or at least 0.9 wt%, based on the total weight of the composition. In some embodiments, the concentration of HPM or PBM is at most 5 wt%, at most 3 wt%, at most 2 wt%, or at most 1.5 wt%, based on the weight of the hair styling composition. In certain embodiments, the concentration of HPM or PBM is between 0.1 and 5 wt%, between 0.25 and 5 wt%, between 0.5 and 5 wt%, between 0.5 and 3 wt%, between 0.9 and 2 wt%, or between 0.9 and 1.5 wt%, based on the weight of the hair styling composition.

[0105] 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 may induce premature and undesired polymerization.

[0106] Generally, when a crosslinking agent is used, a low concentration is required, and such a concentration generally corresponds to the stoichiometric amount theoretically capable of crosslinking through all crosslinkable groups of the monomer and the corresponding functional groups of the crosslinking agent. In some embodiments, the total concentration of crosslinking agent (if two or more) present in the hair styling composition is at most 10 wt%, at most 5 wt%, at most 2.5 wt%, at most 2 wt%, or at most 1.5 wt%, based on the weight of the composition (e.g., an oil-in-water emulsion). In some embodiments, the total concentration of crosslinking agent is at least 0.05 wt%, at least 0.1 wt%, or at least 0.5 wt%, based on the weight of the composition. In certain embodiments, the crosslinking agent is present in a total concentration of between 0.05 and 10 wt%, between 0.1 and 5 wt%, or between 0.5 and 1.5 wt%, based on the weight of the composition. When considering the weight ratio between the HPM(s) or PBM(s) and their crosslinker, this ratio can be between 1:15 and 5:1, between 1:10 and 2.5:1, or between 1:5 and 5:1. When the curing process involves thermal energy, the crosslinker is preferably selected to provide curing at a sufficiently slow rate at elevated temperatures relative to ambient temperature and / or room temperature to prevent or reduce natural curing during storage and / or application of the hair styling composition. The curing temperature of a suitable crosslinker need not be too high (e.g., between 50°C and 60°C for hair fibers) to allow for use on live subjects, and both the curing temperature and curing rate of the crosslinker can be selected to provide curing under reasonable conditions.

[0107] In some embodiments, the total concentration of the cure accelerators (if there are two or more) is at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 10 wt%, at most 9 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, or at most 5 wt%, based on the weight of the HPM(s) or PBM(s), and the cure accelerators are optionally present at at least 0.01 wt% of the HPM(s) or PBM(s). Considering the amount of cure accelerators 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 accelerators is at most 5 wt%, at most 3 wt%, or at most 2 wt%, based on the weight of the hair styling composition, and the cure accelerators are optionally present at at least 0.001 wt% of the hair styling composition.

[0108] When peroxides are used as cure accelerators for addition polymerization, their amount must be carefully considered in terms of their ability to bleach hair. Thus, the amount of peroxide should be sufficient to activate the polymerization, but small enough not to significantly bleach the hair.

[0109] In some embodiments, the concentration of cure accelerator present in the hair styling composition (i.e., the combined concentration of the crosslinker and cure accelerator used in the addition or condensation polymerization) is between 0.05 wt % and 15 wt %, between 0.1 wt % and 13 wt %, or between 0.5 wt % and 10 wt % of the total hair styling composition.

[0110] In some embodiments, the single-phase composition or oil-in-water emulsion may further comprise at least one additive adapted to enhance one or more properties of the hair styling composition, such as, for example, a co-polymerizing agent, an emulsifier, a humectant, a thickener, a charge modifier, or other ingredients conventionally included in hair styling compositions (e.g., fragrance).

[0111] In some embodiments, a co-polymerizer may be added to enhance and promote cross-linking of the HPM(s) or PBM(s) or the cross-linker itself. In contrast to the classic cure accelerators described above, which are not necessarily functionalized, such co-polymerizers have at least one functional group that increases the concentration of functional groups available for cross-linking, either along with the polymerizable groups of the HPM or PBM or along with the functional groups of the cross-linker. It is believed that a higher concentration of functional groups in the co-polymerizer contributes to a greater degree of cross-linking promotion. At least in terms of the presence of functional groups, the co-polymerizer is able to bind to the growing polymer network (as opposed to traditional cure accelerators, which do not incorporate into the network without additional cross-linking). Preferably, the functional group density of the co-polymerizer should be high enough to allow the use of co-polymerizers with molecular weights of less than 10,000 g / mol, less than 5,000 g / mol, or less than 3,000 g / mol, without interfering with their ability to penetrate the hair shaft.

[0112] The functional groups contained in the co-polymerization agent can be hydroxyl (-OH), carboxyl (-COOH), amine (-NH), or carbonyl (C=O) groups. Suitable co-polymerization agents can also have functional groups such as anhydrides, isocyanates, and isothiocyanates, which can react with, for example, amine crosslinkers. Other suitable co-polymerization agents can have groups that can be further functionalized by other reactants present in the composition, such as double bonds, which can be cleaved (e.g., by an amine crosslinker, or alternatively, in a Michael addition reaction, or even by a PBM that has been "activated" to contain a reactive radical).

[0113] Exemplary co-polymerization agents can be selected from the following: shellac, rosin gum, alkyl orAryl-substituted maleates and salicylates (e.g., dimethyl maleate and dibutyl maleate), fatty oils with alkene chains of 16 or more carbon atoms, including terpenes and terpenoids (e.g., squalene and lycopene), fatty amines (e.g., oleylamine), and unconjugated 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 unconjugated double bonds, such as pomegranate seed oil, tea seed oil, perilla seed oil, raspberry seed oil, and kiwi seed oil. Alkenes that can function as co-polymerization agents are distinguished from alkenes that can function as crosslinkers 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, the co-polymerization agent having an unsaturated alkene chain can be characterized as having an iodine value of 100 g iodine or more per 100 g of agent, with such value usually not exceeding 400.

[0114] In some embodiments, the co-polymerizers used for the purposes of the present invention are hydrophobic and may also help protect the hair against moisture penetration in addition to enhancing cross-linking within the hair fiber.

[0115] In certain embodiments, the co-polymerizing agent is shellac, a natural bioadhesive resin harvested from insect secretions, which has many synthetic chemical equivalents. Purified wax-free shellac generally has an average molecular weight of about 600-1,000 g / mol, and although its exact 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 functional groups. Shellac can be supplied 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.

[0116] In some embodiments, the co-polymerization agent is present in an amount between 0.01 wt % and 1 wt %, between 0.01 wt % and 0.8 wt %, between 0.02 wt % and 0.6 wt %, or between 0.03 and 0.5 wt %, based on the weight of the composition.

[0117] The hair styling composition may further contain an emulsifier, in the case of an oil-in-water emulsion, to facilitate emulsion formation and / or prolong its stability. In some embodiments, the emulsifier is a nonionic emulsifier, preferably having a hydrophile-lipophile balance (HLB) value on the Griffin scale of between 2 and 20, between 7 and 18, between 10 and 18, between 12 and 18, between 12 and 17, between 12 and 16, between 12 and 15, or between 13 and 16. Suitable emulsifiers are water-soluble (e.g., having an HLB value of 8 to 20), such as polysorbates (often commercially available as Tweens), ester derivatives of sorbitan (often commercially available as Spans), acrylic copolymers (e.g., commercially available as Synthalen® W2000), and combinations thereof, or oil-soluble, such as lecithin and oleic acid (e.g., having an HLB value of between 2 and 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-polymerization agent, can also function as an emulsifier due to its polar head and fatty chain.

[0118] To facilitate penetration of HPM or PBM into hair fibers, the composition must be able to spread adequately on the hair fiber to allow proper contact. Upon application, the composition is expected to sufficiently coat the hair fiber, promoting penetration of the monomer into the hair, likely through capillary action, to form a synthetic polymer capable of constraining 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.

[0119] Previously untreated natural hair fibers generally have a surface energy of approximately 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 higher presence of naturally occurring fatty acids in undamaged hair is believed to contribute to the relatively lower surface tension. Given the above ranges, it can be assumed that adequate wetting will be observed for all hair types when using a composition with a surface tension of less than 25 mN / m. Surprisingly, it has been found that hair styling compositions with too low a surface tension do not produce the expected results as far as monomer penetration is concerned. Counterintuitively, the inventors have discovered that compositions with a relatively higher surface tension than theoretically considered appropriate are more suitable for the purposes of the present invention. Without wishing to be bound by theory, it is believed that the absence of fatty acids within the hair shaft increases the perceived surface energy 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.

[0120] In some embodiments, the compositions of the present invention have a surface tension between 25 and 60 mN / m, between 25 and 55 mN / m, between 25 and 50 mN / m, between 25 and 45 mN / m, between 25 and 40 mN / m, between 25 and 35 mN / m, or between 30 and 40 mN / m.

[0121] The compositions of the present invention that are suitable for natural hair are also suitable for previously treated hair fibers. However, in some embodiments, the styling composition may exhibit a surface tension that is suitable for adequate coverage of damaged hair, but may not be sufficient for coverage of natural hair fibers.

[0122] The wetting agent can be added to the composition at any suitable concentration capable of lowering the surface tension to any of the aforementioned suitable ranges. Examples of wetting agents include silicone-based, fluorine-based, carbon-based, or amine alcohols. Silicone-based wetting agents include silicone acrylates (e.g., SIU 100 manufactured by Miwon Specialty Chemical Co., Ltd.). Fluorine-based wetting agents include perfluorosulfonic acids (e.g., perfluorooctane sulfonic acid) or perfluorocarboxylic acids (e.g., perfluorooctanoic acid). Carbon-based wetting agents 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 humectants (such as amodimethicone or bisaminopropyldimethicone), as well as alkanolamines (such as 2-amino-1-butanol and 2-amino-2-methyl-1-propanol). When humectants are added, they are typically present in the hair styling composition (e.g., an oil-in-water emulsion) at a concentration of at least 0.001 wt%, at least 0.01 wt%, or at least 0.1 wt%, or at most 1.5 wt%, at most 1.4 wt%, or at most 1.3 wt%, or optionally between 0.001 and 1.5 wt%, between 0.01 and 1.4 wt%, or between 0.1 and 1.3 wt%, based on the weight of the composition.

[0123] Alternatively or additionally, some of the components present in the hair styling composition to perform different functions can also 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, cosolvents can also contribute to the wetting ability of the composition to hair fibers.

[0124] In some embodiments, a thickening agent can be added to the oil-in-water emulsion or aqueous phase of the aqueous compartment to provide a desired viscosity. The viscosity must be low enough to allow the composition to be easily applied to the hair so that all individual hair fibers are satisfactorily coated, yet high enough to remain on the hair fiber for a sufficient time to prevent dripping. A relatively low viscosity may also facilitate penetration of the HPM or PBM into the hair by diffusion and / or capillary action. Exemplary thickening agents 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, the thickening agent is generally present at a concentration of at least 0.1 wt %; at most 10 wt %; and optionally between 0.5 wt % and 5 wt % based on the weight of the aqueous phase or single phase.

[0125] To facilitate migration and / or retention of the HPM or PBM to the surface of the hair fiber and subsequently increase its penetration, there should preferably be a difference between the zeta potential of the composition and that of the hair. For example, the zeta potential (or ζ2) of the hair styling composition at its pH should preferably be more negative or more positive than the zeta potential (or ζ1) of mammalian hair fibers at the same pH. In some cases, ingredients used in the composition, in addition to other functions, can provide sufficient charge of the composition to achieve such a gradient in zeta potential values. For example, pH adjusters, humectants, and / or amine-based crosslinkers can contribute to the appropriate charge of the oil-in-water emulsion. In some embodiments, agents dedicated to this effect, called charge control agents, can be added to the composition. For illustrative purposes, a water-insoluble, non-reactive aminosilicone oil can be added to the oil phase of the emulsion to adjust the zeta potential.

[0126] In some embodiments, the difference between the zeta potential ζ2 of the composition and the zeta potential ζ1 of the hair fiber, also referred to as the zeta difference or delta zeta potential (Δζ), is in absolute value at least 10 mV, at least 15 mV, at least 20 mV, at least 25 mV, at least 30 mV, or at least 40 mV. In some embodiments, the absolute value of Δζ is in the range of 10-80 mV, 10-70 mV, 10-60 mV, 15-80 mV, 15-70 mV, 15-60 mV, 20-80 mV, 20-70 mV, 20-60 mV, 25-80 mV, 25-70 mV, 25-60 mV, 30-80 mV, 30-70 mV, 30-60 mV, 35-80 mV, 35-70 mV, or 35-60 mV.

[0127] 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 further detailed herein.

[0128] The composition may contain any other additives conventional for 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 further detailed herein.

[0129] The materials can be mixed and / or emulsified by any method known in the art. While manual shaking is sufficient, a variety of devices can be used, such as vortexers, overhead stirrers, magnetic stirrers, ultrasonic dispersers, high shear homogenizers, sonicators, and planetary centrifugal mills, which generally 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.

[0130] In some embodiments, the hair styling composition can be prepared by mixing or emulsifying the contents of the HPM or PBM compartment and the aqueous compartment, with this combination occurring immediately after each portion is prepared. However, in other embodiments, mixing of the two compartments can be postponed. In particular, when a composition comprising HPM(s) or PBM(s) and at least one cure accelerator (e.g., a crosslinker) tends to separate into different phases in the final composition, it may be desirable to prepolymerize such materials in the same polymerizable compartment. In some embodiments, the prepolymerization step is performed on a single mixture of the HPM(s) or PBM(s) and the cure accelerator, rather than on the entire contents of the HPM / PBM compartment, as this would result in the inclusion of additional materials that could adversely affect or simply slow the process. In other embodiments, prepolymerization is performed on the HPM(s) or PBM(s) alone, prior to combination with the cure accelerator or any other components of the HPM or PBM compartment. Such prepolymerization can be referred to as "auto-prepolymerization." Without wishing to be bound by theory, it is believed that when the PBM(s) contain unsaturated side chains, such as CNSL, such self-prepolymerization occurs by cleavage of the double bond under appropriate conditions (e.g., elevated temperature) to form a radical that is available for polymerization with other CNSL molecules via addition polymerization.

[0131] Such prepolymerization, if necessary, and whether or not a cure accelerator is present, must be long enough to prevent the monomer and cure accelerator from separating into different phases upon mixing with the additives in the HPM / PBM compartment and / or with the contents of the aqueous compartment, thereby significantly slowing polymerization within the hair fiber after application of the mixed composition. However, the prepolymerization must be short enough so that any oligomers that may form in this process (either of the crosslinker itself, the monomer itself, or the crosslinker and the monomer together) remain small enough to penetrate into the hair fiber after application of the composition. This prepolymerization is believed to consume the relevant building blocks (e.g., monomer and / or crosslinker) present in the prepolymerized compartment, 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 heating the mixture. The prepolymerization step can be carried out in an inert atmosphere, such as under argon or nitrogen, to reduce or eliminate environmental factors (e.g., oxygen) that may interfere with the prepolymerization reaction. The prepolymerization conditions, if any, can depend on the type of HPM or PBM and the crosslinker selected. In some embodiments, the prepolymerization can be carried out at a temperature between 20°C and 60°C, between 25°C and 60°C, between 30°C and 60°C, or between 40°C and 60°C, or at an elevated temperature, such as between 100°C and 150°C, or between 150°C and 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. Generally, the duration of prepolymerization will not exceed 24, 18, or 12 hours if carried out at a relatively mild temperature, but can be shortened to less than 8, 5, or 4 hours if carried out at a relatively high temperature (e.g., between 150°C and 200°C).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.

[0132] 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, generally less than 10 μm) provided the HPM or PBM has not fully polymerized in vitro. More generally, a hair styling composition can be used as long as a sufficient amount of HPM or PBM is available to at least partially penetrate the hair fiber and polymerize therein. In some embodiments, a single-phase composition or emulsion is applied to the hair fiber within at most 30 minutes, or at most 20 minutes, at most 10 minutes, or at most 5 minutes of its dissolution or emulsification.

[0133] In some embodiments, before applying the hair styling composition as a single-phase composition or as an oil-in-water emulsion, residual moisture can be removed 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 on the surface of the hair cuticle and / or within the hair shaft. Also, before applying the hair styling composition, residual substances that may be present on the hair, such as hair products, dirt, or grease, can be removed to clean the hair fiber. This can be done by applying a detergent such as sodium lauryl sulfate. If desired, the hair fiber can be washed and then dried before applying the hair styling composition.

[0134] As used herein, unless otherwise clear from the context or stated otherwise, the term "residual moisture" refers to, with respect to hair fibers, water present either on the outer surface of the hair cuticle, between its scales, and / or beneath it (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). Naturally, since hair is constantly exposed to ambient humidity and humidity is never nearly zero, complete removal of residual moisture is very difficult to achieve. Nevertheless, low levels of residual moisture are achievable or can be temporarily achieved by applying primarily 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 iron or curling iron for a sufficient period of time. Regardless of the method used to reduce the amount of water molecules in the hair, such a process can alternatively be referred to as a drying treatment or a drying process.

[0135] When considering hair with at least a wavy appearance, sufficient drying temporarily reduces the waves, making it easy to visually assess whether the hydrogen bonds have been sufficiently broken by the drying pretreatment, and if desired, the hair fibers are completely flattened at the end of such a process. Alternatively, as in the case of straightening hair, the duration of the drying pretreatment can be arbitrarily set depending on the drying device used and the temperature applied to the hair fibers. For example, a flat or curling iron, which can be applied directly to hair at a heat conduction temperature of about 200°C, can sufficiently break hydrogen bonds within a few minutes, while a conventional hair dryer, depending on the distance from the hair used, can apply a relatively low temperature by heat conduction, and a relatively long drying period will be required. Typically, drying of hair fibers can be carried out 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 5 seconds or less at a time, and such a drying process takes up to 5 minutes for the hair bundle if the heating progresses from one end of the hair bundle to the other.

[0136] In some embodiments, the residual moisture level after such drying (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 using, for example, thermogravimetric analysis or near-infrared techniques such as photothermal transient emission radiometry.

[0137] Alternatively, or in addition, heating that may particularly contribute to the cleavage of hydrogen bonds within the keratin polymers and / or within the materials of the hair styling composition that have 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, if any, heating accelerates the rate of diffusion of monomers / oligomers within the hair fiber and / or hardening of the polymer.

[0138] Regardless of whether any drying and / or washing steps have been performed beforehand, a hair styling composition (e.g., an oil-in-water emulsion) is applied to the hair fiber and generally maintained on the hair for at least 5 minutes to swell and open the scales of the hair cuticle, thereby allowing the HPM or PBM and cure accelerator (if present) access into the hair shaft. To facilitate penetration into the hair cortex, molecules involved in or promoting internal polymerization (e.g., HPM or PBM, cure accelerator, cosolvent) 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 once the monomer binds to at least some of the hydrogen bonds of the hair fiber, it can prevent the hair fiber from reforming to its previous, original state upon exposure to water. The HPM or PBM can additionally or alternatively polymerize without binding to previously broken hydrogen bonds. Regardless of the mechanism of action, the polymer resulting from the curing of the monomer impregnated into the hair fiber can constrain the hair fiber into a new shape. The curing compositions of the present invention are believed to prevent water (environmental or applied when wet) from accessing the hair, reducing or delaying the ability of hydrogen bonds to reform and delaying the ability of the hair to return to its native shape. Thus, for simplicity, the method is described in terms of the scission of hydrogen bonds and subsequent disruption of said scission bonds by binding to HPM or PBM or other components that can then polymerize, but this is not meant to exclude further basis for the observed styling effect.

[0139] Sufficient time is allowed for the monomer to soak into the hair fiber and ensure bonding to at least some of the broken hydrogen bonds in the hair fiber. In some embodiments, the composition is 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 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 to 30 minutes, 10 to 60 minutes, 30 to 12 hours, 30 to 5 hours, 40 to 2 hours, or 50 to 2 hours. It should be noted that conventional hair straightening methods may require longer times, sometimes requiring application for 3 to 4 hours, or even 6 to 8 hours.

[0140] The composition can remain applied on the hair fiber at ambient temperature (about 23° C.), although the process can alternatively be carried out at an elevated temperature of at least about 30° C., or at least about 40° C. In some embodiments, the temperature at which the composition can remain in contact with the hair fiber 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 fiber at a temperature range between 15° C. and 23° C., between 23° C. and 60° C., between 25° C. and 55° C., or between 25° C. and 50° C.

[0141] After said time, the composition is allowed to fully penetrate at least a portion of the HPM or PBM within the individual hair fibers, and these monomers are then at least partially cured by the application of energy, optionally in the presence of a cure accelerator, to effect at least partial polymerization.

[0142] Upon polymerization of the HPM or PBM, the resulting polymer undergoes an increase in glass transition temperature (Tg), as can be more easily appreciated in a liquid composition than in a hair fiber. In some embodiments, upon full cure, the resulting HPP or PBM 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 HPM or PBM to remain intact even under hot weather conditions, when washing hair with hot water (about 45°C), or when subjected to elevated temperatures such as a sauna (about 70°C). Because the synthetic polymer formed within the hair fiber remains unaffected by such conditions or treatments due to its Tg, the modified shape of the hair achieved using the compositions and methods of the present teachings is not so affected.

[0143] In some embodiments, the energy that enables at least partial curing of the composition (and thus 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 at most 220°C, or at most 200°C. In certain embodiments, the temperature applied to achieve at least partial curing is within a range of between 80°C and 220°C, between 100°C and 220°C, between 120°C and 220°C, or between 140°C and 200°C. It should be 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 sufficiently long dwell time (the period during which the hair section is exposed to heat), the temperature of the hair fiber may eventually reach the heating temperature, but this is generally not the case; the temperature of the hair fiber at which curing can occur is generally 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 180°C or less, 140°C or less, or 100°C or less. The at least partial hardening can be carried out while styling the hair into a desired shape, for example with a hair dryer, flat iron, or curling iron, to modify its natural shape. This step can alternatively be called a styling step, since during this step the hair fiber is dynamically or statically mechanically restrained (e.g., pulled with a comb or brush, rolled with rollers, or contacted with a styling iron) to modify its shape.

[0144] 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 locally cause partial polymerization of the HPM or PBM within a few 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 needs to be heated, i.e., experience a particular temperature suitable for curing, can depend on the shape of the hair being modified and the new shape that is being formed. Relatively mild modifications may require less time than relatively more dramatic shape changes.

[0145] The period of time that hair fibers should be at the appropriate temperature can be independently tested in vitro by exposing the dissolved or emulsified oil phase of the composition to the temperature intended for hair treatment and measuring the time it takes for the liquid phase to begin solidifying (i.e., hardening). When considering mammalian subjects, the amount of time allotted for the partial hardening step (i.e., 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 provide heat and its temperature. Thus, at the level of the entire scalp of hair, partial hardening may take several minutes, but generally not more than one hour. This concept applies to any other treatment of hair fibers, and the time durations 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 batches of hair fibers, the treatment period for the entire scalp can be the sum of the periods corresponding to the actual number of individual repetitions of the simultaneous treatment. For example, if the simultaneous treatment of the first batch of hair fibers requires 5 minutes and the entire hair scalp consists of four batches, the treatment will be completed in about 20 minutes.

[0146] Prior to at least partial curing, excess liquid composition is optionally removed from the outer surface of the hair fiber by rinsing the hair fiber with a rinse liquid, thereby preventing the formation of a thick coating on the surface of the hair fiber, which would make the hair less sticky and rough to the touch. Rinsed hair fibers may also have improved heat conduction, which may accelerate partial curing.

[0147] Alternatively, or in addition, after application of the composition and its incubation on the hair fibers, and optionally after rinsing, but before hair styling, a second composition consisting of a cure accelerator can be applied to the hair fibers impregnated with HPM or PBM. The composition that can be used in this optional step can be called a curable composition. This is a curing composition containing the same cure accelerator as described above, selected from the crosslinking agents and cure accelerators described above for the hair styling composition, and generally consisting of a cure accelerator. In contrast to hair styling compositions, the cure accelerator (e.g., cure accelerator) can be present in the curing composition in an excess amount (e.g., 5 wt%) that allows the application of the curing composition to the hair fibers to be relatively short (e.g., between 5 minutes and 15 minutes, or less). The curable composition can further serve to rinse the hair fibers in addition to or instead of a rinse.

[0148] After at least partial curing sufficient to achieve the desired modified shape, the hair fibers can optionally be further cured by applying additional energy, preferably heat, to ensure further curing of the composition. Additional energy can be applied using the styling tools described above, such as a hair dryer or styling iron. In some embodiments, the further curing can be carried out at a temperature as described for the at least partial curing of the third step, typically for a significantly longer time than for the partial curing. For example, if hair fibers are treated with a composition that allows at least partial curing at a predetermined temperature with a specific styling device within 20 minutes (established by fibers across the scalp exhibiting the desired modified shape), any additional heating step favoring further curing would be carried out for at least 40 minutes under at least the same conditions. While partial curing is achieved during the modification of the fiber shape, the step referred to herein as further curing is applied once the hair fibers have achieved the desired modified shape, so that simultaneous mechanical restraint of the fibers to conform to the desired shape is no longer necessary. Further curing is expected to increase the degree of polymerization of the HPM or PBM within the hair fiber, but is not expected to result in complete curing (i.e., after which polymerization no longer occurs).

[0149] In some embodiments, after heat curing (e.g., achieved during the styling step and optional further curing), the hair fiber can be kept unwashed to reduce exposure to water, allowing further curing, if applicable. The length of time for 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, relative humidity, the desired modified shape, and the desired duration of said modification. Generally, assuming the hair fiber is maintained at room temperature with a relative humidity of about 40-60% RH, washing of the hair can be performed at least 18 hours after the end of at least partial curing (e.g., styling involving 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, hair styled according to the present method is washed 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 destroying 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 a set accelerator.

[0150] Figure 1A shows a FIB-SEM image of a hair fiber that was washed with hexane and sonicated for 45 minutes in a digital ultrasonic cleaner (PS-60A, Xi'an HEB Biotechnology Co., Ltd., 360 W, 40,000 Hz) to remove any residue and to better visualize the cuticle of an untreated hair fiber (reference). Figure 1A shows a cross-section of the hair fiber, photographed using a Zeiss Crossbeam 340 microscope with scanning electron microscopy (SEM) and focused ion beam (FIB). The cross-section was performed by bombarding the sample with ionized gallium at 30 kV and 300 pA at a 54° angle from the SEM column. The image was captured using an SEM column and in-lens detector at a magnification of 100K, a voltage of 1.20 kV, and a working distance of 5 mm. As can be seen, the scales of the hair cuticle are layered one above the other. To better illustrate the structure of the hair, a schematic diagram is shown in Figure 1B. The scales are indicated by sparsely dotted areas and are separated by dark lines that may represent the cuticle-cuticle cell membrane complex (CMC).

[0151] For comparison, Figure 2A shows a FIB-SEM image of hair treated with a CNSL oil-in-water emulsion of the present invention after curing. The image clearly shows the cured emulsion 20 located between the cuticle scales 21 of the treated hair fiber. Figure 2B is a schematic diagram of the same treated hair structure with the cured CNSL composition, shown by the dashed line, between the cuticle scales, shown by the sparsely dotted line.

[0152] Figure 3A shows a top view of cuticular scales 31 on a hair fiber taken with an SEM (Zeiss Crossbeam 340 microscope, 0.8 kV voltage, 5.3 mm working distance, 20K magnification). The hair fiber was treated with a control composition containing alkaline water (adjusted with ammonium hydroxide) at pH 10 in the presence of isopropyl alcohol, which resulted in the opening of the scales, as can be seen from the "elevated" appearance of scales 31 and the adjacent shadow of area 32. For comparison, Figure 3B shows a top view of scales 33 on a hair fiber treated with a CNSL oil-in-water emulsion of the present invention after curing. As can be seen, the cured emulsion 34 is located underneath the opened scales, as can be inferred from the mildly expanded areas 34 adjacent to the raised scales 33.

[0153] The method of the present invention provides durable hair styling, maintaining hair fibers in a desired shape even after exposure to moisture, whether from atmospheric humidity or after wetting or washing the hair.Even after five or more shampoo washes, the styling shape is not significantly affected in a detectable manner, allowing hair styling to be maintained for a long period of time.As demonstrated in the examples, in some embodiments, the hair styling compositions and methods of the present teachings result in 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.

[0154] Initially, the hair styling composition applied to the hair forms a removable coating on the surface of the hair fiber. This can be observed in Figure 4, which shows an image of a hair fiber taken 48 hours after application of a composition prepared in accordance with an embodiment of the present invention (specifically, emulsion Em31, the preparation of which is described in Example 16), without rinsing or a washing cycle. Figure 4 shows the results of irradiation with ionized gallium at 30 kV and 50 pA, magnification 20K, voltage 10The image was taken at 100 kV and was taken with a FIB-SEM as described above. In this view, the cured hair styling composition can be seen as a light layer deposited on the hair fiber as an outer layer 43, and as a layer 42 that has penetrated between the cuticle 41.

[0155] 5A and 5B are FIB-SEM images of hair fibers treated with the application of emulsion Em31, followed by straightening and 49 washing cycles (both procedures are described in Examples 2, 3, and 13 below). The images are of the same hair fiber at 20Kx magnification and were taken at voltages of 1.2 kV (FIG. 5A) and 10 kV (FIG. 5B) using ionized gallium irradiating the sample at 30 kV and 300 pA. Charging the fiber at a lower voltage, as was done for FIG. 5A, allows for a clearer view of the hair cuticle 51, while charging at a higher voltage, as was done for FIG. 5B, improves the visibility of the cured composition 52, which is clearly visible within the hair fiber without the temporary coating previously observed in the unwashed sample of FIG. 4.

[0156] 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 inventors speculate that such external coatings tend 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 HPM or PBM. It is noted that this temporary diffuse coating is relatively thin, typically not exceeding an initial thickness of 1 μm, and often less than 0.5 μm, which in itself distinguishes hair fibers treated according to the present teachings from conventional styling methods that rely on a continuous external coating of several microns to constrain the fiber in a desired shape. Without wishing to be bound by theory, it is believed that this temporary thin coating on the hair fiber temporarily protects the inner shaft, thereby allowing the internally infiltrated monomers to further promote hardening and strengthen polymerization, thereby extending the durability of hair styling. As exemplified below, hair styling according to the present method is maintained even without the temporary coating.

[0157] As used herein, a composition that provides a modified shape that can withstand 5-9 shampooings is said to have a short-term styling effect, a composition that can withstand 10-49 shampooings is said to provide semi-permanent styling, while a composition that can withstand more than 50 shampooings is said to provide permanent styling.

[0158] It should be noted that in the following examples, such values ​​are generally established on natural hair that has only been treated with the composition of the present invention.Damaged hair fibers (such as those previously bleached or colored by conventional methods, or simply damaged) generally exhibit a higher surface energy than natural hair fibers, and therefore, as a result of, among other things, the surface tension, a composition that can provide short-term styling effects on natural hair may be able to provide a longer styling period (e.g., more shampoo-resistant cycles) on damaged hair.Without wishing to be bound by a particular theory, this may be because the difference between the surface tension of the composition and the surface energy of the hair is greater in the case of damaged hair, and therefore the gradient that promotes the penetration of the monomer is stronger.

[0159] Because methods that rely on such peripheral constraining structures to persistently maintain the shape of straightened hair have often proven detrimental to the health and natural appearance of the hair, it would be advantageous to rapidly eliminate the continuous outer coating (which is not critical to the present long-lasting styling effect).

[0160] Figure 6A shows an image of a naturally untreated curly black hair tress, with the kinks (e.g., peaks and valleys) in the hair fiber clearly detectable. For comparison, Figure 6B shows an image of a curly black hair sample treated with a CNSL oil-in-water emulsion as described in the present invention and then straightened with a flat iron. Figure 6B was taken after 19 shampoo washes, and clearly shows that the tress remains straight and has a dramatically reduced number of kinks compared to the untreated reference. Furthermore, the treated hair exhibited a healthy, shiny appearance essentially identical to its pre-treatment appearance.

[0161] While alternatives are generally often harmful to hair or 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, allowing hair fibers to return to their natural shape after 2-4 shampoo washes.

[0162] Figure 7 shows the results of DSC tests demonstrating that the hair styling method of the present invention preserves hair without damaging it, unlike conventional methods. As can be seen, the curve for the hair fiber sample treated with the composition of the present invention is comparable to the curve for the untreated natural hair sample, indicating no significant structural changes, and therefore no damage, to the hair. In contrast, the DSC curve for a commercially available hair straightener (organic, made in Japan) is significantly altered from the natural hair curve, indicating the structural changes expected when using such a dramatic hair styling method. DSC measurements are described in further detail in Example 8 below.

[0163] Advantageously, hair fibers treated with a composition according to the present teachings 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.

[0164] Figures 9A and 9B show the results of tensile tests measuring various mechanical parameters on treated and untreated hair fibers, as described in Example 20 below. The results demonstrate that the mechanical properties of hair fibers treated with the compositions of the present invention are unchanged, if not superior, to the mechanical properties of similar untreated fibers. For comparison, fibers styled with a conventional organic hair relaxer are shown to have poorer mechanical properties compared to untreated fibers and even poorer compared to fibers treated according to the present invention.

[0165] The mechanical parameters of hair fibers treated with the present invention are superior in terms of breaking stress, or the pressure (or force per cross-sectional area) required to break the hair, as measured at the break point of the strain-stress curve. An example of the results is shown in Figure 9A. Hair fibers treated with the compositions and methods of the present invention (specifically, with Em25 prepared in Example 14 and Em31 prepared in Example 16) were shown to be stronger and more stress-resistant than untreated fibers, even after at least 13 washes. They were also found to be stronger than hair fibers treated with conventional organic curly hair, which in turn weakened the fibers.

[0166] The results of hair toughness, as assessed by the amount of energy the hair can absorb before breaking (i.e., the area under the strain-stress curve), are shown in Figure 9B and show that fibers treated with the compositions of the present invention performed equally well, even better, than untreated hair, even after at least 13 washes. Hair treated with conventional organic hair straighteners exhibited substantially less toughness. Additionally, when tested for elastic modulus, or the ability of hair fibers to resist elastic deformation, fibers treated with the methods of the present invention were found to be comparable to untreated hair (results not shown).

[0167] These mechanical properties clearly distinguish hair fibers styled according to the present teachings from hair conventionally treated to achieve the same effect. 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 strength 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 tenacity of similar untreated hair fibers.

[0168] The method of the present invention is suitable for any desired hairstyle and shape, such as straightening, curling, or creating intermediate shapes, where the hair is relaxed into a shape that is less wavy than its natural, unaltered shape.

[0169] Advantageously, the compositions of the present invention allow for restyling without the need for fresh application of the composition. Thus, once the method of the above-described embodiment, which functions to modify the shape of a hair fiber from its native shape to a first modified shape, is completed, 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 step, and is therefore sometimes referred to as "at least partial softening." During and / or after such at least partial softening, the hair fiber is formed into the desired second shape. Thereafter, by lowering the temperature below the Tg or softening temperature while maintaining the hair in the desired shape, the polymer can regain a restraining structure suitable for retaining the second shape. Alternatively, the temperature can be actively lowered, such as by applying cool air to the hair. The second modified shape can be the same as or different from the first modified shape. While this innovative restyling method has been described with respect to softening the polymer previously impregnated within the fiber, it is believed that the heat applied to achieve this softening may also function to reduce moisture content. As explained above, the removal of residual moisture is believed to affect hydrogen bonding and enhance the effectiveness of the reformed polymer when softening ceases.

[0170] Advantageously, the composition of the present invention allows for "de-styling" as needed, which means that hair fibers treated according to the present invention can regain their original shape without waiting for the styling effect to wear off over time or for the natural regrowth of hair fibers.This can be achieved by subjecting 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 to soften the polymer and allow water to penetrate the hair fibers.Without wishing to be bound by theory, it is believed that such de-styling treatment may result in the softening of the polymer, thereby potentially breaking some of the bonds that the polymer would have formed with parts of the hair fibers that are prone to forming 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 takes upon cooling to a low temperature that no longer supports softening, destyling may be partial or complete, and the hair may accordingly return to a partial or closer 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 may be subjected to further styling treatments, as described above for restyling.

[0171] The Tg or softening temperature of a synthetic polymer in a hair fiber can be experimentally evaluated, for example, in vitro. A sample of hair to be restyling or destyling is taken from the scalp of the subject's hair to be treated by such a method and placed in the desired re / destyling solution (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 its modified shape and returns to its natural shape is deemed appropriate for at least partial softening of the polymer. The appropriate temperature may also depend on the duration of sample incubation; 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 duration of time required to subject the hair fiber to such temperatures to achieve restyling or destyling can also be determined. Generally, 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 or 3 hours, with higher temperatures requiring shorter softening times. Hair styling compositions can, if desired, be sold with instructions regarding the temperatures and times required for restyling or de-styling.

[0172] 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 hair growth, these sites will be found increasingly farther from the scalp, and the newly grown hair adjacent to the scalp will lack such an internal styling skeleton. Following this hair growth, hair styling compositions applied at later times will likely act primarily on the newly grown sites, with the previously treated sites already "occupied" by the pre-formed synthetic polymer. However, as explained above, the existing polymer allows for restyling or de-styling of the hair fiber, so it can functionally integrate with the polymer that will be newly formed at the new site, providing "styling continuity" along the entire fiber, both existing and newly grown.

[0173] The present invention further provides a liquid composition for styling mammalian hair fibers, the liquid composition comprising: at least one monomer selected from HPM and PBM, as described herein; Water, and one or more co-solvents; a single-phase composition comprising: The liquid composition has a pH adapted to promote penetration of the monomers into the hair fiber.

[0174] The present invention further provides a liquid composition for styling mammalian hair fibers, the liquid composition comprising: an oil phase containing at least one monomer selected from HPM and PBM, as described herein; and an aqueous phase containing water with a pH adapted to promote penetration of the monomers into the hair fiber; a hardenable oil-in-water emulsion comprising: Each of the oil phase and the aqueous phase optionally further comprises one or more co-solvents; The oil phase is dispersed in the water phase, the oil-in-water emulsion having a pH adapted to promote penetration of the monomers into the hair fiber.

[0175] In some embodiments, the single-phase composition or 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.

[0176] In some embodiments, the liquid hair styling composition (e.g., an oil-in-water emulsion) optionally further contains at least one additive selected from the group comprising emulsifiers, humectants, thickeners, co-polymerization agents, and charge control agents, as described above and in further detail herein.

[0177] Advantageously, hair styling compositions according to the present teachings are devoid of known carcinogenic compounds.For example, in some embodiments, hair styling compositions contain acceptable trace amounts of such compounds, and depending on jurisdiction, 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 level 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 even no formaldehyde at all, based on the 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-releasing agents), glutaraldehyde, and products that may generate or act as glutaraldehyde (e.g., 2-alkoxy-3,4-dihydropyrans). These hazardous compounds, including their respective precursors or substituted forms (also known as formaldehyde-generating compounds or formaldehyde-releasing agents), include, for example, quaternium-15 (e.g., Dowicil 200; Dowicil 75; Dowicil 100; Dowco 184; Dowicide Q, and Dow Chemical Company); imidazolidinyl urea (such as Germall™ 115, Ashland); diazolidinyl urea (such as Germall™ II); bromonitropropanediol (Bronopol); polyoxymethylene urea; 1,2-dimethylol-5,6-dimethyl (DMDM) hydantoin (marketed as Glydant); tris(hydroxymethyl)nitromethane (trisnitro); tris(N-hydroxyethyl)hexahydrotriazine (Grotan® BK); and sodium hydroxymethylglycinate, which may be referred to herein individually and collectively as small molecule reactive aldehydes (SRAs).

[0178] 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 a member of a further chemical family, so long as it is capable of forming (e.g., by hydrolysis, decomposition, reaction, etc.) harmful aldehydes, such as formaldehyde and glutaraldehyde. Such formation can be triggered by conditions common in hair styling, such as the application of heat. While some such precursors can be fully converted to formaldehyde or glutaraldehyde, and one molecule of SRA, optionally via intermediate products, will generate one or more molecules of formaldehyde under ideal conditions, this is an extreme case, and other precursors can only be partially converted. Heximinium salts are an example of the latter.

[0179] 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 may be formed thereby. In certain embodiments, the hair styling composition contains less than 0.5 wt% SRA, less than 0.2 wt% SRA, less than 0.1 wt% SRA, less than 0.05 wt% SRA, less than 0.01 wt% SRA, less than 0.005 wt% SRA, less than 0.001 wt% 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 process (e.g., upon heating the composition).

[0180] 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 the treated hair fibers.The reaction products of formaldehyde depend on the amino acid with which it reacts; for example, reaction with cysteine ​​produces thiazolidine and hemithioacetal, reaction with homocysteine ​​produces thiazinane and hemithioacetal, reaction with threonine produces oxozolidine, and reaction with homoserine produces 1,3-oxazinane.These reaction products can be detected in hair fibers by standard methods, such as nuclear magnetic resonance (NMR).

[0181] Thus, mammalian hair fibers styled according to the methods or with the compositions 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 significantly lacking 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 measured by NMR. Because cysteine ​​can account for up to 18% of the amino acid repeats in normal human keratin proteins, 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.

[0182] 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 their synthetic and / or modified (e.g., hydrolyzed) forms, and the absent peptides may be smaller fragments of such proteins. For simplicity, such peptides may be named according to the larger protein 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.

[0183] While amino acids, peptides, or proteins, particularly keratin, collagen, and their related peptides, constitute 1 wt% or less of the composition, compositions according to the present invention are substantially devoid of such substances, preferably with their respective concentrations being 0.5 wt% or less, 0.1 wt% or less, or 0.05 wt% or less, based on the 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).

[0184] Thus, mammalian hair fibres styled according to the methods or with the compositions of the present invention may additionally or alternatively be characterized as being significantly devoid of peptides and proteins other than those formed in nature. Where hair fibres have been conventionally treated with naturally occurring proteins or related peptide fragments thereof, hair fibres styled according to the methods of the present invention may, in contrast, be characterized as being significantly devoid of peptides of proteins naturally occurring in the hair fibre.

[0185] In summary, mammalian hair fibers containing therein at least partially cured PBM of the present invention forming a synthetic polymer within the fiber have the following characteristics: i) having less than 0.2 wt. % of reaction products of formaldehyde and amino acids based on the weight of the hair fiber, wherein said reaction products are selected from the group comprising thiazolidines, hemithioacetals, thiazinane, oxozolidines, and 1,3-oxazinane thiazolidines; 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 of at least 95%, at least 100%, at least 105%, at least 110%, at least 115%, or at least 120% of that of similar untreated hair fibers as measured by tensile analysis; and v) having less than 0.2 wt. % of small reactive aldehydes (SRAs) selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals, based on the weight of the hair fiber; It can be characterized by at least one of the following:

[0186] In one embodiment, the mammalian hair fiber meets at least feature i) listed above. In one embodiment, the mammalian hair fiber meets at least feature ii) listed above. In one embodiment, the mammalian hair fiber meets at least feature iii) listed above. In one embodiment, the mammalian hair fiber meets at least feature iv) listed above.

[0187] In one embodiment, the mammalian hair fiber satisfies at least the features i) and ii) listed above. In one embodiment, the mammalian hair fiber satisfies at least the features i) and iii) listed above. In one embodiment, the mammalian hair fiber satisfies at least the features i) and iv) listed above. In one embodiment, the mammalian hair fiber satisfies at least the features i) and v) listed above. In one embodiment, the mammalian hair fiber satisfies at least the features iii) and iv) listed above. In one embodiment, the mammalian hair fiber satisfies at least the features i), iii) and iv) listed above. In one embodiment, the mammalian hair fiber satisfies at least the features i), ii), iii) and iv) listed above. In one embodiment, the mammalian hair fiber satisfies at least the features i), ii), iii), iv) and v) listed above.

[0188] The present invention also provides a kit for styling mammalian hair fibers, the kit comprising: a) a first compartment containing at least one monomer selected from HPM and PBM; and b) a second compartment containing either water or at least one pH adjuster, the pH of which is adapted to promote penetration of the monomers into the hair fiber; Including, 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 in further detail herein.

[0189] 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 that may reduce the efficacy of the composition during storage of the kit. 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.

[0190] In some embodiments, at least one HPM or PBM is prepolymerized before being placed in the first compartment of the kit.

[0191] The kit may further include at least one cure accelerator, which may be a condensation-curable crosslinker or an addition-curable crosslinker. The cure accelerator may also be a cure accelerator, as described above, used to accelerate polymerization. The cure accelerator (either a crosslinker or a cure accelerator) may be placed in the first or second compartment depending on its reactivity with one of the components in those compartments. For example, a polyamine-based crosslinker may be included in the first compartment because it does not react with HPM or PBM at room temperature. Alternatively, if the cure accelerator tends to spontaneously react with either component, it may be placed in another additional compartment. A reactive silane crosslinker is one such example; it would react even at room temperature if placed in the same compartment as PBM, and therefore would be placed separately in the kit.

[0192] The kit may optionally further comprise at least one of a cosolvent, an emulsifier, a humectant, a thickener, an auxiliary polymerization agent, and a charge control agent, as detailed above, which may be contained in any one of the compartments described above or in another additional compartment. When considering the location of such additives, it is preferable to place oil-soluble components in a compartment containing a large amount of oil-based components (e.g., the first compartment), and water-soluble components in a compartment containing a large amount of aqueous components (e.g., the second compartment).

[0193] The kit typically includes a leaflet directing the end user to mixing the various compartments, the order of which may depend on the nature and / or content of the ingredients in each compartment. Generally, the suggested mixing and application method will allow for the preparation of an effective and safe composition, applied within a time frame 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 that the accelerator should be mixed with the HPM or PBM first, followed by the addition of 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.

[0194] In some embodiments, the ingredients of the various compartments are mixed as may be directed 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.

[0195] 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 a 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. [Example]

[0196] 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. Unless otherwise noted, all materials were purchased at the highest purity available. N / A indicates information not available.

[0197] [Table 1] JPEG0007765089000006.jpg205153JPEG0007765089000007.jpg91153

[0198] 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."

[0199] Device Flat Iron: Babyliss® I-Pro 235 Intense Protect Agitator: Digital orbital shaker TOU 50 (MRC Lab, Israel) Stirring hotplate: C-MAG HS 7 Control (IKA, Germany) Oven: Heraeus oven, UT 12 (Thermo Scientific, USA) Hair dryer: Itamar superturbo Parlux 4600 (Parlux®, Italy) Differential scanning calorimeter: DSC Q2000 (TA Instruments, USA) Viscometer: Brookfield DV-II (Brookfield Engineering Laboratories Inc., USA) Water bath: BL-30 (MRC, UK) Vortex mixer: Vortex-Genie 2 (Scientific Industries, USA) Confocal laser microscope: Lext 5000 (Olympus, Japan) Tensile testing machine: MTT157 (Dia-Stron, UK) Centrifuge: Tabletop centrifuge Z383 (Hermle, Germany) Rotary evaporator: Hei-VAP Value (Heidolph, Germany) Gas chromatograph GC-MS: GCD G1800A (HP, USA)

[0200] Example 1: Preparation of an oil-in-water emulsion containing a condensation-curable PBM PBM mixture: 0.2 g of CNSL was placed in a 20 ml vial, and 0.2 g of Dynasylan® AMEO was added using a glass rod and mixed in. 0.4 g of IPA was then added and mixed manually for approximately 10 seconds until the contents of the vial were completely dissolved, as confirmed by light microscopy.

[0201] Aqueous mixture: Alkaline water with a pH of 10 was prepared by adding 5 drops of ammonium hydroxide (amount of base of approximately 0.075 g) to 100 g of deionized water. In a separate 100 ml plastic cup, 15.8 g of alkaline water with a pH of 10 was mixed manually with 2 g of IPA for approximately 10 seconds.

[0202] Oil-in-water emulsion: The contents of the vial containing the PBM mixture (also referred to as the PBM compartment) were added to the cup containing the aqueous mixture (also referred to as the aqueous compartment) and mixed vigorously by hand for approximately 10 seconds until an emulsion was obtained (a "milky" appearance).

[0203] This composition (Em1) is reported in Table 2, which shows further compositions prepared according to the procedure described above, each containing different components, additives and their respective amounts in each of the two compartments as specified in the table. The values ​​given in the table correspond to the concentration of each component in weight percent (wt%) relative to the weight of the total emulsion.

[0204] [Table 2]

[0205] The emulsions prepared in this manner all had a pH in the range of approximately 9 to 11, were stored at room temperature until further use, and were typically applied to hair samples within 1 minute of emulsification. After application to hair samples, the emulsions prepared in this manner are expected to polymerize primarily by condensation curing.

[0206] The zeta potential values ​​of compositions Em1, Em2 and Em3 were measured using a Zetasizer Nano Z (Malvern Instruments) equipped with a folded capillary cell DTS1070 and were found to be −22.2 mV, −19.3 mV and −28.6 mV, respectively, demonstrating that the compositions of the present invention provide a more positive zeta potential at each pH compared to native fibers, which are known to have a zeta potential of approximately −70 mV at pH 10.

[0207] Example 2: Straightening hair with PBM compositions The hair tresses used to test the hair straightening ability of the oil-in-water emulsions of the present invention were either black, curly hair of Indian origin obtained from Vogue hair extensions (approximately 40 cm long, Natural curly indianremihairextensions.com) or coily / kinky hair of Ethiopian origin obtained from a volunteer (approximately 20 cm long). Each tress was held together by gluing one end with epoxy adhesive and weighed approximately 0.6-1.3 g including the glued tip.

[0208] All curly or coiled hair tresses were washed with tap water containing 5% sodium lauryl sulfate at 38–40°C to remove any material adhering to the hair (e.g., dirt or oil) and then hung to dry at room temperature for at least 1 hour, during which time the tresses regained their original shape.

[0209] The basic treatment and straightening procedure applied to clean hair samples is described below and is represented diagrammatically in Figure 8, which shows a simplified diagram of the different steps. For simplicity, the composition or method may be referred to as "straightening", which in this example is intended to describe, among other things, the specific hair styling effect of "complete flattening" of the hair fiber, and to encompass any significant shape modification in which the hair is relaxed into a shape that is less wavy than its natural shape.

[0210] procedure: 1. Hair fiber pre-treatment (as depicted in step S01 of Figure 8): Residual moisture was removed from the dry, clean hair tresses and a flat iron was passed over the tresses four times at a temperature of 200°C to obtain straightened hair tresses. 2. Composition Application (as depicted in step S02 of FIG. 8): The heat-straightened hair tresses were then immersed in a 100 ml plastic cup containing approximately 15-20 g of a hair styling composition (e.g., an oil-in-water emulsion) comprising PBM, as prepared in Example 1. 3. Incubation of the compositions (as depicted in step S03 of FIG. 8): Cups containing hair tress samples soaked in various PBM emulsions were gently shaken using a digital orbital shaker for predetermined periods ranging from 30 minutes to 120 minutes at set temperatures ranging from room temperature (approximately 23° C.) to 60° C. Unless otherwise noted, all preliminary experiments were conducted at room temperature with a 2-hour incubation period. 4. Rinsing of the hair fibers (as depicted in step S04 of Figure 8): The hair tresses thus treated were rinsed thoroughly to eliminate excess composition in view of the method of experimental application. Unless otherwise stated, the hair fibers were rinsed with tap water at a temperature of about 38-40°C, dried twice with a towel, dripped or dried using a hair dryer for 2-3 minutes. 5. Styling the Hair Fiber (as depicted in step S05 of FIG. 8): The rinsed hair tresses were then straightened (approximately 15-50 passes) using a flat iron at a temperature of 220° C. for 2-5 minutes, 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). 6. Hardening of the Polymerizable Styling Composition (as depicted in step S06 of FIG. 8): Hair tresses straightened and dried according to step 5 were subjected to additional heat using a hair dryer or oven to ensure further hardening of the PBM polymerized therein. For further hardening of the PBM, PBO, or PBP within the hair fibers using a hair dryer, the hair sample was held on a brush, and a hair dryer blowing air at a temperature of 150-220°C was moved rapidly over the hair tress at close range approximately 15 times, causing the hair fibers to experience a temperature increase of up to 220°C for several seconds. For further oven hardening, the hair sample was maintained at 200°C for 4 minutes to replicate the conditions of standard hair drying techniques.

[0211] Photographs of each hair sample were taken after pre-washing, when the fibers were still in an unmodified curled or coiled state, and after completion of treatment, when the fibers had been straightened or otherwise modified and the PBM content had at least partially hardened.

[0212] As supported by the following examples, it should be noted that not all steps described in this example, which are performed to illustrate the effectiveness of the present compositions and methods in a laboratory environment, are necessary for conventional use of such compositions and methods (e.g., at home or in a beauty salon). For example, the composition can be applied to clean hair and / or hair treated to remove residual moisture, but such pretreatment of the hair fiber prior to application of the composition is not essential. In other words, step S01 is optional, and therefore the block surrounding it in Figure 8 is outlined with a dashed line. Similarly, for the purpose of quickly evaluating effectiveness, all hair samples were subjected to further curing (S06), but this process could be completed in the daily use of a hair styling composition according to the present teachings by following the styling step (S05) upon sufficient drying to achieve the desired modified shape.

[0213] Conversely, additional steps can be used or existing steps can be modified, as shown in the following examples. For example, after the optional rinsing step (S04), a curable composition containing an excess amount of a curing accelerator can be applied for a short time, or rinsing can be performed with a dedicated solution other than tap water. Similarly, before styling the hair fiber (S05), the hair can be treated with a formulation that protects the hair from damage that may result from the temperatures applied during styling. Such a thermal protection formulation can include or consist of an oil that has a relatively high smoke point at temperatures higher than those applied for styling. Silicone oil can be used for this purpose.

[0214] Example 3: Durability of hair straightening Hair tresses treated with the compositions of the present invention, as described in Example 2, were subjected to a series of washes either immediately after curing step 6 of Example 2 or 48 hours thereafter. In each wash cycle, the tresses were massaged twice between the practitioner's fingers with a standard shampoo (Shea Natural Keratin Shampoo, manufactured by Saryna Key, Israel) for approximately 30 seconds, ensuring complete coverage and close contact from tip to tip, rinsed with tap water at approximately 40°C, wiped dry, and hung to dry for at least 10 minutes. This wash cycle was performed no more than twice a day to mimic the frequent washing of a human subject.

[0215] The number of washes that the hair strands remain "straightened," including any type of modified shape obtained at the end of the straightening procedure of Example 2, after washing indicates the durability of the hair styling provided by the present compositions and methods. This number can also be referred to as the "wash resistance" achieved by a particular composition under the conditions applied and tested. Wash resistance can be qualitatively assessed visually by a trained operator, with the results indicating the number of wash cycles following which 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 a desired number of wash cycles and / or by counting the number of deviations from straight hair (e.g., peaks and valleys) in a representative number of fibers. Length can be measured by placing the hair fiber along a ruler without stretching or pulling the hair fiber. The number of "kinks" in the hair fiber is obtained by counting the number of deflection angles (minimum and maximum) observed on the fiber. The number of twists can be normalized by hair length, and the straightness efficiency can be calculated by dividing the normalized number of twists after the considered treatment by the normalized number of twists before the treatment (reference value).The straightness efficiency can be expressed as a percentage of the reference value.As long as the measurements (e.g., length, number of twists, straightness efficiency) before washing and during the considered washing cycle are similar (e.g., within 10% of each other), or as long as trained operators cannot detect any visual changes, the hair fiber is "wash-resistant".Similarly, this method can be used to evaluate the effectiveness of hair styling compositions.

[0216] Table 3 shows the wash resistance of the composition of Example 1 applied to hair tresses that were treated and straightened as described in Example 2, and the results were assessed qualitatively by trained operators.

[0217] [Table 3]

[0218] It should be noted that while all compositions were resistant to 5 or more washes, supporting at least partial penetration of the PBM with the hair fiber and polymerization therein, the results provided for Em1 and Em2 are not conclusive, as detailed in Example 4.

[0219] Additionally, the wash resistance of chemically treated hair was tested. Hair tresses previously bleached using a commercial bleaching powder mixed with 2 times its weight of a cream developer containing 9% hydrogen peroxide for 1 hour were treated with Em1 and straightened as described in Example 2. Wash resistance was assessed as described in Example 3 and found to be 26.

[0220] Hair treated with Em1 and washed 30 times was tested for suitability for coloring using conventional coloring methods. Wella Koleston Natural - Blueberry Black was applied according to the manufacturer's instructions. Interestingly, hair styled using the method of the present invention can be more successfully colored to achieve the intended color, in contrast to some conventional methods that may affect the color developed or formed before straightening, generally resulting in a deviation from the intended color.

[0221] In an additional experiment, a hair styling composition prepared according to Em1 was similarly tested, the additional composition containing N-[3-(trimethoxysilyl)-propyl]-ethylenediamine instead of AMEO, and the respective amounts of all components remained the same. Hair treated with this hair styling composition was successfully straightened, and the styled hair was able to withstand 23 washes.

[0222] Example 4: Re-styling of hair treated with a PBM-containing emulsion Hair samples treated with Em1 and Em2, which had withstood 50 washes in Example 3, were subjected to this test. The hair samples were straightened as described in step 5 of Example 2. In this case, the heat treatment was not intended to achieve partial cure of the monomer; the hair samples' resistance to 50 shampoo washes confirmed the formation of PBPs within the fibers. Instead, the treatment was intended to soften the polymer sufficiently to reform the hair fiber, as confirmed by the observed results. In this example, the hair samples were restyled to have the same flat modified shape as the original styling, but without limitation, any other second modified shape could have been applied to the fibers. The hair samples were allowed to cool to room temperature, allowing the polymer to regain its stiff / unsoftened structure, at which point they were subjected to a wash cycle as described in Example 3. Both restylized hair samples exhibited resistance to at least 50 additional washes.

[0223] Example 5: Emulsions containing different crosslinkers and PBM - effect on wash resistance A new series of oil-in-water emulsions was prepared, where each PBM mixture was prepared with a different crosslinker, according to the procedure described in Example 1. The contents of each composition in each of the PBM and aqueous compartments are reported in Table 4, where the concentration of each component is reported as wt% of the total emulsion.

[0224] [Table 4]

[0225] These compositions (all having a pH in the range of about 9-11) were easily applied to clean hair tresses as described in Example 2, and the hair samples were immersed in the emulsion for 120 minutes at room temperature as described in step 3. A curing step 6 was performed using a hair dryer. All emulsions resulted in straightening of the hair fiber.

[0226] The durability of the straightening effect provided by these compositions was measured according to Example 3 after the hair tresses were kept at room temperature for 48 hours. All three emulsions withstood more than five washes. This result suggests that the PBM of CNSL penetrates well into the hair fiber in the presence of various crosslinking agents.

[0227] Example 6: Emulsions containing different co-solvents and PBM - Impact on wash resistance A new series of oil-in-water emulsions was prepared according to the procedure described in Example 1, in which the PBM and / or aqueous mixtures were prepared using co-solvents other than or in addition to IPA. The contents of each composition in each of the PBM and aqueous compartments are reported in Table 5, where the concentration of each component is reported as wt% of the total emulsion.

[0228] [Table 5]

[0229] Em12 of this example was a close relative of Em1 of Example 1, replacing isopropyl alcohol (CHCHOHCH) with ethyl alcohol (CHCHOH) in the PBM compartment. These compositions (all having a pH in the range of about 9-11) were easily applied to clean hair tresses as described in Example 2, and hair samples were immersed in the emulsion for 120 minutes at room temperature as described in step 3. Curing step 6 was performed using a hair dryer. All four emulsions achieved straightening of the hair fiber.

[0230] The durability of the straightening provided by these compositions was measured according to Example 3 after the hair tresses were kept at room temperature for 48 hours. All four emulsions provided durability for more than eight washes. This result suggests that the PBM of CNSL penetrates well into the hair fiber in the presence of various co-solvents.

[0231] Example 7: Emulsion containing PBM and hydrolysis promoter Following the procedure described in Example 1, a new series of oil-in-water emulsions were prepared to test the effect of including a hydrolysis promoter on hydrolysis.

[0232] Composition Em15 was prepared using a crosslinker that was at least partially hydrolyzed with water prior to mixing with the other components of the PBM compartment. Specifically, 0.2 g of Dynasylan® AMEO, otherwise stored under a dry, inert atmosphere, was mixed with 0.008 g of deionized water (pH 7) in a 20 ml plastic cup and allowed to at least partially hydrolyze for 5 minutes at room temperature. After partial hydrolysis, the AMEO was transferred to a 20 ml plastic cup, where it was mixed with 0.2 g of CNSL and 0.4 g of IPA to obtain a partially prehydrolyzed PBM mixture. The aqueous mixture was the same as Em1, and the two compartments were emulsified together as described in Example 1.

[0233] Compositions Em16 and Em17 were prepared using dry Dynasylan® AMEO that had not been pretreated with water, and Em16 was prepared by adding the hydrolysis promoter salicylic acid to the PBM mixture.Composition Em17 was prepared by adding the hydrolysis promoter salicylic acid to the aqueous mixture.

[0234] The contents of each composition in each of the PBM and aqueous compartments are reported in Table 5, where the concentration of each component is reported as wt % of the total emulsion.

[0235] [Table 6]

[0236] These compositions (all having a pH in the range of about 9-11) were easily applied to clean hair tresses as described in Example 2, and the hair samples were immersed in the emulsion for 120 minutes at room temperature as described in step 3. A curing step 6 was performed using a hair dryer. All three emulsions resulted in straightening of the hair fiber.

[0237] The durability of the straightening effect provided by these compositions was measured according to Example 3 after the hair tresses were kept at room temperature for 48 hours. All three emulsions withstood more than seven washes. This result suggests that the PBM of CNSL penetrates well into the hair fiber, regardless of the presence or absence of processes or agents that promote hydrolysis.

[0238] Example 8: Differential Scanning Calorimetry (DSC) Studies Keratin hair fibers exhibit characteristic endothermic peaks in many thermal analysis methods, each representing a chemical change occurring around a different temperature. In this study, the following hair samples were analyzed by DSC: i) untreated curly black hair fiber used as a reference, ii) hair fiber treated with a conventional semi-permanent organic hair straightener, iii) hair fiber treated with a conventional Japanese permanent hair straightener, and iv) hair fiber treated with Em1 prepared as described in Example 1 according to the straightening procedure of Example 2 and cured with a hair dryer. All straightening treatments were applied to a curly black hair sample similar to the untreated reference.

[0239] 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 was placed in a 70 μl DSC platinum crucible. The crucible was kept open during the measurement.

[0240] The sample was placed in a differential scanning calorimeter and subjected to DSC measurement, specifically, heating under nitrogen at a rate of 10°C / min up to 400°C while data were acquired and stored.

[0241] The stored data were plotted to obtain a DSC curve for each sample, and the four resulting curves are depicted in the thermograms in Figure 7. For comparison between the various hair straightening techniques, the absolute value of the heat flow, generally plotted on the y-axis, is not important (and therefore not shown), and only the temperatures at which a physical change in the fiber was observed were identified.

[0242] The solid line at the bottom of the plot represents the curve for untreated black hair fibers. Two endotherms were observed at 234.5°C and 250°C, which are characteristic temperatures for hair fibers. The first endotherm near 234.5°C represents the dissolution of α-keratin in the fiber, while the second endotherm near 250°C is thought to represent the decomposition of keratin and the cleavage of disulfide bonds.

[0243] The dotted line above the reference curve shows the behavior of hair samples treated with the oil-in-water emulsion of the present invention. Two endotherms are observed at 234.6°C and 247°C, indicating that treating and styling hair with this method did not substantially alter the molecular structure and intrinsic properties of the hair fiber. The lowest endotherms are within 0.1°C of each other, and the highest endotherms are within 3°C of each other.

[0244] The top two curves in the plot show the behavior of hair fibers after treatment with a commercial hair straightening procedure. The top short-dashed curve is for hair treated with a Japanese hair straightener, which exhibits two endotherms at 226.9°C and 238.8°C. The bottom long-dashed curve is for hair treated with an organic hair straightener, which exhibits two endotherms at temperatures of 229°C and 240.1°C. The DSC curves for both conventional procedures show changes in hair structure and / or properties, consistent with the harsh nature of these straightening procedures. That is, the minimum endothermic temperatures for the Japanese hair straightener and the organic hair straightener are within 7.6°C or 5.5°C, respectively, of the values ​​for natural, untreated hair, while the maximum endothermic temperatures are within 11.2°C or 9.9°C of the values ​​for natural, untreated hair. A deviation of at least one endotherm temperature of the modified hair from the value of the corresponding endotherm in untreated, natural hair by at least 5°C is believed to indicate a significant adverse modification of the physicochemical properties of the hair fiber as a result of the styling. Conversely, the inventors believe that a difference of less than 4°C between at least one pair of corresponding endotherms in untreated and treated hair is indicative of a relatively harmless treatment. Preferably, the two temperatures at corresponding endotherms should be within 3°C, 2°C, or 1°C of each other.

[0245] Such measurements may alternatively be obtained from other thermal analysis methods, such as thermomechanical analysis (TMA) or dynamic mechanical analysis (DMA).

[0246] Example 9: Emulsions containing different wetting agents and PBM - effect on wash resistance A new series of oil-in-water emulsions was prepared and a wetting agent was included in the composition according to the procedure described in Example 1. The addition of the wetting agent slightly altered the relative concentrations of the monomer and its crosslinker, but the new compositions are comparable to Em1 and Em2.

[0247] The contents of each composition in each of the PBM and aqueous compartments are reported in Table 7, where the concentration of each component is reported as wt % of the total emulsion.

[0248] [Table 7]

[0249] The durability of the straightening provided by these compositions (all having a pH in the range of about 9-11) was measured according to Example 3 after the hair tresses were kept at room temperature for 48 hours. All five emulsions provided durability of over 8 washes on average. This result suggests that the PBM of CNSL penetrates well into the hair fiber in the presence of various humectants.

[0250] Example 10: Destyling of hair treated with an emulsion containing PBM Originally curly hair samples that had been treated with Em1 or Em3 and then straightened were washed according to Example 3 for the number of cycles as specified in column 2 of Table 8 to establish stability of their altered (flattened) shape. Samples that were still styled were then subjected to the main test in which the hair was allowed to resume its original (unaltered) shape.

[0251] The styled hair samples were subjected to a destyling treatment in which each sample was immersed in a 100 ml plastic cup containing approximately 15 g of destyling solution, either tap water or an ammonium solution at pH 10.5. The cup was then placed in a digital orbital shaker and shaken for a set period of time at a set temperature, as specified in Table 8. As can be seen from the table, all destyling methods allowed the previously styled (straightened) hair fibers to return to their original curly shape.

[0252] [Table 8]

[0253] We speculate that the destyling process is not caused by the removal of synthetic polymers entrapped within the hair fibre, which was confirmed by the ability to further restyle the hair samples, as previously described.

[0254] Example 11: Preparation of a single-phase composition containing PBM A single-phase hair styling composition was prepared as follows: 1.5 g of CNSL was placed in a plastic vial and mixed with 0.15 g of Dynasylan® AMEO using a glass rod. 15 g of dipropylene glycol methyl ether (DPGME) and 6 g of alkaline water (pH 10) were then added, and the contents of the vial were mixed by hand for approximately 10 seconds until completely dissolved, as observed by the formation of a clear solution and confirmed by light microscopy.

[0255] This composition (Sol 1) is reported in Table 9, which shows additional single-phase compositions prepared according to the procedure described above, each containing different components, additives, and their amounts as specified in the table. The values ​​given in the table correspond to the concentration of each component in weight percent relative to the weight of the total single-phase composition.

[0256] [Table 9]

[0257] The single-phase compositions were applied to hair fiber styling as previously described for oil-in-water emulsions, and their ability to provide durable styling was evaluated by monitoring the number of shampoo cycles that each treated hair sample withstood. Both solutions provided wash resistance of up to approximately 20 shampoo cycles.

[0258] Example 12: Prepolymerized Hair Styling Composition and Method of Use Hair styling composition Em1' was prepared similarly to composition Em1 of Example 1 in terms of the identity and amounts of the components, but with the following differences in the preparation method. The PBM and crosslinker were heated together before combining with the cosolvent according to the following procedure: a vial (equipped with a magnetic stirrer) containing CNSL and AMEO was placed on a stirring hotplate and maintained at a temperature of approximately 50°C for 1 hour while stirring. This step was carried out to ensure at least partial prepolymerization of these polymerizable materials. The viscosity of the mixture was measured at 25°C before and after the heating step using a Brookfield DVII viscometer and a water-cooled condenser (BL-30, MRC). The viscosity of the polymerized material was observed to increase from 28 mPa·s to 33 mPa·s, confirming partial prepolymerization.

[0259] Room temperature IPA was then added to the viscous hot mixture and stirred to obtain a PBM mixture. The procedures for preparing the aqueous mixture and the resulting oil-in-water emulsion (which was combined with the PBM mixture of this example) were followed as described in Example 1.

[0260] The hair straightening procedure of Example 2 and the durability analysis of Example 3 were then performed, as reported in Table 10, with the following modifications. Each row in the table represents a separate test, designated as Em1'a through Em1'e. For convenience, the conditions described for Em1 of Examples 1-3, as modified in this example, are provided for quick reference. The equal sign = indicates that the conditions for the test performed with the Em1' composition for a particular step were as described for Em1 of Examples 1-3. NP means that the step was not performed. The curable composition applied in Test Em1'e was an aqueous solution containing 5 wt % zinc acetate dihydrate, which was applied for 5 minutes onto rinsed hair fibers. Each test was performed on Brazilian curly hair from nine different sources.

[0261] [Table 10]

[0262] After each of the above hair styling procedures, the hair tresses were washed as described in Example 3 and the durability of the hair straightening was measured by drying using a hair dryer after each washing cycle.

[0263] In contrast to previous examples, in which washing cycles were spaced apart to allow for two washing cycles per day, ten washing cycles were performed per day to expedite the assessment of wash resistance.This rapid test of wash resistance is considered more vigorous for polymers that are at least partially polymerized in hair fibers, since polymerization may still be incomplete depending on the test conditions.Therefore, hair styling compositions and / or methods that provide relatively frequent washing resistance of at least 10 washings as performed in this example are expected to be resistant to at least less than 10 washings or more than that in conventional hair washing by human subjects.

[0264] All hair tresses treated with Composition Em1' and styled according to the method with specific steps as described in Table 10 (i.e., Em1'a-Em1'e) remained straightened after 10 washes in one day. This observation was repeated for all nine hair samples in each test. For comparison, hair samples treated with Em1 (lacking prepolymerization of PBM with crosslinker) yielded less reproducible results, and wash resistance varied among the nine hair samples, despite all being Brazilian curly hair. On average, all samples treated with Em1 using the styling method of Example 2 without any special modifications yielded resistance to approximately six washes, with some hair samples surviving 10 washes. Therefore, it is believed that the prepolymerization performed on Em1' at least improves the reproducibility of the hair styling method and may result in a shorter incubation period.

[0265] Additional compositions similar to Em1' were prepared by varying the prepolymerization conditions. While Em1' involved stirring the polymerizable components CNSL and AMEO for 1 hour at approximately 50°C before adding the remaining components of the hair styling composition, in this series of experiments, the same polymerizable materials were prepolymerized by stirring at room temperature (approximately 23°C) for 5, 15, 30, 60, or 150 minutes. All final compositions containing these prepolymerized mixtures were applied to hair and tested for styling ability and wash resistance of the achieved styling, as described above. All provided long-lasting styling that was resistant to at least 10 washes, and 150 minutes of prepolymerization allowed for up to 25 washes. These results suggest that prepolymerization can be performed under a variety of conditions, including milder temperatures and shorter times.

[0266] The effect of prepolymerizing the polymerizable components of the PBM compartment was further examined by varying the absolute amounts of CNSL and AMEO and the weight ratio of CNSL to AMEO. Briefly, Em1' and related compositions contained CNSL and AMEO in amounts constituting 1.1 wt% of the final emulsion, and IPA was added to the PBM compartment after prepolymerization in an amount constituting 2.2 wt% of the final emulsion. A series of hair styling compositions of Em1' were prepared by prepolymerizing equal amounts of CNSL and AMEO, i.e., a 1:1 CNSL:AMEO weight ratio. In a new series of experiments, the amount of CNSL was halved to constitute 0.55 wt% of the final composition, while the amount of AMEO was reduced to one-quarter of its previous concentration to constitute approximately 0.275 wt% of the final composition, resulting in a 2:1 CNSL:AMEO weight ratio. A series of compositions were prepared by prepolymerizing the low amounts of the polymerizable components described above at room temperature for 15 minutes up to 24 hours, then adding 3.575 wt. % IPA to the PBM compartment and emulsifying with the aqueous compartment as described above. All final compositions containing such prepolymerized mixtures were applied to hair and tested for styling ability and wash resistance of the achieved styles as described above. All produced long-lasting styles that withstood five washes. The compositions were incubated on hair fibers for 2 hours, as in the previous examples, or for as short as 30 minutes. Hair treated with this shortened procedure was also able to be styled (e.g., straightened), and the style could be sustained for five wash cycles without detectable changes in the styled shape of the hair fiber, similar to longer incubation times. These results suggest that styling compositions can be applied to hair for relatively short periods of time.

[0267] Example 13: Hair Styling Composition Containing PBM Prepolymerized with Copolymerizer 4.75 g of cardanol (as PBM) was placed in a 20 ml cup, and 0.25 g of shellac flakes (as a co-polymerization agent) was added and mixed in. The cup was placed on a hot plate equipped with a magnetic stirrer, and the contents were stirred at 140° C. for 30 minutes to obtain an at least partially prepolymerized mixture of cardanol and shellac (referred to as the prepolymerized PBM phase).

[0268] In a separate 20 ml cup, 0.2 g of the prepolymerized PBM phase was placed, followed by the addition of AMEO and IPA to obtain a PBM mixture, which was then combined with the aqueous mixture as described in Example 1 to obtain oil-in-water emulsion Em23.

[0269] Another oil-in-water emulsion, Em24, was prepared similarly, in which AMEO was added to the prepolymerized mixture of cardanol and shellac and stirred at room temperature for approximately 80 minutes before adding IPA to promote the reaction of the crosslinker with PBM.

[0270] Compositions Em23 and Em24 are reported in Table 11. The values ​​reported in the table correspond to the concentration in weight percent of each component relative to the weight of the total emulsion, except for the value in the cardanol-shellac mixture entry, which corresponds to the respective weight percent in the particular prepolymerized PBM mixture.

[0271] Next, Brazilian curly hair was subjected to the straightening treatment of Example 2 without the pre-treatment step 1 to remove residual water. After maintaining the treated fibers for 48 hours, a durability analysis was performed as described in Example 3, and the wash resistance results are also detailed in the last row of Table 11.

[0272] [Table 11]

[0273] Example 14: Prepolymerized Hair Styling Compositions Containing Condensation-Curable PBM CNSL was placed in a 20 ml cup and kept in an oven at 190 °C for 3 hours to induce at least partial prepolymerization. The cup was then placed on a hot plate equipped with a magnetic stirrer, and 2–5 wt% (calculated as a percentage of the total amount of PBM and shellac) shellac flakes were added as an auxiliary polymerization agent. The mixture was then kept at 140 °C for 30 minutes with stirring until the shellac dissolved in the CNSL.

[0274] In a separate 20 ml cup, 0.2 g of the mixture of prepolymerized CNSL and shellac (referred to as the prepolymerized PBM phase) was placed, a crosslinker was added as reported in Table 12, the resulting mixture was maintained at room temperature for about 80 minutes, and then IPA was added to obtain a PBM mixture, which was then combined with the aqueous mixture as described in Example 1 to obtain oil-in-water emulsion Em25.

[0275] Other PBM mixtures were similarly prepared and kept at room temperature for approximately 80 minutes, but after addition of IPA were combined with the aqueous mixture to give oil-in-water emulsions Em27 and Em28.

[0276] In the PBM mixture of composition Em26, tannic acid was used as the crosslinker instead of AMEO, pH and charge adjustment was achieved with oleylamine (which also served as a co-polymerization agent), and the PBM mixture was directly combined with the aqueous mixture without first being kept at room temperature for 80 minutes.

[0277] Compositions Em25-Em28 are reported in Table 12, each containing different components, additives, and their amounts in each of the two compartments as specified in the table. The values ​​reported in the table correspond to the concentration of each component in weight percent relative to the weight of the total emulsion, except for the value for the prepolymerized PBM phase, which corresponds to the weight of such component in that particular PBM mixture.

[0278] A straightening procedure was then performed on curly Brazilian hair as described in Example 13, and the emulsion so prepared is expected to polymerize largely by condensation curing. A durability analysis was also performed as described in Example 13, and the wash resistance results are detailed in the last row of Table 12.

[0279] [Table 12]

[0280] Example 15: Prepolymerized Hair Styling Compositions Containing Addition-Curable PBM 1 g of CNSL was placed in a 20 ml cup and kept in an oven at 190 °C for 3 h to induce at least partial prepolymerization. The cup was placed on a hot plate equipped with a magnetic stirrer, and 0.02 g of shellac flakes (as a co-polymerization agent) was added. The mixture was then stirred at 140 °C for 30 min until a homogeneous mixture was obtained.

[0281] 0.25 g of benzoyl peroxide (BPO) was added to the vial placed on a hot plate, and the mixture was further stirred at 100°C for 60 minutes.

[0282] In a separate 20 ml cup, the CNSL-BPO mixture prepared above (referred to as the prepolymerized PBM phase) was placed, and 0.4 g of IPA was added to obtain a PBM mixture. This PBM mixture was then combined with the aqueous mixture as described in Example 1 to obtain oil-in-water emulsion Em29. Similarly, composition Em30 was prepared without shellac. The resulting compositions are detailed in Table 13, where the reported values ​​correspond to the concentration of each component in wt % relative to the weight of the total emulsion, except for the value in the prepolymerized PBM phase, which corresponds to the weight of such component in that particular PBM mixture.

[0283] A straightening procedure was then performed on curly Brazilian hair as described in Example 13, and the emulsion so prepared is expected to polymerize largely by addition curing. A durability analysis was also performed as described in Example 13, and the wash resistance results are detailed in the last row of Table 13.

[0284] [Table 13]

[0285] Example 16: Prepolymerized Hair Styling Compositions Containing Condensation and Addition Curable PBM 2 g of CNSL was placed in a 20 ml metal can under an argon atmosphere and kept in an oven at 190° C. for 3 hours to induce at least partial prepolymerization.

[0286] The at least partially prepolymerized CNSL was placed in a 20 ml cup equipped with a magnetic stirrer, 0.04 g of shellac flakes (as a co-polymerization agent) was added, and the mixture was placed on a hot plate at 140°C and mixed for 30 minutes until a homogeneous mixture was obtained.

[0287] After cooling at room temperature for approximately 5 minutes, 0.4 g of linoleic acid was added, the contents of the vial were vortex mixed, and then 2 g of AMEO was added. The resulting mixture was stirred at room temperature for 80 minutes.

[0288] In a separate 20 ml cup, 0.4 g of the stirred mixture was placed and 0.4 g of IPA was added to obtain a PBM mixture, which was then combined with the aqueous mixture as described in Example 1 to obtain oil-in-water emulsion Em31.

[0289] Composition Em32 was similarly prepared, but in this case, the CNSL was first purified from any residues or contaminants prior to prepolymerization. This was accomplished by placing 5.5 g of CNSL and 30 g of IPA in a centrifuge tube and centrifuging at 7,500 rpm for 15 minutes, then separating the liquid phase from the precipitate and centrifuging again three more times at the same speed for the same time to obtain purified CNSL. The purified CNSL was transferred to a flask and placed in a rotary evaporator to evaporate the IPA at 45°C and 27 mbar for 2 hours, followed by heating to 120°C to remove residual IPA for another 2 hours. The pure CNSL was then carried on to the prepolymerization step, as described above, and then to the remaining steps of the composition preparation.

[0290] Compositions Em31 and Em32 are reported in Table 14, each containing different components, additives, and their amounts in each of the two compartments as specified in the table. The values ​​reported in the table correspond to the concentration of each component in wt% relative to the weight of the total emulsion, except for the value for the prepolymerized PBM phase, which corresponds to the weight of such component in that particular PBM mixture.

[0291] A hair straightening procedure was then performed on Brazilian curly hair as described in Example 13, where the hair tresses were incubated in the PBM composition for 1 hour, and the straightening procedure was performed with blow drying of the fibers and without post-styling step 6. The emulsions thus prepared are expected to polymerize by both condensation and addition curing after application to hair samples.

[0292] Alternatively, following the rinsing and drying with a hair dryer carried out in step 4, four drops of the silicone oil decamethylcyclopentasiloxane were applied and spread by hand on the hair tresses treated with composition Em32 to act as a protectant against the high temperatures of the hair straightening device.

[0293] Durability analysis was also performed according to Example 13, and the results of wash resistance are detailed in the last line of Table 14.

[0294] [Table 14]

[0295] The presence of aldehydes, particularly formaldehyde, was tested in composition Em31 by gas chromatography-mass spectrometry (GC-MS) according to standard methods (NIOSH 2539 for aldehydes in general and NIOSH 2541 for formaldehyde in particular). A sample of composition Em31 was maintained at a temperature of 100°C for 1 hour to allow evaporation of volatile compounds present or formed during such procedure. A second sample of Em31 was maintained at an elevated temperature of 220°C for 1 hour to further allow at least partial curing of the PBM. Both samples were found to contain aldehyde and formaldehyde concentrations below detection levels, i.e., less than 1 ppm (i.e., less than 0.0001 wt%). As can be readily appreciated, the hair composition is substantially devoid of such SRAs, and therefore hair fibers treated with the hair composition are substantially free of such materials.

[0296] Example 17: Condensation-curable oil-in-water emulsions containing other PBMs and co-polymerizers In a 20 ml cup, 1 g of dibutyl maleate as a co-polymerization agent was added and combined with 1 g of phenyl salicylate as a PBM. The cup was heated with a hair dryer for 20 seconds to dissolve the phenyl salicylate in the dibutyl maleate, then vortex mixed and cooled to room temperature.

[0297] 0.2 g of the above mixture (referred to as PBM stock) was placed in a separate 20 ml cup and combined with 0.2 g of AMEO and 0.04 g of pomegranate seed oil and vortex mixed to obtain a PBM mixture, which was then combined with the aqueous mixture as described in Example 1 to obtain oil-in-water emulsion Em33.

[0298] This composition (Em33) is reported in Table 15, which shows further compositions prepared according to the procedure described above, each containing different ingredients, additives and their amounts in each of the two compartments as specified in the table.

[0299] Oil-in-water emulsion Em37 was similarly prepared, in which a mixture of glycol salicylate (as the PBM) and 2% shellac (as a co-polymerization agent) was first prepared by mixing and heating as described above, followed by combining 0.2 g of the above mixture with 0.2 g of linoleic acid and 1 g of AMEO (also as described above) to obtain a PBM stock. 0.4 g of the resulting PBM stock was combined with 0.4 g of IPA and vortex mixed to obtain a PBM mixture. This PBM mixture was then combined with an aqueous mixture as described in Example 1 to obtain oil-in-water emulsion Em37, also shown in Table 15.

[0300] The values ​​reported in the tables correspond to the concentration of each component in weight percent relative to the weight of the total emulsion, except for the value for PBM stock, which corresponds to the weight of that component in that particular PBM mixture.

[0301] The straightening procedure of Example 13 was performed on curly Brazilian hair, where the hair tresses were incubated in the PBM composition for 1 hour. The straightening procedure also involved blow-drying the fibers and was performed without post-styling step 6. The emulsion thus prepared is expected to polymerize primarily by condensation curing after application to the hair samples. Durability analysis was performed according to Example 13, and the wash resistance results are detailed in the last row of Table 15.

[0302] [Table 15]

[0303] Example 18: Prepolymerized Hair Styling Composition Containing PBM and Emulsifier The PBM mixture was prepared as described for the preparation of Em31 in Example 16, in the absence of IPA as a co-solvent.

[0304] The aqueous mixture, excluding the cosolvent, also contained an emulsifier and was prepared as follows: 0.25 g of Synthalen® W2000 emulsifier was placed in a 100 ml plastic cup, and 99.75 g of distilled water was mixed by hand for 5 seconds. The cup was placed on a stirring hotplate, and 0.1 ml of a 25 wt% ammonium hydroxide solution was added with stirring until a pH of 10 was achieved.

[0305] In a separate 20 ml cup, 0.4 g of the PBM mixture was placed, 15.8 g of the aqueous mixture was added, and the contents of the cup were mixed by hand for 5 seconds until emulsion Em38 was obtained.

[0306] The straightening procedure was then performed on curly Brazilian hair as described in Example 17. A durability analysis was performed according to Example 13 and showed that hair styled with Em38 withstood 25 washes.

[0307] Example 19: Prepolymerized Hair Styling Composition Containing PBM and Thickener The PBM mixture was prepared as described in Example 16 for the preparation of Em31.

[0308] An aqueous mixture, excluding the cosolvent and further containing the thickener, was prepared as follows: 15.8 g of alkaline water at pH 10 (prepared according to Example 1) was placed in a 20 ml cup on a stir plate, 0.158 g of hyaluronic acid was added, and the resulting mixture was kept at room temperature with stirring for 12 hours.

[0309] In a separate 20 ml cup, 0.4 g of the PBM mixture was placed, the aqueous mixture prepared above was added, and the contents of the cup were mixed by hand for 5 seconds until emulsion Em39 was obtained.

[0310] The straightening procedure was then performed on curly Brazilian hair as described in Example 17. A durability analysis was performed according to Example 13 and showed that hair styled with Em39 withstood 20 washes.

[0311] Example 20: Tensile Strength Results The contribution of the compositions of the present invention to the tensile strength of hair treated with these compositions was evaluated and compared to untreated hair. Four hair samples of curly black hair tresses were used: i) Untreated hair, used as reference: ii) Hair treated with a conventional semi-permanent organic hair straightener for comparison: iii) hair treated with composition Em25 prepared as described in Example 14, applied according to the procedure of Example 13 and washed 13 times according to the procedure of Example 13; and iv) Hair treated with composition Em31 prepared as described in Example 16, applied according to the procedure of Example 13 and washed 21 times according to the procedure of Example 13.

[0312] Ten hair fibers from each of the four samples were standardized by maintaining them under the same conditions (temperature 25°C, relative humidity 45%) for three days. The hair fibers were then cut into 30 mm lengths, and their cross sections were measured using a confocal laser microscope, taking into account both the maximum and minimum radii of a typical elliptical hair fiber. The tensile strength parameters of break stress, tenacity, and modulus were measured for hair fibers tested using a tensile tester (100% extension limit, 20 mm / min extension rate, 2 g gauge force, 5 g break detection limit, 2000 g maximum force). The average results for the 10 fibers from each hair sample are shown in Figures 9A and 9B for the first two parameters as a percentage of the untreated hair sample (which itself is shown as 100% in the first column of each figure).

[0313] The stress at break results are shown in Figure 9A, where samples iii) and iv) treated according to the present invention exhibited stress at break values ​​that were 18% and 28% higher, respectively, compared to untreated hair, suggesting that the composition improves the mechanical properties of hair even after multiple wash cycles, which are considered to remove the temporary coating. The organic straightener comparison sample ii) showed lower stress at break: 12% lower than untreated hair sample i) and 40% lower than hair sample iv) treated with the present composition Em31s.

[0314] The hair tenacity results are shown in Figure 9B, with sample iv) showing an 18% increase in tenacity compared to untreated hair sample i), and sample iii) showing a slight decrease of 5%, while sample ii) treated with the organic hair straightener showed significantly lower tenacity: 38% less than untreated hair sample i) and 56% less than the fibers of sample iv) treated with composition Em31.

[0315] The elastic modulus was also measured in the same manner, and the fibers treated with Em25 or Em31 showed results equivalent to those of untreated hair fibers (results not shown).

[0316] In summary, hair fibers treated with the compositions of the present invention demonstrated at least equivalent, if not superior, tensile strength results compared to untreated hair fibers, and were proven to exhibit significantly better results than hair treated with conventional organic hair straighteners.

[0317] It is understood that certain features of the present disclosure, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the present disclosure that are, for brevity, described in the context of a single embodiment may also be suitably provided separately or in any suitable subcombination, or in any other described embodiment of the present disclosure. Certain features described in the context of various embodiments should not be considered essential features of those embodiments, unless the embodiments cannot function without those elements.

[0318] While the present disclosure has been described in terms of various specific embodiments thereof, presented for purposes of illustration only, such specifically disclosed embodiments should not be considered limiting. Many other alternatives, modifications, and variations of such embodiments will occur to those skilled in the art based on applicant's disclosure herein. It is therefore intended to embrace all such alternatives, modifications, and variations and to be bound only by the spirit and scope of the disclosure and any changes that come within the meaning and range of equivalents thereof.

[0319] 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, and it is understood that compositions of the present teachings also consist essentially of or consist of the recited components, and that methods of the present teachings also consist essentially of or consist of the recited process steps.

[0320] 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.

[0321] 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 is eligible and can be selected.

[0322] Unless otherwise stated, when outer boundaries of ranges for features of embodiments of the present technology are set forth in a 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.

[0323] As used herein, unless otherwise specified, adjectives such as "substantially," "approximately," and "about" modifying the condition or relationship property of one or more features of embodiments of the present technology define the condition or property as being within a tolerance range acceptable for operation of the embodiment for its intended use or within the variation expected 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 specified, terms (e.g., numbers) used in this disclosure should be interpreted as having a tolerance range that may deviate from the exact meaning of the associated term even without such adjective, but that allows the invention, or relevant portions thereof, to operate and function as described and as understood by those skilled in the art.

[0324] While the present disclosure has been described in terms of particular 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 understood that the present disclosure is not limited by the particular embodiments described herein.

[0325] Certain marks referenced herein may be common law or registered trademarks of third parties. Use of these marks is exemplary and is not intended to construe or limit the scope of this disclosure to material relating solely to such marks.

Claims

1. 1. A method of styling mammalian hair fibers having a natural shape, the method comprising: a) applying to individual hair fibers a hair styling composition, wherein said hair styling composition comprises at least one water-insoluble energy-curable phenolic monomer (PBM) having a solubility in water of 5 wt % or less, each having an average molecular weight of 10,000 g / mol or less, at least one cure accelerator and co-polymerization agent miscible with said PBM, and water; b) leaving the hair styling composition in contact with the hair fiber for at least 5 minutes; and c) applying energy to at least partially cure at least a portion of the PBM within said hair fiber, wherein said curing occurs while said hair fiber is at a temperature of at least 50°C, so as to obtain a treated hair fiber; Including, The method, wherein the hair styling composition contains less than 0.2 wt. % of a small reactive aldehyde (SRA), the SRA being selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals.

2. The at least one water-insoluble energy-curable PBM has Formula I: 【Chemistry 1】 wherein: i) R １ , R ２ , R ３ and R ５ are each independently a hydrogen atom, a hydroxyl, a linear, branched or cyclic, substituted or unsubstituted C １ ~C ２０ Alkyl, C １ ~C ６ alkoxy, C4-C9 allyl, phenyl ester, or glycol ester; and ii) R ４ is a hydrogen atom, a hydroxyl, or a saturated or unsaturated C Ｘ H Ｙ alkyl, 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. 3. The method of claim 2, wherein the at least one PBM is cashew nut shell liquid (CNSL) or a component thereof.

4. The hair styling composition comprises at least one of: I. at least one cure accelerator selected from crosslinkers and cure accelerators, said at least one cure accelerator adapted to be in the same phase as said PBM within the hair fiber; II. at least one co-polymerization agent containing 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; and III. At least one co-solvent in an amount sufficient to form an oil-in-water emulsion, wherein the at least one PBM is present in the oil phase of the emulsion, and the at least one co-solvent is adapted to be in the same phase as the PBM in the hair fiber. The method of any one of claims 1 to 3, further comprising:

5. (I) before applying the hair styling composition to the hair fiber, A- the at least one PBM, and / or the at least one cure accelerator, and / or the at least one co-polymerization agent are pre-polymerized before mixing with water, and / or B- the hair fiber is pre-treated by at least one of a) washing the hair fiber; and b) drying the hair fiber; and / or (II) The method of any one of claims 1 to 4, wherein the energy is applied while the hair fiber is in a desired modified shape, the modified shape being different from the native shape.

6. 6. The method of any one of claims 1 to 5, wherein the treated and untreated fibers exhibit at least one endothermic temperature within 4°C of each other as measured by thermal analysis.

7. 7. The method of any one of claims 1 to 6, wherein the hair styling composition has a pH that allows penetration of the monomer into the hair fiber, the pH being in a range other than the isoelectric point of the hair.

8. 1. A hair styling composition for modifying the shape of mammalian hair fibers, the composition comprising: a) at least one water-insoluble energy-curable phenolic monomer (PBM) having a solubility in water of 5 wt % or less, each having an average molecular weight of 10,000 g / mol or less, at least one cure accelerator and a co-polymerization agent miscible with the PBM; and b) water; the hair styling composition having the following characteristics: a- the hair styling composition contains less than 0.2 wt. % small reactive aldehyde (SRA), the SRA being selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals; b- said hair styling composition contains less than 1 wt% amino acids; c- the hair styling composition contains less than 1 wt% peptides; and d- said hair styling composition contains less than 1 wt% protein; The hair styling composition as defined above, further characterized by one or more of:

9. The at least one water-insoluble energy-curable PBM has Formula I: 【Chemistry 2】 wherein: 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, C4-C9 allyl, C8-C15 phenyl ester, or C １ ~C ８ glycol esters; and ii) R ４ is hydroxyl or saturated or unsaturated C Ｘ H Ｙ alkyl, 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 8.

10. 10. The hair styling composition of claim 9, wherein the at least one PBM is cashew nut shell liquid (CNSL) or a component thereof.

11. i. has a pH that allows penetration of the monomer into the hair fiber, said pH being in a range outside the isoelectric point of the hair; and / or ii. the total concentration of the at least one water-insoluble energy-curable PBM is at least 0.1 wt % and at most 5 wt % based on the weight of the hair styling composition; A hair styling composition according to any one of claims 8 to 10, characterized by:

12. I. at least one cure accelerator selected from crosslinkers and cure accelerators, said at least one cure accelerator adapted to be in the same phase as the PBM within the hair fiber; II. The at least one co-polymerization agent further comprises at least one functional group capable of cross-polymerizing with at least one of the PBM and the cure accelerator, wherein the functional group is selected from hydroxyl, carboxyl, amine, anhydride, isocyanate, isothiocyanate, and double bond; III. C having at least one hydroxyl group １ ~C １０ a co-solvent selected from the group consisting of alcohols, water-miscible ethers, aprotic solvents, esters, and mineral or vegetable oils, in an amount that controls the form of the composition, wherein the form of the hair styling composition is an oil-in-water emulsion or a single-phase composition; and IV. Additives selected from the group including emulsifiers, wetting agents, thickeners, and charge control agents The hair styling composition of any one of claims 8 to 11, further comprising at least one of:

13. (i) the at least one curing accelerator is at least one 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 diglycidyls, diisocyanates, allyl compounds, polyphenols, acrylates, and linear, branched, or cyclic alkene compounds containing up to 15 carbon atoms and containing multiple double bonds capable of forming at least two radicals upon cleavage of the double bonds; and / or (ii) the at least one curing accelerator is a curing accelerator suitable for at least one of condensation polymerization and addition polymerization, and is selected from a metal complex, a metal soap, a metal salen, and an organic peroxide; and / or (iii) the at least one co-polymerization agent is selected from the group comprising shellac, rosin gum, alkyl or aryl substituted maleates and salicylates, unsaturated fatty oils having an alkene chain of 16 or more carbon atoms including terpenes and terpenoids, fatty amines, fatty acids, and triglycerides of said fatty acids; A hair styling composition according to any one of claims 8 to 12.

14. 1. A mammalian hair fiber comprising at an inner portion at least partially cured energy curable phenolic monomer (PBM)(s) that form a synthetic polymer having a softening temperature, said hair fiber comprising: i) having less than 0.2 wt % of reaction products of formaldehyde and amino acids, wherein said reaction products are selected from the group including thiazolidines, hemithioacetals, thiazinane, oxozolidines, and 1,3-oxazinane thiazolidines; ii) exhibiting at least one endothermic temperature within 4°C of untreated hair fiber as measured by DSC; iii) having a breaking stress that is at least 5% greater than the breaking stress of a similar untreated fiber; iv) having 95% or more of the toughness of similar untreated hair fibers; and v) having less than 0.2 wt % small reactive aldehydes (SRAs) selected from formaldehyde, formaldehyde-forming chemicals, glutaraldehyde, and glutaraldehyde-forming chemicals; characterized by at least one of The mammalian hair fibre, wherein the PBM corresponds to at least one PBM of a hair styling composition according to any one of claims 8 to 13.

15. 1. A kit for styling mammalian hair fibers, comprising: (a) a first compartment containing at least one water-insoluble energy-curable phenolic monomer (PBM) having an average molecular weight of 10,000 g / mol or less and a solubility in water of 5 wt % or less; (b) i. Water with a pH selected to enhance penetration of the PBM(s) into the hair fiber; or ii. at least one pH adjusting agent; and (c) at least one cure accelerator selected from a crosslinker and a cure accelerator, and a co-polymerization agent, miscible with said PBM(s), each having an average molecular weight of 10,000 g / mol or less; Including, mixing these compartments to form an oil-in-water emulsion; and 14. The kit, wherein the PBM(s), the cure accelerator(s), and / or the co-polymerization agent(s) are adapted to form a hair styling composition according to any one of claims 8 to 13.

16. A - said at least one water-insoluble energy-curable PBM is prepolymerized; and / or B- said kit comprising: i) a co-solvent; and ii) an additive selected from the group comprising emulsifiers, wetting agents, thickeners, and charge control agents; and further comprising at least one of 16. The kit of claim 15, wherein any one of the cure accelerator(s), the co-polymerization agent(s), the co-solvent(s), and the additive(s) is / are independently located in the same or a different compartment so as not to react with other components of the compartment during storage of the kit.

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