Method for activating and preparing keratin fiber coatings, preferably color coatings.

Abstract

A coating, preferably color coating, method for keratin fibers is described, which includes three steps: activation, pretreatment, and bonding. The activation step includes one or both of the Praeparatur and Fundamenta procedures to produce modified fibers. The pretreatment step applies a pretreatment composition of at least PTH alkoxysilanes having PTH as a thiol, protected thiol, or thiol-complementarily reactive group to the modified fibers to form pretreated fibers. The bonding step applies a film-forming composition to the pretreated fibers to form a color coating.

Description

[Background technology]

[0001] Over the past 20 years, significant effort has been made toward the development of external hair coloring technologies that can be characterized as permanent but avoid the penetration of bleach and dye precursors into the keratin fiber cortex. This technology primarily involves coloring the hair without the involvement of the cortex. Hair coloring can be achieved by coating the surface of the keratin fibers with a cosmetically acceptable polymer film containing pigment particles, or a multilayer polar attractant film containing coloring dyes instead of pigments. However, non-cortex hair coloring presents numerous challenges. Water-soluble polymer films are easily removed by shampoo. Water-insoluble multilayer films appear to have better persistence, but these also typically only withstand two to three shampoo washes. Film inflexibility, film irregularity, film thickness, inability to properly distribute color throughout the hair strand, film weakness, and film dissolution by solvation, polar and / or ionic interactions with shampoo, organic liquids and other hair dressing components result in undesirable tactile responses and physical displacement of the polymer film. These difficulties can lead to peeling, hair damage, an artificial appearance, and uneven, undesirable color removal.

[0002] Hair coloring technology has advanced over the past five years in addressing these challenges. Various techniques have achieved better persistence and elasticity of color coatings on hair. Further improvements include the development of techniques for combining various pigments and pigment distributions designed to mimic, at least to some extent, natural highlights in hair.

[0003] These types of coatings, preferably color coatings, range from organic silicone and organosilicone compositions to biological protein derivative compositions. Mixtures and layers of coatings, preferably color coatings, are typical in this regard. However, the suitability and compatibility of such mixtures and layers, as well as their interaction with hair and scalp, remain problematic. These coatings, especially color coatings, still exhibit peeling, roughness, rigidity, irregular film formation, lack of flexibility, rough texture, tactile feel, and lack of persistence. Internal coating connections can lead to coatings, especially color coatings, exhibiting rigidity, peeling, thick texture / tactile feel, and extreme difficulty when attempting to remove and / or replace the coating with another coating. Rapid curing and lack of fluidity of compositions for application can result in uneven coverage instead of continuous coating formation.

[0004] When such coatings, particularly color coatings, are combined with keratin fibers such as hair, it has been found that, due to the inherent properties of anagenic hair, it is currently impossible to achieve aesthetically satisfactory coloration with long-lasting persistence. To date, experiments in developing keratin fiber coloring, such as hair coloring, have focused on the use of hair traces or samples. These traces are formed from natural hair but are separated from their source (human) and are usually pre-treated to make them easier to use for experimental purposes. Such traces do not allow for experimentation and development of solutions to the challenges and problems inherent in anagenic hair, i.e., hair growing from human scalp. Anagenic hair differs from hair traces due to differences in color between the root, middle, and tip of the anagenic hair, differences in keratin structure between the root, middle, and terminal portions of the growing hair, and continuous sebum secretion extending from the root to the tip of each anagenic hair. Individual differences in chemical composition between people include differences in sebum composition, anagenic hair dimensions, individualized topographic characteristics of the hair surface, and differences in fatty acids or the F layer. Tertiary hair characteristics also differ between people, including variations in curl and color in different areas of anagenic hair on the scalp, as well as scalp skin issues. Further differences between anagenic hair and hairless hair include, but are not limited to, the lack of cleanliness of anagenic hair, but are not limited to, the presence of existing hair treatments including hair styling formulations, the application of permanent oxidation dyes, permanent wave and / or curl treatments, the application of oils and smoothing compositions, and conditioning treatments typically applied to anagenic hair. Further challenges include regulatory requirements, as well as the need to avoid tissue damage and / or environmental damage from sunlight, UV, wind, rain and airborne chemicals, biodegradable chemicals in water and hair care and dyeing compositions, and sweat and sebum.

[0005] However, even with recognition of the outstanding properties of anagenic hair, achieving long-lasting persistence combined with softness, low keratin damage, and the absence of toxic and / or irritating chemicals has been a challenging goal. These color coatings continue to result in stiff hair, hair coagulation, an undesirable lack of fluffiness, and uneven coloring, not to mention toxicity, high skin irritation, and prohibition due to ingredient regulations.

[0006] Achieving truly successful hair coating and coloring technologies that solve these problems focuses on developing long-lasting hair color for anagenic hair that exhibits softness, fluffiness, and the feel and appearance of untreated anagenic hair, while simultaneously avoiding the hair damage typically associated with oxidative permanent dye technologies. Current hair coatings using pigments offer a starting point, but due to these inherent problems and challenges, this technology has not yet been able to be applied to anagenic hair. This technology has not demonstrated success in terms of persistence, natural color imitation, and approximation of the quality of anagenic hair when transitioning from anagenic hair to anagenic hair. In particular, the signaling goal of this technology remains the development of hair color that can be achieved by permanent oxidative dye technologies without significant damage to anagenic hair. [Overview of the project]

[0007] These and other difficulties are addressed by embodiments of the present invention. The present invention satisfies these objectives through the design and application of methods that enable the development of hair coating technologies, including hair repair and hair styling technologies, preferably hair coloring technologies for surface coatings, preferably but not limited to, hairtress, hairtress designed to mimic anagenic hair, anagenic hair, eyebrows and eyelashes, more preferably anagenic hair on the human scalp. The design and application of methods of the present invention features several embodiments, but not limited to, initiating an activation process to prepare the keratin fiber surface for chemical and / or physically interactive acceptance of a coating, preferably a color coating, provided by a pretreatment composition and a film-forming composition. Further embodiments concern the adjustment of each component of the method, as well as the control of parameters, conditions and additives for the method. These multiple design features enable a rapid method for activating keratin fibers and applying the dressing composition to the activated modified keratin fibers, preferably anagenic hair.

[0008] These multiple design features enable slow dressing, but also allow for rapid coating formation under processing parameters that enable continuous coating formation if desired. These multiple design features enable robust persistence, long abrasion resistance, a pleasant texture quality, uniform and / or diverse color distribution, as well as the establishment of triggers for coating and color coating removal.

[0009] These multiple design features also enable the resolution of “downstream problems” that may be associated with anagenic hair. Such downstream problems include, but are not limited to, the development of strong yet flexible interconnections between the coating, pigment and hair surface; the effect of sebum and the F layer on such coating interconnections; root specificity affecting the interaction between the coating, preferably the color coating and the keratin fiber surface; and the effect of incomplete or ineffective removal of dirt, grime, and stains on anagenic hair. In addition, the multiple design features of the color coating help in the color placement, distribution, and maintenance of the color of anagenic hair, as anagenic hair is attacked by environmental factors, including, but not limited to, ultraviolet rays, shampooing, brushing, combing, rinsing, rain, wind, covering with scarves and hats, friction and drying with towels and hair dryers, hair conditioners, styling hairsprays, hot iron curling, and other environmental and hair care factors. At the same time, these multiple design features according to the present invention provide at least substantially the same tactile, visual, and auditory sensations as untreated anagenic hair.

[0010] The embodiments of the present invention include, but are not limited to, embodiments of a method for obtaining a coating, preferably a color coating, for keratin fibers, preferably an anogenic hair, and embodiments of a color composition and its components. These embodiments further include the quality of a coating, preferably a color coating, that imparts the above-mentioned characteristics for hair coloring to keratin fibers.

[0011] Embodiments of these methods relate to an activation step, a pretreatment step, and a binder step. The activation step involves contacting keratin fibers with either or both of the Praeparatur and Fundamenta steps to form modified keratin fibers. The Praeparatur step includes at least washing of the keratin fibers. The Fundamenta step includes at least chemical disruption of keratin proteins and / or binding lipids on the surface and possibly beneath the surface of the keratin fibers. The pretreatment step is carried out concurrently with or sequentially with the activation step and involves applying a pretreatment composition to the keratin fibers. The pretreatment composition comprises at least a PTH alkoxysilane compound, including embodiments such as PTH organo-alkoxysilanes and / or PTH organomultidimethylsiloxanylalkoxysilanes and / or their disulfide and tetrasulfide forms, where PTH is a symbol representing a functional group such as a thiol (-SH or mercaptan), a protected thiol, a hydroxyl, and a complementary group that can react with thiols. The binder step involves applying a film-forming composition to modified keratin fibers pre-coated with a pretreatment composition. The film-forming composition comprises an organosilicone or organosilicone binder having a binder functional group. The binder may be a unitary organosilicone or organosilicone polymer having a single binder functional group. Alternatively, the binder may be a dual polymer binder comprising first and second organosilicone or organosilicone polymers having different binder functional groups. If the binder is unitary, it has a single binder functional group that may be self-reactive or interact with components of the pretreatment composition. If the binder is a dual polymer binder, it comprises a first polymer component and a second polymer component having different structures, and their different binder functional groups include complementary pairs comprising at least a) alkenoyloxy and amine, b) alkenoyloxy and thiol, and c) carboxyl and carbodiimide.

[0012] A first aspect of the present invention, which aims to achieve coating, preferably color coating, on keratin fibers, particularly on anogenic hair, relates to embodiments for activating the surface and any subsurface of keratin fibers. These embodiments are achieved through the implementation of a Praeparatur procedure and a Fundamenta procedure. The Praeparatur procedure deeply cleanses the surface of the keratin fibers, and the Fundamenta procedure disrupts, modifies, and / or chemically alters the keratin proteins and / or binding lipids on the surface and possibly subsurface of the keratin fibers to produce modified keratin fibers, including but not limited to chemically modified keratin fibers.

[0013] Embodiments of Praeparatur technology include, but are not limited to, mild stirring with an aqueous surfactant composition, strong interaction with an aqueous or aqueous organic medium containing anionic surfactants, and / or washing with an organic solvent and / or optionally rinsing with an aqueous medium having pH adjustment. Additional steps include any mechanical stirring with such aqueous medium, as well as combing, brushing, vibrating, ultrasonic and similar friction and / or scrubbing of the surface of the keratin fibers.

[0014] Embodiments of the Fundamenta method, though not limited to these, involve the removal, reconstruction, and destruction of the F layer of the hair surface, including one or more of the following: chemical reconstruction with acidic or basic oxidizing agents such as persulfates, ozone, or peroxides, such as benzoyl peroxide or hydrogen peroxide; reductive chemical reconstruction with reducing agents; reconstruction by non-thermal equilibrium plasma treatment; or chemical reconstruction with interphase-transfer tensides such as fatty-alkyltrimethylammonium halides.

[0015] The activation step sets up a stage for interaction between the pretreatment composition, which contains at least the above-mentioned PTH-alkoxysilane compound, and the keratin fiber surface and any subsurface. The activation techniques of Praeparatur and Fundamenta may be carried out before the pretreatment step with the PTH-alkoxysilane compound, or in combination with the application of the pretreatment composition.

[0016] Accordingly, a second aspect of the present invention relates to an embodiment of a pretreatment step. The pretreatment step includes adding a pretreatment composition to modified keratin fibers. Embodiments of the pretreatment composition include at least a PTH alkoxysilane compound comprising one or more PTH organo-alkoxysilanes and / or PTH organomultidimethylsiloxanyl alkoxysilanes. Each of these two PTH alkoxysilane compounds has at least one PTH group and at least one alkoxysilane group. The PTH group may be a thiol, a protected thiol, or a thiol complementary reactive group. More specifically, the PTH group is R 3 S-[wherein, R 3 [Contains hydrogen or sulfur protecting groups]. In addition, the PTH group contains OHC-, H2C=CR 10 -CO2- and HO-[wherein R, R 10 The thiol-reactive group can be hydrogen or a thiol-reactive group such as C1-C6, preferably a C1 alkyl group. PTH alkoxysilane compounds having PTH as SH can also be configured as multisulfide forms of the thiol group (e.g., disulfide and tetrasulfide). Preferably, the pretreatment composition comprises a PTH organoalkoxysilane having at least PTH as a thiol and / or a PTH organomultidimethylsiloxanylalkoxysilane having PTH as a thiol, and more preferably, the pretreatment composition comprises at least a thiol organoalkoxysilane.

[0017] Embodiments of the pretreatment composition may also further include an aminoorgano-alkoxysilane and / or an organoPTH compound having one or more PTH groups.

[0018] A third aspect of the present invention relates to embodiments of a binder process. The binder process includes the application of embodiments of a film-forming composition. The film-forming composition comprises one of four embodiments of a binder polymer having a binder functional group. In two of these embodiments, the binder polymer may be a unitary organosilicone or organosilicon component having a single binder functional group. In the other two embodiments, the binder polymer may be a first organosilicone or organosilicon component and a second organosilicone or organosilicon component, wherein the first and second components have complementary binder functional groups.

[0019] In a first embodiment of the film-forming composition, the binder polymer is unitary and may include an in situ self-crosslinkable organic polymer binder having two or more pendant and / or terminal alkoxysilane groups, preferably at least one terminal alkoxysilane group.

[0020] In a second embodiment of the film-forming composition, the binder polymer is unitary and may comprise an organic polymer of one or more monomer units selected from olefin carboxylate ester units, olefin carboxamide units, carbon-hydrogen olefin units, ester monomer units, amide monomer units, urethane monomer units, urea monomer units, and any combination thereof. In this second embodiment, the organic polymer further comprises at least one, preferably at least two, pendant and / or terminal binder-functional monogroups containing carboxylic acid groups. Optionally, the organic polymer may also be substituted with pendant organoalkoxysilane groups. For this second embodiment, the pretreatment composition may also comprise an aminoorganoalkoxysilane in addition to the PTH alkoxysilane compound. The aminoorganoalkoxysilane introduces amino groups into the condensed pretreatment layer. These amino groups are thought to enable electrostatic interactions with the carboxyl groups of the film-forming composition.

[0021] In a third embodiment of the film-forming composition, the binder polymer is a dual binder comprising different first and second polymer components. The first component may comprise an organosilicon or oganosilicon polymer having at least one pendant and / or terminal first binder functional group. The second component of this third embodiment may comprise a low molecular weight, prepolymer, or polymer having at least one pendant and / or terminal second binder functional group. The first and second binder functional groups of this third embodiment each comprise an alkenoyloxy group and an amine and / or an alkenoyloxy group and a thiol complement, also known as a Michael adduct. The thiol and hydroxyl groups of PTH alkoxysilane compounds, as well as any amine groups of aminoorganoalkoxysilanes of pretreatment compositions, are also considered to interact with the alkenoyloxy group of the first component of the film-forming composition.

[0022] In a fourth embodiment of the film-forming composition, the binder polymer is a dual binder comprising different first and second components. The first component may comprise an organosilicon or organosilicon polymer having at least one pendant and / or terminal first binder functional group. The second component of this fourth embodiment may comprise a low molecular weight, prepolymer, or polymer having at least one pendant and / or terminal second binder functional group. The first and second binder functional groups of this fourth embodiment each comprise a complementary pair of a carboxylic acid group and a carbodiimide group. Although not limited, thiol or hydroxyl groups of PTH alkoxysilane compounds and any amine groups of aminoorganoalkoxysilanes of pretreatment compositions are also considered to interact with carbodiimide and / or intermediates formed from carboxylic acid and carbodiimide.

[0023] Furthermore, preferred versions of the second, third, and fourth embodiments of the film-forming composition, and generally for the first embodiment, may optionally, preferably, contain alkoxysilyl groups and binder functional groups as the unitary polymer (second embodiment) or as the first and second components (third and fourth embodiments). The first embodiment already contains alkoxysilyl groups as primary binder functional groups. The alkoxysilyl groups in these embodiments of the film-forming composition enable supplemental interconnections between the polymer of these film-forming compositions and the alkoxysilyl groups of the pretreatment composition. These supplemental interconnections are in addition to the silicon-oxygen-silicon interconnections of the first embodiment, the carboxyamine electrostatic interactions of the second embodiment, the Michael addition interconnections of the third embodiment, and the carbodiimide-carboxyl interconnections of the fourth embodiment.

[0024] Therefore, an additional aspect of the functionality of the PTH alkoxysilane compound in the pretreatment composition is its interaction with the film-forming composition. The film-forming composition also preferably has alkoxysilyl groups. Together, these alkoxysilyl groups hydrolyze and interact to form silicon-oxygen-silicone bonds. These bonds bind the pretreatment composition and the film-forming composition together as a coating, preferably a color coating.

[0025] The action of the Praeparatur and / or Fundamenta procedure on keratin fibers to generate modified keratin fibers, combined with the application of the pretreatment composition to the modified keratin fibers, is thought to result in chemical interactions between the PTH alkoxysilane compound and keratin protein on and below the surface of the anogenic hair. The Fundamenta procedure is thought to function, through chemical interactions, to generate modified protein moieties on and below the surface of the keratin fibers, including, but not limited to, protein molecules having one or more of the following groups: thiol / mercapto groups, oxidized sulfur groups, carboxyl groups, and hydroxyl groups. From a chemical standpoint, the PTH alkoxysilane compound of the pretreatment composition is adapted to react with these modified keratin protein groups to form adducts such as disulfide groups, thioester groups, β-thioethylcarboxyl adducts resulting from the addition of thiols to α,β-unsaturated carboxyl groups, and sulfonyl and sulfate ester groups resulting from the addition of hydroxyls to partially oxidized sulfur groups, particularly disulfide adducts. This interaction is thought to be the basis for immobilizing PTH alkoxysilane compounds and the resulting self-condensed PTH alkoxysilane oligomers on and potentially beneath the surface of keratin fibers. In addition, the thiol and disulfide versions of PTH alkoxysilane compounds themselves can also function as reducing / recombining agents for di-cysteine ​​disulfide groups in keratin proteins, forming disulfide bonds with cysteine ​​groups on and beneath the keratin surface.

[0026] The result of sequential or simultaneous implementation of the Praeparatur / Fundamenta technology and pretreatment steps is the formation of a pretreatment silicone polymer network that adheres closely to the deeply cleaned and chemically modified surface of the keratin fibers. The final step of this coating method, preferably this coloring method, is set by the introduction of a film-forming composition carried out according to a binder step. After the formation of a pre-coating of the pretreatment composition on the modified keratin fibers, the film-forming composition is applied to form a combination of the pretreatment composition and the film-forming composition on the modified keratin fibers. This combination composition is an uncured combination of its components. The combination composition can be cured to provide a coating, preferably a color coating, on the modified keratin fibers. The adhesion and chemical interaction between the molecules of the pretreatment network and the molecules of the network formed from the film-forming composition produce a highly persistent coating, preferably a highly persistent color coating, on the anogenic hair.

[0027] Embodiments of the film-forming composition and pretreatment composition can be applied separately or together to keratin fibers according to the method of the present invention and cured (e.g., interbonded) to produce a coating, preferably a color coating, of an interconnected, overlapping, and / or intermixed composite film interconnected with keratin fibers, such as the surface of anogenic hair. The coating, preferably a color coating, on keratin fibers, preferably on anogenic hair, exhibits desirable properties including, but not limited to, persistence, washability, and resistance to environmental damage. In the case of keratin fibers, preferably anogenic hair, the coating, preferably a color coating, provides elastomer flexibility that allows free movement of the coated keratin fibers, pleasant texture properties similar to uncoated hair, tensile strength that resists peeling and breakage, and, in the case of a color coating, color imitation of a suitable shade for the root, middle, and tip of the keratin fiber.

[0028] According to the methods of the embodiments of the present invention, embodiments of the pretreatment composition are applied to keratin fibers simultaneously with and / or sequentially thereafter to the Fundamenta procedure, particularly the acid oxidation process, the reduction process, or a combination of the reduction process followed by the acid oxidation process. In some examples, the pretreatment composition can be applied and treated at least partially before the application of the film-forming composition to promote the condensation curing of some of its alkoxysilyl groups. In other examples, the pretreatment composition can be applied, and then the film-forming composition can be applied immediately and subsequently treated to cure the binder functional groups and any alkoxysilyl groups of the film-forming composition together with the PTH groups and alkoxysilyl groups of the pretreatment composition. In yet another example, the pretreatment composition and the film-forming composition can be combined together and applied to keratin fibers as a mixture. The use of catalysts in the film-forming composition can provide a favorable condensation rate for the pretreatment composition and the film-forming composition, whether they are applied separately from the intermediate curing, applied sequentially and rapidly, or applied pre-combined as a mixture. Although not limited to the present invention, regardless of the order of addition, the pretreatment composition is thought to preferentially distribute to the surface of keratin fibers in order to enable interaction with the characteristics of keratin proteins on the surface of the keratin fibers.

[0029] The coatings of the present invention, preferably the color coating embodiments (cured coatings), include, at least partially, a coating formed through a composition comprising a film-forming composition and a pretreatment composition, preferably through the reciprocal chemical interaction features of the color composition components and modified keratin fibers, preferably a three-dimensional network of the color coating. It is believed that the chemical interaction between the modified keratin fibers and PTH alkoxysilanes forms disulfide bonds and other entanglements, enabling close network interactions with the keratin fiber surface and network interactions with the components of the film-forming composition. Demonstrated results of this method are experiments showing that the initial residual sebum coating on an anagenic hair and subsequent sebum secretion to the anagenic hair do not remove the coating, preferably the color coating, from the surface of the anagenic hair at least partially. In other words, the persistence of the coating / color coating resulting from the implementation of the method of the present invention lasts longer in its coverage of the hair extending to the hair root than the persistence of the coating / color coating not produced according to the steps of the method of the present invention. These results demonstrate the bonding and bonding interactions between the keratin fiber surface and the cured coating of the pretreatment composition and film-forming composition, as well as between them.

[0030] The methods of the present invention, comprising parameters, conditions, and techniques for forming a coating, preferably a color coating, on keratin fibers, relate to forming a coating, preferably a color coating, by combining an activation step and a pretreatment step together with a binder step. Embodiments of these methods require the application of the Praeparatur and / or Fundamenta steps to keratin fibers, preferably anogenic hair, simultaneously with or sequentially with the application of the PTH alkoxysilane of the pretreatment composition. The methods of the present invention further involve parameters, conditions, and techniques for the application of the pretreatment composition to modified keratin fibers, preferably modified anogenic hair, before, simultaneously with, mixed with, or combined with the application of the film-forming composition.

[0031] According to the present invention, the desirable properties of a coating, preferably a color coating, on keratin fibers, preferably anogenic hair, can be demonstrated by coloring tests on hairtresses prepared from unbleached natural white human hair (hereinafter referred to as untreated hairtresses), hairtresses prepared from bleached natural white human hair (hereinafter referred to as treated hairtresses), and untreated hairtresses specially prepared with synthetic sebum to mimic anogenic hair (hereinafter referred to as mimic hairtresses). After the formation of a coating, preferably a color coating, on the mimic hairtresses, the coated mimic hairtresses are recoated with synthetic sebum and shampooed to closely represent the sebum secretion process in anogenic hair on a human scalp. The sebum recoating and shampooing are repeated several times to evaluate the persistence. Furthermore, the damage state of the keratin fibers prepared according to the method of the present invention can be evaluated. The results of these tests demonstrate significant persistence and lack of fading, as well as minimal damage, when embodiments of the present invention are carried out.

[0032] For the efficiency of experimental implementation, the above-described mimic hair traces have been developed to closely mimic the behavior of anagenic hair, particularly the root segment of anagenic hair, as closely as possible. Through the use of mimic hair traces, it was surprisingly found that the Praeparatur and Fundamenta procedures, along with the PTH alkoxysilane compound pretreatment network combined with the film-forming composition, maintain the persistence of the coating on the mimic hair, preferably the color coating. However, coatings on mimic hair prepared without the application of the Praeparatur and / or Fundamenta procedures, preferably the color coating, exhibit significant to near-complete fading during multiple sebum-shampoo applications designed to examine persistence under real-world conditions. [Brief explanation of the drawing]

[0033] [Figure 1]Figures AB show versions of the color coating prepared by three different experimental processes S4-S6 in Table 11. Salon model hair was washed 15 times over several days after the color coating treatment. Figure 1A is a color photograph of the salon model hair coloring by the three different treatments S4, S5, and S6. The difference in persistence between S4, S5, and S6 is indicated by the degree of coloring up to the hair root. The coloring of S6 extends closer to the root, while the coloring of S5 and S4 extends further away from the root. Due to the anagenic hair and scalp bioactivity, color persistence at the hair root is more difficult to achieve than at the tip. Figure 1B is a grayscale (black and white) photograph of the color photograph in Figure 1A. The black and white photograph does not show the difference between the S4, S5, and S6 treatments shown by the color photograph in Figure 1A. [Figure 2] Figure 2A shows a wavelength measurement (Wlm) photograph of the salon model hair shown in Figure 1A. This measurement indicates the degree of redness present in the hair. The Wlm photograph is a grayscale photograph, but it shows the differences between the S4, S5, and S6 treatments shown in Figure 1A. Figure 2B is the same Wlm photograph as Figure 2A, but it is marked to show the degree of redness in the root region of the hair. [Figure 3] Figure AB shows the opposite side of the same salon model hair after 15 washing cycles. This other side of the hair was prepared using three different experimental processes S1-S3 in Table 11. Figure 3A is a color photograph showing the results of the three different processes. The difference in red extending to the hair root is clearly visible. Figure 3B shows a grayscale photograph of the colored hair from Figure 3A. The difference in color from Figure 3A is not shown. [Figure 4] Figures AB represent the Wlm photograph of hair in Figure 3A. Figure 4A shows the difference in unmarked color spread. Figure 4B shows the marked limits of coloring. [Figure 5] Figures A and B compare the Wlm photographs in Figure 2B and Figure 4B. Figure 5A reproduces Figure 2B. Figure 5B reproduces Figure 4B. [Modes for carrying out the invention]

[0034] definition Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art.

[0035] As used herein and in the appendices, the singular forms "a," "an," and "the" refer to multiple objects unless the context explicitly indicates otherwise.

[0036] In the context of this application, the term "may" means "permitted" or "possible," and is a synonym for the term "can." As used herein, the term "may" does not imply possibility or opportunity.

[0037] In the context of this application, the term "and / or" means one or the other or both. For example, aqueous solutions of A and / or B mean aqueous solutions of A alone, aqueous solutions of B alone, and aqueous solutions of a combination of A and B.

[0038] The molecular weight of the polymer or oligomer used according to the present invention may be measured by weight-average molecular weight, and the distribution of molecules of different molecular weights of the polymer used according to the present invention is determined by its polydispersity. Molecular weight is expressed as dalton (Da), kilodalton (KDa), and megadalton (1 million dalton or (MDa)). The acronym Mw represents the weight-average molecular weight, and Mn is the number-average molecular weight of a given polymer. Polydispersity is a unitless number that indicates the width of the distribution of polymer molecular weights and is defined as Mw / Mn.

[0039] The term "approximately" is understood to mean ±10 percent of a number, a number, or a range of numbers that is listed.

[0040] The term "approximately 0% by weight" is understood to mean that, assuming detectability can be determined on a parts per million basis, the substance, compound, or material referred to by zero (0) is not present in negligible but detectable amounts.

[0041] If any feature or aspect of the present invention is described in relation to the Markush group, a person skilled in the art will recognize that the present invention also describes any individual member or subgroup of a member of the Markush group. For example, if it is described that X is selected from the group consisting of methyl, ethyl, or propyl, then the claims that X is methyl, X is ethyl, and X is propyl are fully described. Furthermore, if any feature or aspect of the present invention is described in relation to the Markush group, a person skilled in the art will recognize that the present invention also describes any combination of individual members or subgroups of a member of the Markush group. Thus, for example, if it is described that X is selected from the group consisting of bromine, chlorine, and iodine, and Y is selected from the group consisting of methyl, ethyl, and propyl, then the claims that X is bromine and Y is methyl are fully described.

[0042] When the value of a variable that is always an integer, such as the number of carbon atoms in an alkyl group or the number of substituents on a ring, is given as a range, e.g., 0 to 4, it means that the value can be any integer between 0 and 4 (including both ends), i.e., 0, 1, 2, 3, or 4. Similarly, values ​​expressed in range form should be interpreted flexibly to include not only the numbers explicitly listed as limits of the range, but also all individual numbers or subranges contained within that range, as if each number and subrange were explicitly listed. For example, the range "approximately 0.1% to approximately 5%" should be interpreted to include not only approximately 0.1% to approximately 5%, but also the individual values ​​within the indicated range (e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%).

[0043] Keratin fibers refer to any natural material containing keratin protein, including hair, eyebrows, and eyelashes. Natural keratin fibers include, but are not limited to, those derived from and / or on mammals, including humans, primates, ruminants, camelids, equids, rodents, and minks (Neovison), as well as cattle, sheep, deer, goats, buffalo, llamas, alpacas, camels, guanacos, vicuñas, horses, antelopes, moose, elk, rats, mice, beavers, rabbits, minks, monkeys, apes, and similar species. Natural keratin materials may include hair and fur. Keratin fibers include scalp hair, eyebrows, and eyelashes. Keratin fibers can be extracted from their sources, such as hair cut from the scalp of a living person, or can mimic anagenic hair when treated with sebum. As used herein, keratin fibers include cut hair and anogenic hair. For experimental purposes, keratin fibers are formed into a tresse. A tresse is a strand of keratin fiber, e.g., hair, held in a clamp at one end and free at the other. The average weight of hair on a person's head is approximately 100g. A tresse is formed with approximately 1 gram of hair, or about 1 / 100 of the weight of hair on a person's head. A typical commercially available hair product for application to hair weighs approximately 100-200g, which translates to approximately 1g of product per gram of human hair. This relationship establishes the amount of experimental product to be applied to the hair tresse, 1g of experimental product per tresse weighing approximately 1g.

[0044] As used herein, “anagenic hair” means hair that is directly connected to a hair follicle in one of the following states: growth, regression, or resting. Anagenic hair exists on the human scalp in one of these states. Anagenic hair follicles produce long-chain fatty acids, the so-called F layer, which form a water-resistant coating on the cuticle of the hair shaft. Connecting to the hair follicle channel are the sebaceous glands, which secrete sebum to the hair shaft and scalp. As hair grows from the hair follicle and extends from the scalp, the sebum produced in the hair follicle spreads out of the follicle, continuing to coat the hair. Sebum is removed from the ends of the hair, at least partially, by shampooing, but is replenished by this continuous production. Hair cut from a living person is no longer anagenic hair.

[0045] As used herein, the terms “covalent, coordination, electrostatic, ionic, dipole, and entanglement or entanglement interaction” mean a chemical relationship between two atoms or two groups of atoms. Interactions include covalent bonds between atoms, such as the covalent bond between two carbon atoms in ethane. Interactions include those between sulfate anions (SO4). -2 Interactions include coordinate bonds between two or more atoms, such as the coordinate bond between oxygen and sulfur in a salt, or between zinc and EDTA complexes. Interactions include electrostatic or ionic interactions between two charged atoms or particles, such as the interaction between sodium and chloride in a salt, or between ammonium and acetic acid in ammonium acetate. Dipole interactions include hydrogen bonds, such as the interaction between water and the hydroxyl in methyl alcohol. Interactions include entanglement or twisting, which are lipophilic interactions or mechanical / physical twists, such as those present in polyethylene molecules.

[0046] As used herein, adhesion generally refers to an arrangement in which a substance formed from polymers, oligomers, or small molecules exhibits a manner of connection with another material, such as another polymer, oligomer, small molecule, or keratin protein, through forces such as covalent bonds, hydrogen bonds, coordination interactions, electrostatic interactions, dipole interactions, small force interactions, or dispersion forces, as a result of at least entropy, molecular entanglement, and mechanical interactions, as can be indicated at the molecular level by molecular chain wrapping around irregular topographic features of a surface. Adhesion in this context may, but is not necessarily, be indicated by the inability to remove the bonded material from the substance without exerting any force.

[0047] As used herein, entanglement generally refers to a configuration in which a chain crosses an arbitrary plane three times. In this case, the chain is entangled. If the chain is short and crosses only twice, it can be pulled in the middle, with both ends free and unconstrained. In the case of three crossings, when the chain is pulled at one point, it will capture another polymer chain at a different location.

[0048] As used herein, the terms “transfer resistance” or “friction resistance” generally refer to the quality exhibited by a colored coating that is not easily removed by contact with another material, such as clothing or skin. Transfer resistance can be evaluated by any method known in the art for evaluating such transfer. For example, the transfer resistance of a colored coating can be evaluated by the amount transferred from the wearer to any other substrate after a certain period of time has elapsed since the colored coating was applied to the hair. The amount of colored coating transferred to the substrate can then be evaluated and compared. For example, a colored coating may be transfer-resistant if the majority remains on the wearer's hair. Preferably, little or no colored coating is transferred from the hair to the substrate.

[0049] As used herein, “modified keratin fiber at application” generally means having a modified state of keratin protein at least on the surface of the fiber. Modified states include one or more of the following chemical changes to keratin protein: cysteine ​​disulfide cleavage, amide group cleavage, ester group cleavage, sulfone formation, esterification, thioesterification, and similar chemical changes. The state of modified keratin fiber can be assessed, for example, using ATR FT-IR for oxidative damage as described later, or through tensile testing methods known to those skilled in the art for evaluating fiber strength using equipment such as the apparatus designed and sold by Dia-Stron®.

[0050] As used herein, the term “conversion” means, but is not limited to, the chemical reaction of covalently co-reactive pairs of components of a composition, such as binders and linkers of a film-forming composition, to produce a reaction form such as a chain-extended and / or cross-linked polymer that functions as a coating or film. Conversion is achieved by applying an activity designed to induce covalent bonding of a pair of reactive groups or co-reactive components. Activities that enable conversion include, but are not limited to, drying, heating, curing, and any other activities that can affect the reactivity and / or reaction rate of the co-reactive components, such as curing / reacting the co-reactive components together and allowing the co-reactive components to be combined or mixed under standard conditions without further intervention, addition of catalysts, or changes in the pH of the composition.

[0051] The term "persistence" refers to the preservation of a substance's original properties, such as color, attached to or bound to a substrate, when subjected to processes that can, though not necessarily, remove the substance from the substrate. An example of persistence is the ability of a color coating on a substrate, such as paint on wood, to withstand environmental and cleaning factors that can remove the coating from the substrate, such as wood. An example of persistence in cosmetic applications is the ability of a coating, such as a hair styling composition, to resist removal by water, such as rain, or by rinsing. The degree of persistence can be measured by the ability of a substance to maintain its original size, color, intensity, hue, and other original characteristics when subjected to multiple treatments that can remove the substance. An example of the degree of persistence in cosmetic coatings is demonstrated by the ability of a color coating on anogenic hair to maintain its original color intensity, hue, and shade, and avoid fading, while being treated with a commercially available shampoo preparation. The degree of persistence in this example is measured by the number of shampoos required to begin fading and / or loss of original properties. The persistence test is described in the Examples section under the title "Full Root Simulation Color Remanence Test".

[0052] "Aliphatic substituents, groups, or components" refers to any non-aromatic organic group. This includes acyclic and cyclic organic compounds composed of carbon, hydrogen, and optionally oxygen, nitrogen, sulfur, and other heteroatoms. The term encompasses all organic groups except for the aromatic and heteroaromatic groups defined below. Examples of such groups, but not limited to, include alkyl, alkenyl, alkynyl, corresponding groups with heteroatoms, cyclic analogues, heterocyclic analogues, branched, dendritic, stellate or fullerene-like and linear versions, and groups that may be substituted with functional groups. These groups and other groups that satisfy this definition of "aliphatic" are defined below.

[0053] "Aromatic substituents, groups, or components" refers to any and all aromatic groups, including but not limited to aryl, aralkyl, heteroalkylaryl, heteroalkylheteroaryl, and heteroaryl groups. The term "aromatic" is general in that it includes all compounds containing aryl groups that may be substituted with functional groups (all-carbon aromatic groups) and all compounds containing heteroaryl groups that may be substituted with functional groups (carbon-heteroatom aromatic groups), and these groups and other groups that satisfy this definition of "aromatic" are defined below.

[0054] As used herein, the term "optionally" means that the corresponding substituent or thing may or may not be present. This includes both possibilities.

[0055] "Alkyl" refers to a linear or branched, dendritic, star-shaped, fullerene-like, or cyclic hydrocarbon chain group consisting only of carbon and hydrogen atoms, unless specifically stated to have additional heteroatoms or heterogroups. Alkyl groups are unsaturated and have 1 to 24 carbon atoms (e.g., C1 to C24). 24 Alkyl). Whenever it appears herein, for example, but not limited to, a numerical range such as "1 to 24" refers to each integer within a given range; for example, "1 to 24 carbon atoms" means that an alkyl group can consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to 24 carbon atoms, but this definition also covers occurrences of the term "alkyl" where no numerical range is specified. In some embodiments, this is a C1 to C4 alkyl group. In other examples, this is a C1 to C6 alkyl group, and in yet another example, this is a C1 to C 24These are alkyl groups. Typical alkyl groups, though not limited to these, include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butylisobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, hexyl, septyl, octyl, nonyl, and decyl. For example, alkyl groups such as methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (iso-propyl), n-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), 3-methylhexyl, and 2-methylhexyl are bonded to the rest of the molecule by single bonds.

[0056] "Alkyrenyl" refers to a straight or branched, dendritic or star-shaped divalent hydrocarbon chain consisting only of carbon and hydrogen atoms, unless specifically stated to have additional heteroatoms or heterogroups. An alkylenyl group is unsaturated and has dangling valence bonds at both ends of the chain to bond to the other two parts. Unless otherwise specified, an alkylenyl group may have a carbon number range of 1 to 24 carbon atoms. In all cases, the general and specific numerical ranges of carbon atoms include each integer within the range. An example of a divalent C4 hydrocarbon chain designated as an alkylenyl group is: -CH2-CH2-CH2-CH2-; a dash (-) indicates a valence bond to other atoms or parts not shown. This example of an alkylenyl group is butyrenyl.

[0057] "Cycloalkyl" is a subcategory of "alkyl" and refers to monocyclic or polycyclic groups containing only carbon and hydrogen, which may be saturated or partially unsaturated. Cycloalkyls include one or more rings, such as two, three, or four rings linked or fused together in tandem or through an alkyl group. Cycloalkyl groups have 3 to 24 ring atoms (i.e., C3-C3). 24It includes (cycloalkyl). Whenever it appears in this specification, and not limited thereto, a numerical range such as "3 to 24" refers to each integer within the given range; for example, "3 to 24 carbon atoms" means that the cycloalkyl group can consist of 3 carbon atoms etc. up to a maximum of 24 carbon atoms. In some embodiments, this is a C3 - C8 cycloalkyl group. In some embodiments, this is a C3 - C5 cycloalkyl group. According to the definition of alkenylenyl, a cycloalkyenyl group is a monocyclic or polycyclic group having two dangling valences for bonding to two other moieties. Exemplary examples of cycloalkyl groups include, but are not limited to, the following moieties: cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, etc.

[0058] "Alkoxy" refers to an -O-alkyl group containing 1 to 24 carbon atoms in a linear, branched, dendritic, star-shaped or cyclic configuration and combinations thereof bonded to the parent structure through oxygen. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, cyclohexyloxy, etc. "Lower alkoxy" refers to an alkoxy group containing 1 to 6 carbons. In some embodiments, the alkyl is an alkyl group that encompasses both linear, branched, dendritic, star-shaped or fullerene-like chain alkyl of multiple carbon atoms. As used herein, when there is no further definition of the number or carbon atoms present, the term "alkoxy" such as in an alkoxysilyl group means C1 - C6, preferably C1 - C4, more preferably C1 - C2 alkoxy, such as methoxy and ethoxy.

[0059] The terms alkoxysilane and alkoxysilyl are synonyms and have the formula -Si(R’) 3-t (OR) t [In the formula, R' is a C1-C3 alkyl group, preferably methyl or ethyl; R is 1-6, preferably 1-3, more preferably a 1- or 2-carbon alkyl group, such as methyl or ethyl; and t is an integer of 1, 2, or 3.] This refers to the group of alkoxysilanes. Preferably, an alkoxysilane has three OR groups. Furthermore, depending on the structure of the compound substituted with the alkoxysilane group, the alkoxysilane group may also have one of the OR groups as an OH group. Compounds having this configuration may be the result of hydrolysis of a Si-OR bond [wherein R is alkyl]. Thus, the term alkoxysilane means that a silicon atom is bonded to one, two, or three alkoxy groups, and in some examples of compounds having an alkoxysilane group, the alkoxy group may incidentally be a hydroxyl group. The dangling valence of the silicon atom in an alkoxysilane is not limited to that, but depending on the nature of the moiety to which the alkoxysilyl group is bonded, such as organic compounds, siloxane compounds, organosiloxane compounds, organic polymer skeletons, silicone polymer skeletons, or organosilicone skeletons, the silicon atom is bonded to either a carbon or oxygen group, either an organic group or a dialkylsiloxanyl group. Also, since the hydrolysis intermediate of each alkoxy in an alkoxysilyl group is a hydroxyl group as well as a hydroxysilyl group, the hydroxysilyl / hydroxysilane group is included in this definition discussed above. Furthermore, one of the alkoxysilyl groups can be hydrolyzed, and the resulting hydroxysilyl can condense with another hydroxysilyl group derived from another alkoxysilyl group to form a Si-O-Si bond. Because there are three alkoxy groups in this region, the formation of a silicon-oxygen-silicon bond can occur up to three times for a single alkoxysilyl (trialkoxysilyl) group. Whether the alkoxysilyl group is a pendant or terminal on a molecule such as a low molecular weight, oligomer, or polymer, this multiple Si-O-Si bond configuration for a single alkoxysilyl group means that a molecule having a single alkoxysilyl group can undergo multiple condensations. A molecule having an alkoxysilyl can be chain-extended with another molecule having an alkoxysilyl to produce a linear-extended molecule. This linear-extended molecule contains additional Si-OR functional groups to this Si-O-Si chain extension. These additional Si-OR functional groups can again condense with the corresponding Si-OR functional groups of another linear-extended molecule.The result is crosslinking in the intermediate portion of these molecules that have Si-O-Si links. These additional Si-ORs in separate chain elongation molecules can therefore condense and crosslink the separate chain elongation molecules.

[0060] "Amino" or "amine" is -N(R a )2 groups [where each R a [These terms independently refer to hydrogen or an alkyl group consisting of 1 to 3 carbon atoms, such as methyl, ethyl, or propyl.]

[0061] "Aryl" is a subcategory of aromatic compounds that refers to a conjugated π-ring or multiple rings having 6 to 22 ring atoms. An aryl group has at least one ring (e.g., phenyl, fluorenyl, naphthyl, and anthracenyl) with a conjugated π-electron system that is carbocyclic. Partially saturated aryl rings, such as tetrahydronaphthyl, are included.

[0062] "Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" contain alkyl, alkenyl, and alkynyl groups, which may be substituted, and have one or more skeletal chain atoms selected from atoms other than carbon, such as oxygen, nitrogen, sulfur, phosphorus, or combinations thereof. A numerical range, e.g., C1 to C1, refers to the total chain length. 24 A heteroalkyl group may also be given, which in this example may be about 24 atoms long. For example, the -CH2OCH2CH3 group is called a "C4" heteroalkyl group and includes a heteroatom center in the description of the atomic chain length. Connection to the rest of the molecule may be via either heteroatoms or carbons in the heteroalkyl chain.

[0063] A "heteroaryl" or heteroaromatic is a 5-membered, 6-membered, or 10-membered aromatic group (e.g., C5-C5) comprising one or more ring heteroatoms selected from nitrogen, oxygen, and sulfur, and which may be a monocyclic, bicyclic, tricyclic, or tetracyclic ring system, or a conjugated ring system, such as a cyclopentadienyl having a bridging atom that provides conjugation, such as pyrrole or thiophene. 13This refers to heteroaryl groups. Whenever a numerical range appears herein, it refers to each integer within a given range. The N-containing “heteroaromatic” or “heteroaryl” moiety refers to an aromatic group in which at least one of the ring's skeletal atoms is a nitrogen atom. Polycyclic heteroaryl groups may be monocyclic or amonocyclic. The heteroatoms of the heteroaryl group may be oxidized. One or more nitrogen atoms, if present, may be quaternized. The heteroaryl is bonded to the rest of the molecule through any atom of the ring. Examples of heteroaryls include, but are not limited to, pyrrolyl, furanyl, thiophenyl, imidazolyl, pyranyl, pyridinyl, pyrimidinyl, benzimidazole, benzothiophenyl, quinolinyl, quinazolinyl, and similar heteroaryl compounds of 1, 2, or 3 heteroatoms containing any combination of 6 to 12 carbon atoms and nitrogen, oxygen, and sulfur.

[0064] "Heterocyclic" refers to any monocyclic or polycyclic moiety containing at least one heteroatom selected from nitrogen, oxygen, and sulfur. As used herein, the heterocyclyl moiety may be a partially saturated aromatic ring or a saturated monocyclic or polycyclic ring, and the ring may be formed from 3 to 8 atoms.

[0065] The term "polymer" or "poly" refers to one or more organosilicone or organosilicone compounds formed from two or more monomer units. The units may be identical or a combination of units of different properties. The number of units present can range from at least two to a very large number of units in a compound. The typical weight-average molecular weight of a polymer can range from less than 100 Da to more than 1,000,000 Da.

[0066] Polymers, alkyls, alkylenyls, carbon or silicone chains, carbon or silicon skeletons, compounds and groups comprising multiple carbon aliphatic groups, heteroforms of any of the aforementioned compounds and groups, and groups comprising aromatic, heteroaromatic cycloalkyl heterocycloalkyl or heteroforms thereof having any of the aforementioned compounds and groups, may have linear, branched, or stellated or dendritic structural configurations, which are subcategories of branched. Preferred configurations are branched or linear, and more preferred configurations are linear. The use of any of these terms without specifying a particular configuration encompasses all of these configurations, meaning that linear and / or branched are preferred, and linear is most preferred.

[0067] The terms "in situ bonded," "in situ bondable," and "crosslinkable" refer to the possibility at a future point in time of forming a covalent bond to provide intermolecular interactions and / or connections. The terms "in situ bonded" and "crosslinked" mean that a covalent bond has already formed in the present state.

[0068] "In situ" is a Latin phrase meaning its original location. In the context of this invention, this refers to cross-linking activity occurring on hair.

[0069] As used herein, the average reactive functional group equivalent refers to the ratio of the weight-average molecular weight of a polymer, oligomer, or low molecular weight containing a reactive functional group to the average number of that reactive functional group in the polymer, oligomer, or low molecular weight, for complementary reactive functional groups. If the Mw of the polymer is 1 kDa and the average number of reactive functional groups in the polymer is 2, then the Mw of the reactive functional group equivalent is (1 kDa) / 2 or 500 Da.

[0070] The coefficient of thermal expansion refers to the partial increase in length of a species per degree Celsius increase in temperature at a constant pressure, starting at a temperature of 25°C.

[0071] The zeta potential of pigment microparticles represents the interfacial kinetic potential of minute particles suspended in a colloidal dispersion. This is caused by the net charge at the particle contact surface with the suspended fluid. This is an indicator of the stability of the colloidal dispersion. The magnitude indicates the degree of electrostatic repulsion between adjacent similarly charged particles in the dispersion. At zero or minimal positive or negative potentials, rapid coagulation can occur. Good colloidal stability is maintained at positive or negative zeta potentials above approximately 40 mV. The zeta potential can be measured using methods known to those skilled in the art. For example, the zeta potential of components can be evaluated using the Zetasizer Nano Z from Malvern Panalytical Ltd, Malvern UK.

[0072] As used herein, microfibril length generally refers to the distribution of lengths of any given microfibrils, while fiber length refers to the average fiber length evaluated over a minimum of 10 fibers randomly selected from a sample of microfibrils. Length refers to the distance from end to end along the long axis of the material and is not a measure of cross-sectional width.

[0073] Hansen solubility parameters constitute a technique for characterizing the solubility, dispersion, diffusion, chromatography, and related topics of specific materials. Materials such as solvents or solutes can be characterized by three parameters: δD (van der Waals) for dispersion, δP (related to dipole moment) for polarity, and δH for hydrogen bonding. See "Hansen Solubility Parameters - A User's Handbook," CRC Press, Boca Raton, 2007, ISBN-10:0849372488.

[0074] A hydrogen bond refers to a weak bond between two molecules resulting from the electrostatic attraction between a proton in one molecule and an electronegativity atom in another molecule. Conversely, an ionic bond refers to a type of chemical bond involving the electrostatic attraction between charged ions.

[0075] Young's modulus, or Young Modulus, is a mechanical property that measures the stiffness (e.g., elasticity) of a solid material. It defines the relationship between stress (force per unit area) and strain (proportional deformation) of a material in the linear Hooke elastic regime of uniaxial deformation. In other words, under longitudinal tension or compression, the ability of a material to withstand changes with length.

[0076] The term Tg, or glass transition temperature, refers, but is not limited to, the temperature range in which a material, such as a polymer, transitions from amorphous, solid-like or glass-like properties at lower temperatures to viscous or rubber-like properties at higher temperatures. The transition is not a phase transition, such as from solid to liquid. Embodiments of color coatings on imitation hair, treated hair, and untreated hair typically exhibit a Tg range far below room temperature, resulting in films that are flexible, elastomeric, and have smooth physical properties.

[0077] The term "extreme compression" refers to the amount of compression that a given material can experience under a specific test method before failure occurs and the material breaks.

[0078] Nanoemulsions are liquid / liquid, liquid / solid, liquid / gas, or gas / gas compositions in which at least one discontinuous phase is dispersed in a continuous phase, and the average particle or micelle diameter of the discontinuous phase is in the range of 10 nm to 300 nm.

[0079] The term "sebum" refers to an oily, waxy substance produced by the sebaceous glands of the human body. Sebum coats, moisturizes, and protects the skin and hair. Sebum is mainly composed of triglycerides (approximately 41%), wax esters (approximately 26%), squalene (approximately 12%), and free fatty acids (approximately 16%). The sebum used to form imitation hair is Hautfett nach Bey, sold by Wfk-Testgewebe GmbH, which contains 18.0% free fatty acids, 32.8% beef tallow, 3.6% triglycerides, 18.3% wool tallow, 3.7% cholesterol, 12.0% hydrocarbons, and 11.6% cutina.

[0080] The term "surface energy" quantifies the breakdown of intermolecular bonds that occurs when a surface is formed. Surface energy can be defined as the excess energy of a material's surface compared to the bulk, or the work required to construct a particular area of ​​the surface. Perhaps the most widely used definition of surface energy is, historically, that of Zisman ("Relation of Equilibrium Contact Angle to Liquid and Solid Constitution," WAZisman, ACS Advances in Chemistry Series No. 43, 1961, pp. 1–51). Zisman defines the surface energy of a solid as equal to the surface tension of the highest surface tension liquid (real or hypothetical) that completely wets the solid at a contact angle of 0°. This stems from the widely observed tendency for the contact angle to decrease as the liquid surface tension decreases on the same solid sample. A Zisman plot is created for a test surface using a series of different probe liquids with known surface tensions, where the known surface tensions are plotted on the x-axis and the cosine of the resulting contact angle with the test surface is plotted on the y-axis. The surface energy of the test substrate is determined to be the highest surface tension when the cosine of the contact angle reaches 1. The Owens / Wendt theory (Owens, DK; Wendt, RC; Jour. of Applied Polymer Science, 13, 1741, (1969)) is a further development for measuring the surface energy of a test substrate. This theory considers the surface energy to consist of two components: a dispersion component and a polar component. The dispersion component explains van der Waals and other non-site-specific interactions that the surface may have with the applied liquid. The polar component theoretically explains dipole-dipole, dipole-induced dipole, hydrogen bonding, and other interactions that the surface may have with the applied liquid. Owens and Wendt developed a two-parameter model to explain surface interactions, in contrast to Zisman's one-parameter model. The unit of surface energy is mN. -1 That is the case.

[0081] The terms “priming,” “deep cleansing,” and “chemical modification” refer to the substantial to essentially complete removal of sebum and F-layer substances from the surface of anogenic hair, the removal of synthetic sebum and F-layer substances on mimic hair treatments, and the chemical breakdown / cleavage of chemical bonds in keratin proteins on and beneath the surface of keratin fibers. Chemical bonds include at least cysteine-cysteine ​​disulfide bonds, protein chain and side-chain amide bonds, and side-chain ester bonds. Oxidation and reduction of groups such as thiols, amines, hydroxyls, and similar amino acid functional groups are also included. Praeparatur and Fundamenta techniques achieve priming, deep cleansing, and chemical modification of the keratin fiber surface. The implementation of these priming, deep cleansing, and chemical modification techniques can achieve the modification of the keratin fiber surface to expose a variable surface topography and, not limited to, to obtain close interaction with chemically active agents such as thiols.

[0082] Detailed explanation The present invention relates to methods and compositions for developing coatings, preferably color coatings, on keratin fibers, particularly anagenic hair, and especially on anagenic hair on human scalp. These methods and compositions may also be applied to keratin fibers relating to all sources, such as hair mites, animal hair, and similar keratin fibers. The quality and characteristics of the activation, pretreatment, and binder aspects of the method contribute to, enhance, and promote the quality of the resulting coating, preferably color coating, such that the coated keratin fibers, particularly coated imitation hair and anagenic hair, exhibit significant persistence while also exhibiting performance similar to that of young, uncoated, vibrant, attractive scalp hair.

[0083] Embodiments of this method cover three steps: activation, pretreatment, and binding. Embodiments of the activation step cover either or both of the Praeparatur and Fundamenta procedures. Embodiments of the Praeparatur procedure cover cleaning keratin fibers with a cleaning composition comprising a surfactant and any other compound capable of solubilizing, dispersing, and / or lifting dirt, grime, grease, and other undesirable contaminants. Embodiments of the Fundamenta procedure cover one or more processes including acidic oxidation, basic oxidation, plasma treatment, PETT treatment, reduction, or any combination thereof. The implementation of the activation step is thought to remove sebum from keratin fibers, particularly anogenic hair, and to chemically disrupt the surface and subsurface of the keratin fibers to form modified keratin fibers. Disruption is thought to break the chemical bonds of keratin proteins on and under the fiber surface. Disruption is thought to generate thiol groups, sulfone groups, and other binding groups on and under the fiber surface. The order in which these two steps of the activation process are performed at least partially affects the properties of the coating on the keratin fibers, preferably the color coating.

[0084] The first implementation order of the Praeparatur procedure and the Fundamenta procedure combines the Praeparatur procedure with each of the processes of the Fundamenta procedure and some combinations of the processes of the Fundamenta procedure. The second implementation order consists of only each of the processes of the Fundamenta procedure and combinations of some of the processes of the Fundamenta procedure without the Praeparatur procedure. The first implementation order preferably combines the Praeparatur procedure with each of acidic oxidation, basic oxidation, plasma treatment, PETT treatment, and reduction, with treatment by a mild or medium or strong surfactant composition. Further, the first implementation order may combine the Praeparatur procedure with reduction followed by acidic oxidation. In this first implementation order, the Praeparatur procedure is carried out first, followed by any rinsing as appropriate. Each of the processes of the Fundamenta procedure may sequentially follow this Praeparatur procedure, may start during an intermediate stage of the implementation of the Praeparatur procedure, or may be carried out simultaneously with the processes of the Praeparatur procedure and the Fundamenta procedure.

[0085] The second implementation order involves only the Fundamenta procedure. Each of the processes of the Fundamenta procedure can be carried out alone, i.e., without the Praeparatur procedure. These include acidic oxidation, basic oxidation, plasma treatment, PETT treatment, and reduction. The first and last steps can be combined as reduction followed by acidic oxidation.

[0086] Embodiments of the pretreatment step relate to the application of the pretreatment composition to modified keratin fibers. Embodiments of the pretreatment composition relate to at least PTH alkoxysilane compounds (collectively PTH alkoxysilane compounds, PTH is defined abstractly and hereafter herein) comprising PTH organo-alkoxysilane and / or PTH organomultidimethylsiloxanyl alkoxysilane, as well as protected thiol derivatives of PTH alkoxysilane compounds having PTH as a thiol, and disulfide dimers and tetrasulfide dimers of PTH alkoxysilane compounds having PTH as a thiol. Additional embodiments of the pretreatment composition involve adding aminoorgano-alkoxysilane and / or PTH organic compounds to the composition containing the PTH alkoxysilane compound. Preferably, the pretreatment composition comprises at least PTH organo-alkoxysilane having PTH as a thiol. The pretreatment step is carried out immediately after an activation step, which may or may not include a rinsing step prior to the start of the pretreatment step. Alternatively, the pretreatment step may be carried out simultaneously with or overlapping with at least some embodiments of the activation step.

[0087] Embodiments of the binder process are directed to the application of a film-forming composition. The film-forming composition can include a binder polymer composition that includes a unitary organosilicon or organosilicone polymer having a binder functional group, or a dual polymer including a first organosilicon or organosilicone component having a first binder functional group and a second organosilicon or organosilicone component having a second binder functional group. The first component and the second component are different due to at least the nature of the first binder functional group and the second binder functional group. When the binder polymer includes a single organosilicon or organosilicone polymer binder, the binder functional group can be either a) an alkoxysilane, or b) a carboxylic acid. When the binder polymer includes a dual polymer, the first functional binder group and the second functional binder group are different and the first component and the second component are different. In this dual binder polymer situation, the first binder functional group and the second binder functional group form complementary pairs including a) alkenoyloxy and amine, b) alkenoyloxy and mercapto, c) carboxylic acid and carbodiimide.

[0088] To achieve the above quality of coatings on keratin fibers, preferably color coatings, aspects of the method involve at least partially the application of a dual-activation step and a PTH alkoxysilane compound to the surface of the keratin fibers. Not limited to the present invention, the activation step is likely to disrupt keratin proteins and keratin-lipid conjugates, such as 18-methyleicosanoic acid thioesters, on and beneath the surface of the keratin fibers, providing thiol / mercapto groups, sulfide groups, sulfoxyl groups, and intermediates of these groups. PTH alkoxysilane compounds having PTH as a thiol or disulfide or tetrasulfide dimer may also contribute to the disruption. The disruption is thought to include, but is not limited to, at least cleavage and / or disruption and / or rearrangement of keratin protein bonds, such as amide bonds, ester bonds, thioester bonds and disulfide bonds, that are present in the keratin proteins. In combination with the PTH alkoxysilane compounds of the pretreatment composition, as well as their corresponding protective versions, disulfide and tetrasulfide, the PTH groups of the PTH alkoxysilane compounds are coupled with the thiol and other groups of the broken keratin protein molecules, thereby causing the reformation, rearrangement, and recoupling of broken keratin protein bonds to the PTH alkoxysilane compounds. The PTH groups of the PTH alkoxysilane compounds, including the -SH group and / or aldehyde group and / or α,β unsaturated carboxyl group and / or hydroxyl group and / or protective sulfur group, are thought to interact with these keratin protein groups to form chemical bonds. The chemical bonding of the PTH alkoxysilane compounds and keratin proteins on and below the surface of keratin fibers is likely to result in the formation of at least disulfide, thioester, ester, Michael adduct, and sulfone ester bonds. This bonding is thought to enable, at least partially, the development of strong persistence and resistance to sebum migration of the coating, preferably the color coating. Rearrangement and recoupling enable a chemically interconnected pre-coating of the pretreatment composition to the keratin fibers.The alkoxysilane groups of the pretreatment composition also undergo hydrolysis and condensation to form silicon-oxygen-silicon bonds, resulting in the formation of a siloxane polymer. The addition of the film-forming composition in the binder step completes the three steps of the method, forming keratin fibers interconnected in a composite film of the pretreatment composition and the film-forming composition. The complementary first or second binder group is selected so as to react together as a reactive complement, as well as to be able to interact with the functional groups of the PTH alkoxysilane, including a) alkenoyloxy and amine, b) alkenoyloxy and mercapto, c) carboxylic acid and carbodiimide, d) mercapto and carbodiimide, e) mercapto and aldehyde, and f) double bond and mercapto, in the optional presence of a radical initiator. The combination of the bonded PTH alkoxysilane and the film-forming composition provides a chemical bond from the keratin fiber surface to the film-forming composition via the pretreatment composition. Due to the chemical bonding, migration of the coating, preferably the color coating, by means of physical means such as surfactants, sebum, or other nonspecific activities is minimized.

[0089] Damage to anagenic hair from oxidative dyeing processes is an oxidative challenge that is attempted to be avoided by pigment coloring of the keratin fiber surface. For at least the past 15 years, patents and scientific publications addressing surface coloring of keratin fibers have stated that avoiding this damage is a critical aspect of surface coloring. Oxidative damage is most severe when strong basic oxidation is performed. The base makes the cuticle porous to oxidizing agents and low molecular weights, allowing them to penetrate the cortex in which they work. Less powerful but still damaging techniques such as weak basic oxidation, plasma treatment, PETT treatment, reduction, and acidic oxidation also damage keratin fibers. FTIR and tactile testing of keratin fibers allows for the evaluation of this damage by the Fundamenta procedure process and enables the development of a hierarchy of activation / pretreatment (PTH alkoxysilane compound) steps ranging from significant to minimal damage. This hierarchy and adjustment of persistence provide a system for activation and pretreatment step combinations, ranking combinations from best to fair.

[0090] Tables I and II describe various activation processes, PTH alkoxysilane compound pretreatment steps, and binder steps tailored to the resulting combinations for hair damage and persistence. The expected performance of each step combination is ranked as follows: green for excellent, yellow for good, and red for fair. In these tables, the activation process includes the Praeparatur procedure (surfactant shampoo), and the Fundamenta procedure includes acid oxidation, base oxidation, plasma treatment, PETT treatment, and reduction, as well as reduction followed by acid oxidation. The Praeparatur procedure may be performed concurrently with a specific Fundamenta procedure (indicated by the absence of a space between the two activities) or sequentially with a specific Fundamenta procedure (indicated by the presence of a space between the two activities). Pretreatment includes the application of a PTH alkoxysilane compound (OSSI for organosulfur silanes) having at least PTH as a thiol. The binder is a film-forming composition comprising a polyolefin having a pendant / terminal carboxylic acid group (EAA), a single organic polymer (Winnie) having a pendant / terminal alkoxysilane group, two silicone polymers (Michael) having an alkenoyloxy and an amine as a complementary functional binder pair, and organic polymers and oligomers having a carboxylic acid and carbodiimide (CDI) as a complementary functional binder pair. Since the pretreatment composition provides an aminoorgano-alkoxysilane contained together with a PTH alkoxysilane compound, Table II provides the results for the binder EAA. The aminoorgano-alkoxysilane provides the amine group for electrostatic interaction with the carboxylic acid of the EAA.

[0091] The experimental results for these combinations, provided in Tables I and II, show that the Praeparatur procedure combined with acidic oxidation provides the best-performing combination (all green), while the Praeparatur procedure combined with basic oxidation provides the lowest-rated combination. The Fundamenta procedures of PETT, plasma, and reduction all provide fair results, but show significant hair damage in tactile tests. The combination of reduction and acidic oxidation also provides fair results, but shows some hair damage in FTIR tests. Table I TIFF0007862521000001.tif236170 Table II TIFF0007862521000002.tif241170

[0092] The results presented in these tables demonstrate the excellent persistence achieved by the method of the present invention. Compared to coating methods that do not include pretreatment of PTH alkoxysilanes and / or derivatives having PTH as a thiol, in combination with film-forming compositions having alkoxysilane groups, and Fundamenta procedures strong enough to destroy keratin fibers, the method of the present invention represents covalent bonding / coupling of the coating to keratin fibers. The drawings related to the examples in the experimental section titled "Salon Text Examples" show that coating method procedures without PTH alkoxysilane (experiments S1, S2, S3 using MEMO, a non-thiol alkoxysilane, trimethoxysilylpropyl (meth)acrylate ester) produce a coating on anagenic hair (salon model hair) that is removed by shampoo, while the coating by the method of the present invention (experiments S4, S5, S6 using mercaptopropyltrimethoxysilane) is not removed. The anagenic hair on the heads of salon models is living, growing hair. Therefore, sebum and other substances are continuously secreted into the hair follicles. The flow of natural oils, sebum, fatty acids, etc., damages the coating produced without the use of PTH alkoxysilane. As a result, shampoo easily removes this coating. In contrast, the coating produced according to the method of the present invention is not removed by shampoo. The comparison of these results shows that the flow of natural oils, sebum, fatty acids, etc., cannot damage the coating produced according to the method of the present invention. This result is evidence that a bond is formed between the coating and keratin fibers, for example, anogenic hair of a salon model. This evidence provides demonstration of the above reason for the formation of a bond, i.e., a disulfide bond and other covalent bond between the PTH alkoxysilane having PTH as a thiol and the keratin protein on the surface of anogenic hair.

[0093] Further demonstration of covalent bonding between the coating and keratin protein can be shown by Model Example 9, which is presented below in the Examples section. In this model, a membrane having cysteine ​​or di-cysteine ​​disulfide can be used as a simplified characterization of keratin fibers. The modeled method can be tested on a sample of this membrane after the method of the present invention to determine whether the thiol compound binds to the membrane sample. A comparison between the thiol compound test and a similar test using a compound similar to the thiol compound but without a thiol group provides test information that may indicate binding. Alternatively, a color composition having an in situ-bound binder polymer can be applied to such a membrane sample to determine which sample yields better color retention.

[0094] Implementation of the activation steps in the PRAEPARATUR and FUNDAMENTA procedures. Embodiments of the activation process according to the present invention are intended for the cleansing, removal of sebum, and destruction of keratin fibers, particularly anagenic hair, especially anagenic hair on the human scalp, both surface and subsurface. The activation process comprises two steps: Praeparatur and Fundamenta. The Praeparatur step cleanses the keratin fibers to remove dirt, grime, grease, and similar undesirable substances from keratin fibers, such as anagenic hair. The Fundamenta step continues the cleansing process through sebum removal and engages in the chemical destruction of the keratin fibers surface and subsurface.

[0095] PRAEPARATUR Procedure The virtually complete initial removal of sebum coating the surface of anogenic hair results in a cleaned hair surface, exposing the microscopic topographic variability provided by keratin proteins on this surface. To obtain such a keratin fiber clean, a Praeparatur procedure is applied. A Praeparatur procedure can be any cleansing operation that removes sebum from the surface of keratin fibers. An exemplary Praeparatur procedure involves the use of one or more applications of a non-conditioning surfactant or substantially non-conditioning surfactant that does not contain conditioning surfactants or substantially contains conditioning additives such as silicones, e.g., amodimethicone or cetrimonium chloride, and polymers such as polyquaternium versions of cellulose and guar gum derivatives. The procedure requires one or more applications of the surfactant in an aqueous or aqueous-alcoholic medium containing any agents for ionic and pH control, as well as organic liquids and solvents for solubilizing, dispersing, and lifting dirt, grease, and grime, the type and concentration of the components being adjusted to achieve the desired cleansing effect. This procedure involves the use of a mild to moderate aqueous composition of anionic, nonionic, amphoteric, or zwitterionic surfactants in concentrations gradually increasing from about 2% by weight relative to the total weight of the composition to about 30% by weight, preferably up to about 25% by weight, and more preferably up to about 10% to about 25% by weight. The surfactant composition may also contain agents for adjusting viscosity and ionicity, as well as for any adjustment of pH from acidic to neutral to basic. The surfactant composition may start with mild surfactants, such as nonionic surfactants or mixtures thereof, and escalate to higher concentrations of anionic surfactants. Preferred surfactants are anionic surfactants exhibiting amphiphilic properties, such as alkali metal salts of C8-C16 alkyl carboxylates, phosphates, sulfonates, and sulfates, with the intensity of amphiphilic properties increasing from carboxylates to sulfates.The first nonionic surfactant used may be followed by a stronger anionic surfactant, then a solubilizing anionic surfactant having either a PEG group such as PEG-2 to PEG-20, preferably PEG-2 to PEG-5, for increased hydrophilicity, or a PPG group such as PPG-2 to PPG-5 for increased lipophilicity, inserted between the anionic head and alkyl lipophilic tail of the anionic surfactant. Even stronger solubilizing media may be formulated by increasing ionic strength and adjusting the pH. Ionic constructors such as alkali metal sulfates, carbonates, phosphates, nitrates and / or xylene sulfonates may be added. The properties of the media may be adjusted to provide an organic solvent capable of solubilizing oils and sebum. These include C2 to C8 alcohols, preferably isopropanol, isobutanol and neohexanol, as well as acetone, methyl ethyl ketone and other similar organic solvents. This escalating cleansing treatment is designed to escalate in a gentle, stepwise manner to avoid overchallenge of the hair.

[0096] This escalating cleaning process can be combined with mechanical agitation, for example, by a fine-toothed comb and / or by sonic vibrations using an ultrasonic device operating at at least 20 kHz. Mechanical and / or sonic vibrations can agitate the anogenic hair to loosen the coating of sebum, natural oils, and secreted sweat and minerals. The ultrasonic device may be designed as a fine-toothed comb whose teeth vibrate to generate ultrasonic waves. Alternatively, the ultrasonic device may be a portable generator held in combination with a fine-toothed comb passing through the anogenic hair under the above cleaning conditions.

[0097] FUNDAMENTA Procedure The application of the Fundamenta procedure achieves the destruction of the cleaned surface and subsurface of keratin fibers, such as anogenic hair. The Fundamenta procedure can be applied after the Praeparatur procedure or without prior application of the Praeparatur procedure. The Fundamenta procedure structurally destroys the surface topography and chemical composition of the keratin fiber surface and removes the F layer coating on the keratin fiber if present. Exemplary activities include the use of one or more alkali phase-transfer tensides (PETTs) such as acidic oxidation, basic oxidation, reduction, low-temperature plasma discharge, and / or multialkylammonium halides, examples of which are C26-C20 alkyltrimethylammonium chlorides (CTACs) or bromides (CTABs), such as choline halides, cetyltrimethylammonium halides, or stearyltrimethylammonium halides.

[0098] Acidic oxidation can be achieved by exposing anagenic hair or imitation Tres to a dilute acidic oxidizing agent solution. The oxidizing agent solution may be formulated using 0.1 to 6 weight percent, preferably 0.5 to 3 weight percent, of active oxidizing agent (calculated by considering the concentration of oxidizing agent in the solution provided by the supplier) in an aqueous medium with a pH of 2 to 5. The oxidizing agent may be hydrogen peroxide. Persulfates are not preferred for the acidic oxidation process because they are stronger oxidizing agents. Oxidizing agents are typically supplied by commercially available sources as acidic solutions. However, if necessary, the pH can be adjusted with mineral acids such as hydrochloric acid or sulfuric acid, or organic acids such as acetic acid. The oxidizing agent solution is applied to the imitation Tres or anagenic hair and massaged through the hair with either hands or a brush for 10 seconds to about 5 minutes, preferably about 10 seconds to about 1 to 2 minutes. The Tres or anagenic hair, which is then substantially saturated with the oxidizing agent solution, may be rinsed briefly with water, if necessary, to remove excess oxidizing agent solution, but it is not necessary to rinse to the extent that all of the oxidizing agent solution is removed. The presence of a certain concentration of oxidizing agent is thought to be necessary to achieve coupling of the reactive groups of the PTH alkoxysilane compound, such as thiols and aldehydes, particularly thiols, with the sulfur moiety of the disrupted keratin protein, thereby forming disulfide bonds and other coupling bonds.

[0099] Basic oxidizing agent treatment can be achieved by exposing anagenic hair or imitation Tres to a dilute oxidizing agent solution. The oxidizing agent solution can typically be formulated as an aqueous solution of persulfate, hypochlorite, peroxide, or ozone at a concentration of about 0.5% to about 10% by weight, preferably about 0.5% to about 5% by weight, and more preferably about 0.5% to about 3% by weight. The pH of the oxidizing agent solution can be raised to a basic pH of 9 to 10.5 by adding ammonia or MEA, or silicic acid or sodium metasilicate. The oxidizing agent solution is applied to the imitation Tres or anagenic hair and massaged through the hair with either hands or a brush for 10 seconds to about 5 minutes, preferably about 10 seconds to about 1 to 2 minutes. The Tres or anagenic hair, which is then substantially saturated with the oxidizing agent solution, is then repeatedly rinsed with water to remove the oxidizing agent solution.

[0100] The reduction treatment can be achieved by exposing an anagenic hair or mimic tores to an aqueous solution or emulsion of thioglycolic acid at a basic pH of 8.5–9.5, preferably 1–30 percent, preferably 2–25 percent. The contact is maintained for approximately 5–15 minutes, preferably about 10 minutes, after which the hair or tores is rinsed with water and allowed to dry to the touch. Commercial perm step 1 products, such as Wella Creatine(N) Perm Emulsion available from Wella Professionals, can also be used as reducing agents.

[0101] Low-temperature plasma treatment can be achieved by passing a partially ionized gas over an anogenic hair or imitation hair. Low-temperature plasma is a non-equilibrium atmospheric plasma of air or a gas such as oxygen and / or nitrogen, which has an effective gas temperature close to room temperature, although the electron temperature may be much higher. The gas is passed between dielectric coated electrodes at a high AC voltage potential difference or through an RF field. The electromagnetic field creates a cascade of ionization processes that remove some electrons from the gas atoms, resulting in a low-temperature plasma flow. An example is an ozone generator that passes air through a high-voltage spark discharge. Low-temperature plasma generators are commercially available devices designed for the production of room-temperature (low-temperature) plasma. The plasma is transported through a flexible tube to a nozzle. The nozzle through which the plasma flow passes over keratin fibers to achieve plasma treatment. A typical treatment of imitation hair involves passing the nozzle through which the plasma flows over keratin fibers for approximately 1 to 5 minutes, preferably about 1 to about 3 minutes.

[0102] Alkaline phase-transfer tenside treatment is achieved by washing an anagenic hair and / or mimic Tres with an aqueous solution of a phase-transfer tenside containing an alkaline base or a nucleophile such as an alkoxide. The phase-transfer tenside (PETT) is generally a C2-C20 multialkylammonium halide such as choline, preferably a C12-C20 alkyltrimethylammonium chloride or bromide, more preferably cetyl (C16) and / or stearyl (C18) trimethylammonium bromide (CTAB). PETT can be formulated as a 0.1% to 25% by weight aqueous solution. The PETT treatment can be obtained by applying an alkaline or thiol aqueous solution of PETT (basic alkali pH > 10, basic thiol pH > 7) to mimic Tres or ananagenic hair and massaging it through the hair by hand or brush for 5-30 minutes, preferably 5-15 minutes. Subsequently, the Tres or anogenic hair, which is substantially saturated with aqueous basic PETT, is repeatedly rinsed with shampoo in an acidic medium to remove the PETT solution.

[0103] The use of an acidic agent and / or a nucleophilic agent in any of the Fundamenta processes can facilitate the removal of esterified and / or thioesterified 18-methyleicosanoic acid (F-layer acid) from the surface of keratin fibers through interaction with the hydroxyl or cysteine or mercapto groups of the keratin protein. This action hydrolyzes the F-layer bond and enables the dissolution of the resulting free F-layer acid. Examples of such media are thioglycolic acid or thioglycolate in acetone or aqueous acetone, or an alkyl or aromatic thiol such as hexylthiol or thiophenol.

[0104] Any combination of the processes of the Praeparatur procedure and the Fundamenta procedure can be carried out according to the present invention. These combinations include Praeparatur and acidic oxidation, Praeparatur and basic oxidation, Praeparatur and reduction, and Praeparatur and reduction followed by acidic oxidation. Each of these combinations can be carried out sequentially or simultaneously. These combinations further include Praeparatur and plasma treatment and Praeparatur and PETT that can be carried out sequentially.

[0105] Alternatively, each of the processes of the Fundamenta procedure can be carried out alone without the Praeparatur procedure. These include individual implementations of each of acidic oxidation, basic oxidation, reduction, plasma treatment, and PETT treatment alone. In addition, reduction followed by acidic oxidation can be carried out without the Praeparatur procedure.

[0106] Pretreatment composition Significant persistence, abrasion resistance, and resistance to environmental attack of coatings on keratin fibers, preferably color coatings, according to aspects of the present invention may develop through interactions between one or more components of the film-forming composition, pretreatment composition, and modified keratin fibers, preferably anogenic hair. These interactions are complex and involve the coordination of binders and pretreatment low molecular weight components and disrupted keratin proteins on and below the surface of the keratin fibers, preferably anogenic hair, through rearranged covalent bonds, hydrogen bonds, dipole interactions, and molecular entanglement (tangles).

[0107] The amount of PTH as thiols or thiol derivatives (hereinafter referred to as thiols in this paragraph) per unit mass of the pretreatment composition determines the reactivity of the thiol groups to the keratin protein thiols and the potentially reactive groups of the film-forming composition. Although the concentration of thiols becomes very high during the drying process, drying does not affect the value of thiols per unit mass, so the amount per unit mass is a more accurate determinant of the reaction capacity than the overall thiol concentration. This thiol per unit mass can be expressed as the functional group equivalent molecular weight (FEMw), which is the total molecular weight of the molecule or polymer divided by the number of thiol or protected thiol functional groups.

[0108] Embodiments of the pretreatment composition may include a PTH alkoxysilane compound as the pretreatment molecule defined above, incorporating a PTH group and an alkoxysilyl group. In addition to the PTH group as a thiol, the PTH group includes a sulfur-protecting derivative and a complementary reactive group that binds to the thiol of the keratin protein. The pretreatment molecule of the pretreatment composition preferably has a weight-average molecular weight of about 100 Da to about 40 kDa, preferably about 100 Da to about 5 kDa, more preferably about 100 Da to about 3 kDa, and particularly more preferably about 100 Da to about 2 kDa. Optionally, the pretreatment composition may also incorporate aminoorganoalkoxysilanes and thiol organic compounds.

[0109] Embodiments of the PTH alkoxysilane compound in the pretreatment composition include an organic core comprising 1 to 10 carbon atoms or 1 to 100 repeating organic monomer units, preferably 1 to 50 repeating organic monomer units, more preferably 1 to 10 repeating organic monomer units, wherein the monomer units may be olefins, esters, amides, urethanes, ureas, ether units, and any combination thereof. Alternatively, the pretreatment composition may include a silicone core comprising about 1 to about 100 dimethylsiloxanyl units, preferably about 1 to about 50 dimethylsiloxanyl units, more preferably about 1 to about 20 dimethylsiloxanyl units, particularly more preferably about 1 to about 10 dimethylsiloxanyl units, and most preferably about 1 to about 5 dimethylsiloxanyl units. Alternatively, the silicone core may include 1 to 3 silicone units, more preferably 1 or 2 silicone units, in addition to the alkoxysilane group. Embodiments of the organic and silicone core molecules in the pretreatment composition also include one or more PTH groups and one or more alkoxysilyl groups. The number of PTH groups and alkoxysilyl groups present in the pretreatment molecule depends on the type of intermolecular linkage desired in the pretreatment composition. In particular, the pretreatment molecule is thought to contain at least one PTH group for chemical interaction with modified keratin proteins, forming chemical bonds with the modified keratin proteins such as disulfide, sulfone ester, thioester, and similar functional groups. In particular, the pretreatment molecule also contains at least one alkoxysilyl group. PTH and alkoxysilyl group-containing molecules can also be formed in situ from compatible PTH and alkoxysilyl precursors, some examples of which are a) multimercapto molecules and epoxy-alkoxysilyl molecules, b) multimercapto molecules and alkenoyloxy-alkoxysilyl molecules, c) multimercapto molecules and alkene-alkoxysilyl molecules, and d) mercapto-amino molecules and aldehyde-alkoxysilyl molecules. The alkoxysilyl groups form covalent silicon-oxygen-silicon or silicon-oxygen-carbon bonds with the binder and the PTH alkoxysilane compound itself, forming an extended silicone polymer moiety.Examples of PTH alkoxysilane compounds include PTH organoalkoxysilanes and PTH organomultidimethylsiloxanylalkoxysilanes, as described above and by formulas IIIA and IIIB, respectively, as described below.

[0110] In addition to the PTH alkoxysilane compounds themselves, dimers having disulfide and tetrasulfide forms are included. Dimers having disulfide forms are formed from PTH alkoxysilane compounds having PTH as a thiol. These consist of two thiol organo-alkoxysilanes or two thiol organomultidimethylsiloxanyl alkoxysilanes bonded together at their thiol groups, forming bis[organo-alkoxysilanyl]disulfide or bis[organo-multidimethylsiloxanylalkoxysilane]disulfide, respectively. Dimers having tetrasulfide forms of two thiol organo-alkoxysilanes or two thiol organomultidimethylsiloxanyl alkoxysilanes bonded together at their thiol groups in combination with sulfur as S2, forming bis[organo-alkoxysilanyl]tetrasulfide or bis[organo-multidimethylsiloxanylalkoxysilane]tetrasulfide.

[0111] The pretreatment composition further includes any thiol organic component of formula V and any aminoorganoalkoxysilane component of formula VI, as described below.

[0112] The components of the pretreatment composition include at least one compound from the group of PTH alkoxysilane compounds, which includes PTH organoalkoxysilanes, PTH organomultidimethylsiloxanylalkoxysilanes, and / or cyclic thiolalkoxysilanes.

[0113] These PTH alkoxysilane compounds are structurally characterized by formulas IIIA, IIIB, and IV, and include PTH compounds in which the PTH group comprises a free thiol group, sulfide dimers and tetramers, a group that is complementary and reactive with thiols, and sulfur-protected analogs. (PTH-(CH2) k -(Y) l ) d -(ORG) m -SiR 1 3-n (OR) n Formula IIIA PTH-(CH2) k -(SiMe2O) o -SiR 1 3-n (OR) n Formula IIIB TIFF0007862521000003.tif30170

[0114] Formulas IIIA, IIIB, and IV are characterized by the indicators k, l, d, m, n, o, and the substituents PTH, Y, and ORG. The indicators in order of appearance in formulas IIIA, IIIB, and IV are as follows: 1) The indicator k is an integer between 1 and 20, preferably between 1 and 10, and more preferably between 1 and 6. 2) Indicator l is either zero or 1. 3) The indicator d is an integer of 1, 2, or 3. 4) The indicator m is zero or an integer from 1 to 6. 5) The indicator n is an integer between 1 and 3. 6) The indicator o is an integer between 1 and 20.

[0115] The substituent PTH defines the thiol moiety, R 3 S-, as well as OHC-, H2C=CR 10 It may contain a chemical group that reacts with thiols, including -CO2- or HO-. 3The group defines whether the thiol moiety is a free thiol (-SH) or a protected thiol. Therefore, substituent R 3 It may contain hydrogen, cyano, 2-10 carbon alkanoyl, phenyl group, heteroaromatic group, phenylalkyl group or heteroaromatic alkyl group, the heteroaromatic group being pyridyl, pyrimidinyl, pyrrolyl or thiophenyl, and the alkyl group being C1-C4 alkyl group, R 10 It can be hydrogen or methyl.

[0116] The R group defines the alkyl properties of the alkoxy group. Therefore, R may include C1-C4 alkyl, preferably C1-C3 alkyl, more preferably methyl or ethyl.

[0117] The Y group is PTH-(CH2) k This defines how the part is connected to the rest of formula IIIA. The Y group may be absent (l is zero) or present (l is 1). If present, Y may include -COO-, -OOC- (carboxyl, oxycarbonyl), ether oxygen, ether thiol, -NH-, -NMe-, -HNCO-, or -CONH-.

[0118] The ORG group is an organic connecting group that links the left and right halves of formula IIIA. As a connecting group, ORG can be divalent or polyvalent. In the divalent configuration, the left side is (PTH-(CH2) k -(Y) l ) d Connect the part to the right part. The multivalent form has multiple left (PTH-(CH2) k -(Y) l ) d The portion is connected to the single alkoxysilane group on the right. Therefore, the ORD group can contain two different configurations.

[0119] In the first configuration, the ORG group is the left (PTH-(CH2) of formula IIIA k -(Y) l ) d Part and right-SiR 1 3-n (OR2 ) n The group comprises an alkyldithioalkyl, alkyldiazoalkyl, alkyluretanylalkyl, alkylureidoalkyl, alkylcarboxylalkyl, alkylamidealkyl, alkylesteralkyl, or a divalent organic group containing an alkyl, wherein each alkyl group is independently a C1-C20 linear or branched alkyl group in each case, preferably a linear C1-C6 alkyl group, and more preferably a linear C1-C3 alkyl group.

[0120] In the second configuration, the ORG group contains a polyvalent C1-C20 alkylenyl group of the following formula, where f is zero or an integer from 1 to 19: TIFF0007862521000004.tif19170 In this second configuration, (PTH-(CH2) k -(Y) l ) d -(ORG) m The part of equation IIIA that includes equation A This will result in TIFF0007862521000005.tif30170.

[0121] Equation A is an ORG dangling multiple valence with two or three (PTH-(CH2) connected as D k -(Y) l ) d It has two parts. (PTH-(CH2) k -(Y) l ) d When the portion is connected to the dangling multiple valencies of ORG, the third D of formula A may be hydrogen or a C1-C6 alkyl, preferably a C1-C3 alkyl, more preferably a methyl. (CH2) f - The dangling valence of -SiR is right-hand in formula IIIA. 1 3-n (OR 2 ) n It is joined to a part.

[0122] In addition to the PTH alkoxysilane compounds of formula IIIA or formula IIIB, these compounds can be pre-condensed at least partially to form polycondensates of PTH alkoxysilanes of formula IIIA and / or formula IIIB having PTH as a thiol or protected thiol, and the PTH alkoxysilanes of formula IIIA and / or formula IIIB can be formed by themselves or together with and / or alkylalkoxysilanes of formula B [wherein R 8 [A linear or branched alkyl group consists of 1 to 10 carbon atoms]: R 8 -SiR 1 3-n (OR) n Formula B It undergoes at least partial polycondensation to produce a linear or branched oligomeric silicone polycondensate having linear or branched silicone chains of combinations of M, D, and T groups, wherein the polycondensate has pendant alkoxy groups, pendant thioalkyl groups, and pendant alkyl groups, and the polycondensate has M at 350-3500 Da w as well as the functional group equivalents M of thiols and / or protected thiols from 70 to 900. w (FEM w ) and FEM of 50-900 alkoxy groups w It holds.

[0123] Preferably, the pre-condensed PTH alkoxysilane compound is of formula IIIA and undergoes partial pre-condensation alone to form a linear or branched oligomeric silicone polycondensate.

[0124] Any PTH organic compound that does not have an alkoxysilyl group may be included in the pretreatment composition as an auxiliary sulfur compound together with the PTH organic alkoxysilane. Any PTH organic compound provides multiple links between and to the sulfur groups of the proteins of the modified keratin fibers, at least by the film-forming composition. Any PTH organic compound is of formula V Includes TIFF0007862521000006.tif46170.

[0125] For equation V, D is defined above (PTH-(CH2) k -(Y) l The variables of this D group are independent for each example of D. Each of the indicator g is independently zero or 1. The E group can be a bond or a C1-C6 alkylenyl group. The Ak group can be the carbon atom Ak0 or structures Ak1, Ak2, Ak3, Ak4, as shown below. The dangling valencies of the central carbons of Ak0, Ak1, Ak2, and Ak3 are bonded to ED, and the CH2 valency is bonded to D. All dangling valencies of Ak4 are bonded to ED. TIFF0007862521000007.tif62170

[0126] Regarding formula V, Ak2 and Ak3, which have a methyl group bonded to the central carbon, each have one or two of the indicator g of formula V set to zero, and have a methyl group instead of the zeroed ED group. The PHY of Ak4 has -O-(CH2) at its carboxyl terminus. h -O- group and its hydroxyl terminus -(CH2) i -O-(CH2) h -O- group and -(CH2) i Each -O- group is bonded to a CH group, the indicator h is an integer between 2 and 4, and the indicator i is an integer between 1 and 3.

[0127] For all of the aforementioned compounds containing sulfur, the preferred form of PTH is -SH.

[0128] Any aminoorgano-alkoxysilane may be included in the pretreatment composition as an auxiliary amine compound. The aminoorgano-alkoxysilane provides additional electrostatic interaction with the film-forming composition, particularly as an olefin polymer having a carboxyl group. The aminoorgano-alkoxysilane compound is of formula VI. [H2N-(CH2) m -(NH-R 14 ) n ] a -[ROt Me 3-t Si - O] b -(-SiMe2 - O) p -[(-SiMe 2-r [(CH2) m’ -NH2] r -O] s -[A] c -(-SiMe2 - O) u -(SiMe 3-t OR t ) Formula VI contains.

[0129] For Formula VI, R 14 is a C1 - C6 alkenyl group, and R can be methyl or ethyl. The indicators m, n, a, t, b, p, r, m', s, c, and u indicate the presence or absence of the relevant groups. When the relevant groups are present, the corresponding indicators indicate how many of those groups are present. These indicators are as follows. The indicators m and m' can be integers from 1 to 6, preferably from 1 to 3. The indicators b, r, s, c can be zero or 1. The indicator n can be zero or an integer from 1 to 6, preferably zero or from 1 to 3. The indicator a can be zero or an integer from 1 to 3. The indicator t can be from 1 to 3. The indicators p and u can be zero or integers from 1 to 12.

[0130] The groups within the angle brackets, namely the groups with indicators a and b, and the group with indicator s, are terminal groups and pendant groups such that when b is 1 and a is zero, the group with indicator b becomes the terminal group, and when a is 1 and b is zero, the group with indicator a becomes the terminal group. In these examples of terminal groups, the pendant amine group - CH2) m'To provide an amino organo-alkoxysilane having -NH2, when b is 1, a must be non-zero and s and r must be 1. Alternatively, in these examples of end groups, when a is 1, 2 or 3, b must be non-zero.

[0131] The A group, which is the remaining substituent, can be any one of three alternative moieties. These are as follows. 1) The A group can be a divalent group containing dithio, diazo, urethanyl, ureido, carboxyl, amide, ester, or aminoethyloxycarbonyl, which connects the left and right parts of the amino organo-alkoxysiloxane compound, or a C1-C20 alkenylenyl group. 2) The A group can be a polyvalent C1-C20 alkenylenyl group that connects two or three left parts and one right part of the amino organoalkoxysiloxane compound when a is 2 or 3 and b, p, and s are zero. 3) The A group can be a linear or branched polyethyleneimine moiety of 2 to 2000 ethyleneimine units, in which case b, p, s, and u are all zero, and optionally, the -(SiMe 3-t OR t ) group may be replaced by -NH2. 4) The A group can be a terminal group selected from C2-C8 alkenylenyl (meth)acrylate or -(CH2) n -O-CH2-CHOHCH2-O2C(R)=CH2 [where R is H or CH3 and n is an integer from 2 to 8].

[0132] A preferred version of the PTH organo-alkoxysilane of formula IIIA is one that includes OSSI [where k is an integer from 1 to 20, preferably 1 to 6, the plurality of (CH2) chains may be linear or branched, n is an integer from 1 to 3, preferably 3, R 1 is methyl, and R 2 is methyl or ethyl]. HS-(CH2) k -SiR 1 3-n(OR 2 ) n OSSI formula A more preferred version of the OSSI formula is, where n is 3, R 2 The following embodiments of thiol organoalkoxysilanes are provided, with the methyl (Me) or ethyl (Et) being denoted as methyl. HS-(CH2) k -Si(OMe)3 or HS-(CH2) k -Si(OEt)3

[0133] A preferred version of the aminoorgano-alkoxysilane of formula V is given by formula OASI[wherein m is an integer from 1 to 6, n is zero or an integer from 1 to 3, p and u are each independently zero or an integer from 1 to 3, c is zero or 1, R 14 Each example is independently ethyl, propyl, butyl, or isobutyl, where A is a C1-C6 alkylenyl, and R 3 is methyl, and R 4 [contains methyl or ethyl.] H2N-(CH2) m -(NH-R 14 -) n -(SiMe2O) p -A c -(-SiMe2-O] u -SiR 3 3-t Ure 4 t formula OASI A more preferred version of formula OASI is as follows: p, u and c are zero, m is 2, 3 or 4 (butyl or isobutyl), n is 1 or 2, R 14 Each example is independently considered as ethyl, propyl, butyl, or isobutyl, with t set to 3, R 4 Represented as methyl (ME) or ethyl (Et), at least the following embodiments of aminoorganoalkoxysilanes are provided: H2N-(CH2) m -Si(OR 4 )3 or H2N-(CH2) m -(NH-R14 ) n -NH-R 14 -Si(OR 4 )3 or H2N-(CH2) m -NH-R 14 -Si(OR)3.

[0134] Exemplary embodiments of the thiol organoalkoxysilane component of the pretreatment composition include, but are not limited to, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltriethoxysilane, 4-mercaptobutyltriethoxysilane, 1-mercaptomethyltriethoxysilane, bis[3-(triethoxysilyl)propyl]disulfide, 2,2-diethoxy-1-thio-2silacyclopentane, and their trimethoxysilane and trimethoxysilyl versions.

[0135] Table III provides a list of suitable thiol organoalkoxysilane compounds as pretreatment molecules for pretreatment compositions. Table III Thiol organoalkoxysilane pretreatment of small molecules TIFF0007862521000008.tif187170

[0136] Additional preferred thioorganoalkoxysilanes, preferred aminoorganoalkoxysilanes, and other preferred alkoxysilanes of the pretreatment composition are: a) Trimethoxysilylpropyldiethylenetriamine (SCA); b) Trimethoxysilylpropyl (meth)acrylate ester (MEMO); c) Aminopropyltriethoxysilane (APTES); d) Tetraethoxysilane (TEOS); e) 3-mercaptopropylsilyltriol; f)3-mercaptopropyltrimethoxysilane; g) 3-mercaptopropyltriethoxysilane; h)3-Thioglycidyloxypropyltrimethoxysilane; i) 3-Thioglycoloyloxypropyltriethoxysilane Includes.

[0137] Binder process for forming a coating, preferably a color coating, on keratin fibers. Embodiments of a method for forming a coating, preferably a color coating, on keratin fibers involve a binder step as a final step. The binder step requires applying a film-forming composition onto modified keratin fibers having a pre-coating of a pretreatment composition. The film-forming composition may comprise one of four different types of polymer compositions. The first two embodiments of the film-forming composition are based on a unitary binder polymer structure. The first embodiment comprises a unitary binder polymer having monofunctional binder groups containing alkoxysilane groups. The second embodiment comprises a unitary binder polymer having monofunctional binder groups containing carboxylic acids or carboxylic acid bases.

[0138] The third and fourth embodiments of the film-forming composition are based on a dual in situ reactive polymer structure. The third embodiment comprises a binder polymer pair in which the first component binder polymer has a functional binder group containing an alkenoyloxy group, and the second component binder polymer has a functional binder group containing an amine or thiol group. These two functional binder groups constitute a complementary pair or reactive group, commonly known as a Michael addition pair. The fourth embodiment comprises a binder polymer pair in which the first component binder polymer has a functional binder group containing a carboxylic acid group, and the second component binder polymer has a functional binder group containing a carbodiimide group. These two functional binder groups constitute a complementary pair of reactive groups.

[0139] Single polymer alkoxysilane film-forming composition In a first embodiment of the film-forming composition, the binder polymer is unitary, in situ crosslinkable, and comprises an organic polymer binder having two or more functional binder groups, both of which are alkoxysilyl groups. The film-forming composition may further comprise a substance that functions as a catalyst with respect to this in situ crosslinkable polymer. More specifically, the organic polymer binder comprises an in situ crosslinkable self-covalent reactive organic polymer having two or more alkoxysilyl pendants and / or terminal groups, preferably at least terminal alkoxysilyl groups. The organic polymer binder may comprise polymers or copolymers of esters, amides, urethanes, ureas, ethers and / or olefin monomer units or any combination thereof. The binder polymer may be a random or block copolymer and may have a linear or branched, preferably linear, structure.

[0140] In particular, self-reactive organic polymer binders are of formula IA X3Si-R 1 -Ct-[Poly] y -Ct-R 1 -Si-X3 Formula IA It includes. In formula IA, X may be an alkoxy of 1 to 3 carbon atoms, preferably methoxy or ethoxy. 1 The group is a C1-C8 linear or branched alkylenyl group. The Ct group is X3Si-R 1 - is a connector base that joins or connects to Poly.

[0141] The Ct group is represented by formula II: -U 1 -R 2 -U 2 - Formula II It includes. Regarding Equation II, U 1 and U 2 Each of these is independently either a urea group or a urethane group. 1 The base is R 1 It is covalently bonded to U 2 The group is covalently bonded to Poly.2 The group is a C2-C12 linear or branched alkylenyl group, a C6-C16 alkylcycloalkyl group that may contain one or more cycloalkyl rings linked in tandem or by alkyl groups, a C6-C12 aromatic group that may contain one or more aromatic groups, or a C6-C14 alkyl aromatic group that may contain one or more aromatic groups linked in tandem or by alkyl groups. 2 The embodiments of the group are derived from common diisocyanates. For example, hexamethylene diisocyanate (1,6-hexanediisocyanate) generates an alkylenyl group. Isophorone diisocyanate generates an alkylcycloalkyl group. Toluene diisocyanate generates an alkyl aromatic group. Methylenebis(cyclohexaneisocyanate) also generates an alkylcycloalkyl group. Methylenediphenyl isocyanate generates an alkyl aromatic group. Formula II is R 2 - Diisocyanate and X3SiR 1 It is produced by the corresponding hydroxyl or amine combination from -G and G-Poly [wherein each G is independently an amine or a hydroxyl group].

[0142] Poly is a primary binder polymer backbone that provides flexibility, tensile strength, and film formation for coatings, preferably color coatings. Preferably, Poly is an organic backbone having at least terminal alkoxysilyl groups (i.e., trialkoxysilyl groups as defined in the definition section) of monomer units such as esters, amides, urethanes, ureas, and olefin units, but not limited to them. The backbone of Poly can be any configuration, preferably linear or branched, with the linear configuration being the most preferred. In the branched configuration of Poly, any pendant alkoxysilyl groups can be at the ends of the branches. Due to the multiple condensation ability of each alkoxysilyl group of the binder polymer, their condensation to form Si-O-Si bonds produces an in situ crosslinked binder polymer that forms a three-dimensional network. All configurations of Poly, preferably the linear configuration of Poly, produce this binder polymer network having Si-O-Si connections that extend the backbone and interconnect other backbones as crosslinks, because alkoxysilyl groups can condense multiple times with other alkoxysilyl groups. Although not limited to the present invention, in situ crosslinking is thought to occur similarly to pre-treated alkoxysilyl low-molecular-weight molecules, establishing a three-dimensional network across the entire combination of binder polymer and low-molecular-weight molecules.

[0143] The Poly group may have any structural configuration as described in the Definition section, preferably a linear skeleton configuration, and may be formed from monomer units of ester, urethane, urea, amide, or polyol (ether) groups, or any combination thereof. The indicator y is an integer indicating the range of Poly and the number of monomer units of Poly forming the skeleton. Thus, y is an integer from about 2 to a maximum of about 1,000,000, preferably a maximum of about 300,000, more preferably a maximum of about 250,000, and most preferably a maximum of about 200,000.

[0144] When the monomer unit of Poly is an ester, the ester monomer unit may be formed from a C2-C10 linear or branched alkanediol or a C8-C20 aromatic diol and a C3-C10 linear or branched alkanodioic acid or a C8-C10 aromatic dicarboxylic acid, or from a C3-C10 hydroxyalkanoic acid or a C8-C10 aromatic hydroxycarboxylic acid.

[0145] When the monomer unit of Poly is urethane, the urethane monomer unit consists of C2-C10 alkanodiols and R 3 Diisocyanate [wherein R is the formula] 3 It is formed from the following:

[0146] When the monomer unit of Poly is urea, the urea monomer unit consists of a C2-C10 linear or branched alkanodiamine and R 3 It is formed from diisocyanates.

[0147] When the monomer unit of Poly is an amide, the amide monomer unit is formed from a C2-C10 alkanodiamine and a C3-C10 alkanediic acid or a C8-C10 aromatic dicarboxylic acid.

[0148] When the monomer unit of Poly is a polyol, the polyol monomer unit is formed from ethylene oxide (linear) or propylene oxide (branched).

[0149] Preferred ester monomers for Poly are formed from glycol, 1,4-butanediol, or 1,6-hexanediol with malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, terephthalic acid, or any combination thereof; or Poly is formed from glycolic acid or lactic acid, ω-hydroxypropanoic acid, ω-hydroxybutanoic acid, or p-hydroxybenzoic acid. Particularly preferred ester monomers for Poly are formed from glycol (dihydroxyethane) or 1,6-hexanediol with succinic acid, adipic acid, or phthalic acid or terephthalic acid.

[0150] Preferred urethane monomers for Poly are formed from glycol, 1,4-butanediol or 1,6-hexanediol with isophorone diisocyanate, methylenebis(phenyl isocyanate), toluene diisocyanate or 1,6-hexanediisocyanate. Particularly preferred urethane monomers for Poly are formed from glycol or 1,6-hexanediol with isophorone diisocyanate or toluene diisocyanate.

[0151] The preferred urea monomers for Poly are formed from 1,3-propanediamine, 1,4-butanediamine, or 1,6-hexanediamine with isophorone diisocyanate, methylenebis(phenyl isocyanate), toluene diisocyanate, or 1,6-hexanediisocyanate. The particularly preferred urethane monomers for Poly are formed from 1,3-propanediamine or 1,6-hexanediamine with isophorone diisocyanate or toluene diisocyanate.

[0152] The preferred amide monomers for Poly are formed from 1,3-propanediamine, 1,4-butanediamine, or 1,6-hexanediamine with malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, terephthalic acid, or any combination thereof. The particularly preferred amide monomers for Poly are formed from 1,3-propanediamine or 1,6-hexanediamine with succinic acid, adipic acid, phthalic acid, or terephthalic acid.

[0153] The preferred polyols for Poly are PEG-200 to PEG-2000.

[0154] The poly group can be any combination of esters, urethanes, ureas, amides, and / or polyols in block or random arrangement. For example, a) Combinations of polyester blocks and polyurethane blocks may be formed from blocks of diols, dicarboxylic acids, and diisocyanates; b) Combinations of polyester blocks and polyurea blocks may be formed from their respective reactants, and the bonds between the blocks may be formed as urethane connections by reacting a polyester block terminated with hydroxyl with a polyurea block terminated with isocyanate; c) Combinations of polyester blocks and polyamide blocks may be formed from blocks of dicarboxylic acids, diols, and diamines; d) Combinations of polyester blocks and polyol blocks can be formed from polyol and diol and dicarboxylic acid blocks; e) Combinations of polyurethane blocks and polyurea blocks may be formed from their respective reactants, and the bonds between the blocks may be formed as urethane and / or urea connections; f) Combinations of polyurethane blocks and polyamide blocks may be formed from their respective reactants, and the bonds between the blocks may be formed as urea connectors by reacting a polyamide block terminated with an amine with a polyurethane block terminated with an isocyanate; g) Combinations of polyurethane blocks and polyol blocks may be formed from polyol and diol and diisocyanate blocks; h) Combinations of polyurea blocks and polyamide blocks may be formed from their respective reactants, and the bond between the blocks may be formed as a urea connector by reacting a polyamide block terminated with an amine with a polyurea block terminated with an isocyanate; i) Combinations of polyurea blocks and polyol blocks may be formed from polyol and diamine and diisocyanate blocks, and the bonds between the blocks may be formed as urethane connectors by reacting a polyol block terminated with hydroxyl with a polyurea block terminated with isocyanate; j) Combinations of polyamide blocks and polyol blocks may be formed from polyol and diamine and dicarboxylic acid blocks, and the bonds between the blocks may be formed as ester connectors by reacting a polyol block terminated with hydroxyl with a polyester block terminated with carboxylic acid.

[0155] The proviso is U 2 Applies to the selection of the group. If the trialkoxysilylalkylenyl-G starting material is trialkoxysilylalkylenylamine, then U 1 It is always urea. Alternatively, if the trialkoxyalkylenyl-G starting material is trialkoxysilylalkylenyl alcohol (OH), then U 1 It is always urethane. In the following proviso, U 1 This is always a urea derived from a preferred trialkoxysilylalkylenylamine starting material. a) If Poly ends in an ester monomer unit, U 2 It is a urethane group, U 1 It is a urea group. b) When Poly ends in a urethane monomer unit, U 2 It is a urethane group, U 1 It is a urea group. c) If Poly ends in a urea group, U 2 and U 1 Both are urea groups. d) If Poly ends in an amide monomer unit, U 2 and U 1 Both are urea groups. e) If Poly ends in a polyol monomer unit, U 2 It is urethane, U 1 It is a urea group.

[0156] R 2 Similar to the base, R 3 The group may be a C2-C12 linear or branched alkylenyl group, a C6-C16 alkylcycloalkyl group, or a C6-C14 aromatic group. 2 and R 3 Both are organic groups of the diisocyanate reaction substance that form a urethane group and a urea group. Preferably, R 2 and R 3 These can each be independently methylenebisphenyl (like methylenebis(phenyl isocyanate)), toluenelenyl (like toluene diisocyanate), hexanilenyl (like hexamethylene diisocyanate), naphthalenyl (like naphthalendiisocyanate), methylenebiscyclohexylenyl (like methylenebis(cyclohexyl isocyanate) which is hydrogenated methylenebis(phenyl isocyanate)), and isophoronylenyl (like isophorone diisocyanate).

[0157] In each of the organic binder polymers of formula IA, Poly may optionally contain one or more trifunctional groups, such as triols or triamines, that function to provide pendant alkoxysilyl groups to the organic binder polymer.

[0158] The third hydroxyl or amine of the trifunctional group is the same Ct-R as in formula IA. 1 The linkage to the pendant SiX3 is formed through the base. The organic binder polymer in this version is formula IB[wherein Z is Ct-R]. 1[A trifunctional group linked to a third SiX3 through:] X3Si-R 1 -Ct-[(Poly) x -(Z) z -(Poly) a ] y -Ct-R 1 -Si-X3 Formula IB It includes. For formula IB, the Z group is a triol or triamine starting material of formula III. TIFF0007862521000009.tif25170 [wherein the formula, the Y group is hydroxyl or amine] If derived from or if Poly is an ester, the Z group may instead be a tricarboxylic acid. Except for the tricarboxylic acid embodiment, formula IV is a homologous starting material of a diol or diamine starting material for an ester, urethane, urea, amide or polyol monomer unit, and the -R of formula IV 5 -The Y branching group has the same structure as the organic part of the diol or diamine. For example, if Poly is a polyurethane or polyurea constructed from propanediol, the triol compound will be 2-hydroxymethyl-1,3-propanediol, also known as trihydroxymethylmethane. As described above for Z, the pendant Y group (hydroxyl or NH2), which is the third Y group of the triol or triamine, is through Ct to R such that the pendant Y of the triol or triamine starting material of formula IV becomes part of the urethane or urea group, as shown for Ct of formula I. 1 - It is bonded to SiX3. Z is the structure = R 4 -R 5 -Ct-R 1 The resulting complete formula IB, which has -SiX3, The filename is TIFF0007862521000010.tif35170.

[0159] In formula IB, the indicator z represents the number of pendant alkoxysilyl groups present in the binder polymer. For binder polymers with multiple pendant alkoxysilyl groups, Z in formula IB (i.e., = R) is used.4 -R 5 -Ct-R 1 -SiX3) is randomly distributed throughout the binder polymer backbone. Thus, the indicator z is an integer from 1 to 1000, specifying the number of trifunctional groups present in formula I'. Preferably, z is an integer from 1 to 100, more preferably from 1 to 10, particularly more preferably from 1 to 5, and most preferably from 1 to 3. The sum of the integer indicators x, z, and a is equal to y, such that the weight-average molecular weight of the binder polymer of formula I' is the same as the weight-average weight of the binder polymer of formula I.

[0160] The binder polymer version may be all of formula IA or all of formula IB having terminal and pendant alkoxysilyl groups. The binder polymer may also be a mixture of formula IA and formula IB. In the case of a mixture, the ratio of formula IA to formula IB may be in the range of 100:1 to 1:100, preferably 50:1 to 10:9 or 25:1 to 2:1 or 20:1 to 10:1.

[0161] The weight-average molecular weights of formulas IA and IB may range from about 1 kDa to about 1 MDa, preferably about 1 kDa to about 500 kDa, more preferably about 1 kDa to 300 kDa, particularly more preferably at least about 2 kDa to a maximum of about 250 kDa, and most preferably at least about 2 kDa to a maximum of about 150 to about 200 kDa. The indicator y of formula IA is selected to provide an average molecular weight within this range. Similarly, the sum of the indicators x, z, and a of formula IB is selected to be equal to y and the selection of an average molecular weight within this range.

[0162] The choice of the ratio of z to the two terminal alkoxysilyl groups for formula IB may preferably be in the range of 1:2 to 100:2, more preferably 1:2 or 2:2 to 20:2, and most preferably at least 1:2 to a maximum of 5:2 or 10:2. The presence of pendant alkoxysilyl groups provides additional crosslinking between binder polymer molecules and with pre-treated low molecules. Although not limited to the present invention, additional crosslinking is thought to be possible to result in a significant residual coating, preferably a color coating, on keratin fibers.

[0163] A preferred embodiment of the organic binder polymer of formula IA (having only terminal alkoxysilyl groups) is, a) Poly as a polyurethane composed of C4-C6 alkanediols, preferably hexanediols and isophorone diisocyanate, toluene diisocyanate, or methylenebis(phenyl isocyanate), or b) Poly as polyethylene glycol or polypropylene glycol, or c) Polyester composed of C2-C6 alkanediols, preferably ethylene glycol, and succinic acid, adipic acid, or any form of phthalic acid, preferably terphthalic acid. It provides the Ct group, which is formed from C1-C4 alkane diisocyanates. 1 The -SiX3 group is formed from ω-aminopropyl, isobutyltriethoxysilane, or trimethoxysilane homologs.

[0164] A preferred embodiment of the organic binder polymer of formula IB is the same as the Poly, Ct and R described above for the preferred polyurethane and polyester organic binder polymer of formula IA in subparagraphs a and c, except that about 0.1% to about 5% by weight, preferably about 0.5% to about 3% by weight of C4-C6 alkanediols are replaced by 3-(3-hydroxypropane-1-yl)-1,6-hexanediol, except that the ratio of pendant alkoxysilyl groups to terminal alkoxysilyl groups of the preferred formula IB is 1:2 to 5:2, preferably 1:2 to 3:2. 1 It has -SiX3.

[0165] Particularly preferred embodiments of the binder polymer of formula IA include formula V, which is a linear polyester having terminal alkoxysilyl groups: (RO)3Si-(CH2) c -NHCONH-R 10 -NHCOO-[-(CH2) e -O-CO-(R 20 )-COO-] g -(CH2) e -OCONH-R 10 -NHCONH-(CH2) c Si(OR)3 Formula V [wherein c is an integer from 3 to 6, preferably 3, e is an integer from 2 to 8, preferably ethylene, butane, or hexanediol, more preferably ethylene, R 20 This is divalent benzeneyl (i.e., the divalent benzene residue of any benzenedicarboxylic acid, including phthalic acid, isophthalic acid, and terephthalic acid) or (CH2) f [In the formula, f is an integer from 4 to 8], preferably R 20 is a terephthalic acid residue, a succinic acid residue, or an adipic acid residue, more preferably a terephthalic acid residue, g is an integer from 10 to 300,000, and R 10 [where R is a C4-C8 alkylenyl group, preferably hexylenyl, and R is methyl or ethyl].

[0166] The preferred weight-average molecular weights of preferred versions of formulas IA, IB, and V may range from about 5 kDa to about 200 kDa, preferably from about 5 kDa to about 50 kDa to about 100 kDa.

[0167] Versions of Poly monomer exhibiting flexible alkylenyl groups and rigid aromatic groups, as well as block combinations of Poly, can enable the development of rigid and flexible domains within films formed from binder polymers and pretreatment components. The flexibility of long alkylenyl groups and the rigidity of aromatic groups, as well as hydrogen bonding between intermolecular carboxyl groups and ester, amine, urethane, and / or urethane groups, partially act to promote the development of flexible and rigid domains. The presence of rigid and flexible domains contributes, at least partially, to the tensile strength and flexibility of coatings, preferably color coatings.

[0168] catalyst The film-forming composition may further contain a catalyst to control the rate of alkoxysilyl condensation for forming the Si-O-Si network. As a baseline procedure, contact between the binder polymer and water is sufficient to carry out the condensation. However, hydrolysis and condensation of alkoxysilyl groups under neutral conditions are extremely slow. See, for example, A. Issa and A. Luyt, Polymers, 2019, 11, 537 below for the discussion of alkoxysilane condensation. The use of a catalyst to change the pH of the hydrolysis / condensation medium accelerates the condensation, and an acidic medium is preferred. Lewis acids such as organosulfates, organophosphates, organozirconium, organoaluminum, organozinc, boron halides, organoboron, mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid, as well as organic acids such as acetic acid, oxalic acid, and trifluoroacetic acid are useful in increasing the rate of hydrolysis / condensation. Ammonia and organoamine compounds are also useful, particularly in the condensation, which is the second step of the process. The selection of a catalyst can be controlled by considering the cosmetically and pharmaceutically acceptable properties of the catalyst. For this reason, organotin compounds, which are excellent catalysts for this purpose, are unacceptable due to their toxicity. The combination of an acidic agent, such as an organophosphate or organoboronate, followed by basic washing with dilute ammonia or an organic amine, affects the efficient and rapid condensation of the alkoxysilyl groups of the binder polymer and its combination with the pretreatment composition. Preferred acidic catalysts in this regard include bis(2-ethylhexyl) phosphate esters, bis(acetylacetonate), bis(2-ethylhexyl) sulfate esters, methyl sulfate esters, tri(pentafluorophenyl)boron, or mono or diacetoboronates.

[0169] Monopolyolefin carboxylic acid film-forming composition In a second embodiment of the film-forming composition, the binder polymer may comprise a unitary organic binder polymer of one or more monomer units selected from olefin carboxylate ester units, olefin carboxamide units, carbon-hydrogen olefin units, ester monomer units, amide monomer units, urethane monomer units, and urea monomer units. The organic binder polymer further comprises at least one pendant and / or terminal binder-functional monogroup, preferably at least two binder-functional monogroups comprising a pendant and / or terminal carboxylic acid or sulfonic acid group, preferably a carboxylic acid group. In this second embodiment, the pretreatment composition preferably comprises an aminoorganoalkoxysilane in addition to a thiolalkoxysilane compound. The aminoorganoalkoxysilane introduces amino groups into the condensation pretreatment layer. These amino groups enable electrostatic interactions with the carboxyl groups of the film-forming composition. The organic polymer having carboxylic acid or sulfonic acid groups is preferably linear or branched, more preferably linear.

[0170] Binder polymer Embodiments of acid binder polymers having a carboxylic acid group include, in addition to monomer units of olefin carboxylic acid monomer or olefin sulfonate monomer, preferably olefin carboxylic acid monomer, repeating units of hydrophobic monomer or hydrophilic monomer or a combination thereof, preferably a combination of hydrophobic monomer and hydrophilic monomer.

[0171] The hydrophobic monomer in this embodiment of organic polymer may be selected from one or more of the following: olefin carboxylate ester monomers, olefin carboxamide monomers, olefin sulfonamide monomers, olefin monomers, or any combination thereof.

[0172] Olefin carboxylate esters include esters of an olefin carboxylic acid and at least one saturated linear or branched C1-C24 primary or secondary alcohol, or a C4-C24 cyclic or alkylcyclic alcohol.

[0173] Olefin carboxamide monomers comprise an olefinic carboxylic acid and an amide of at least one linear or branched C1-C24 primary amine.

[0174] Olefin sulfonamide monomers comprise an olefin sulfonic acid and an amide of at least one linear or branched C1-C24 primary amine, or a cyclic or alkylcyclic C4-C24 alcohol.

[0175] The olefin monomer of the hydrophobic segment of the organic polymer embodiment is given by formula: H2C=CHR [wherein R is selected from hydrogen, a linear or branched alkyl group of 1 to 24 carbon atoms, an unsubstituted phenyl or a phenyl substituted with one or more linear or branched alkyl groups of 1 to 24 carbon atoms, a carboxylic acid ester of a linear or branched C1-C214 alkanol, or a carboxamide of a linear or branched C1-C24 primary amine; or R is -CR 2 =CHR 1 [In the formula, R 1 R is hydrogen, methyl, ethyl, or phenyl, 2 [is hydrogen or methyl] It holds.

[0176] The hydrophilic olefin monomer of this embodiment of the organic polymer is (i) Hydroxyl esters of olefinic carboxylic acids and linear or branched alkyl diols of 2 to 24 carbon atoms or cyclic alkyl diols of 5 to 24 carbon atoms; (ii) an aminoalkyl ester of an olefinic carboxylic acid and a linear or branched C2-C24 aminoalkyl alcohol or a cyclic C5-C24 aminoalkyl alcohol; (ii) an olefinic carboxylic acid and a mercaptoalkyl ester of a linear or branched C2-C23 mercaptoalkyl alcohol or a cyclic C5-C24 mercaptoalkyl alcohol; (iii) Styrene in which phenyl is substituted with a carboxylic acid ester with methanol, ammonia, sulfonamide, or sulfinamide carboxamide; (iv) vinyl alcohol; (v) Polar olefin compounds of the formula H2C=CHC6H4R [wherein R is selected from hydroxy, sulfonic acid, sulfinic acid, carboxylic acid, or polyester polyol group having terminal and / or pendant hydroxyl groups]; (vi) Vinyl alkylenyl trialkoxysilanes, in which the alkylenyl group is propyrenyl or butyrenyl and the alkoxy is methoxy or ethoxy, providing a pendant alkyltrialkoxysilane group for binder polymers; or (vii) Any combination of (i) to (vi) It can be selected from the following.

[0177] The olefinic carboxylic acid in this embodiment of the organic polymer is an alkenoic acid with 3 to 24 carbon atoms, an alkene dioic acid with 4 to 24 carbon atoms, or a partially hydrolyzed polyacrylonitrile, or any combination thereof.

[0178] Additional embodiments of the organic polymer may include polymers of olefinic acids such as (meth)acrylic acid, crotonic acid, and pentadienyl carboxylic acid, as well as neutral olefin monomers, which may be combined with olefinic acid esters and amides. The organic polymer may include units of olefinic acid monomers, including (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, pentenoic acid, pentadienyl carboxylic acid, isopreneic acid, partially hydrolyzed polyacrylonitrile, and any olefinic acid monomer derivatives that are homologs of these olefinic acid monomers.

[0179] The organic polymer of this second embodiment of the film-forming composition may include units of the olefin carboxylic acid monomer, and in addition, may include one or more monomer units of an ester of the olefin carboxylic acid monomer (the esterified alcohol is a linear, branched, or cyclic alkyl monoalcohol or diol having 1 to 12 carbons for linear alkyl groups (2 to 12 carbons for diols), 3 to 12 carbons for branched alkyl groups, and 3 to 12 carbons for cyclic alkyl groups), and an amide of the olefin carboxylic acid monomer. N-alkylamide of the olefin carboxylic acid monomer, where the alkyl group is a linear, branched, or cyclic alkyl group as described for monoalcohols; N-aminoalkylamide of the olefin carboxylic acid monomer, where the amidated amine is a linear, branched, or cyclic alkyldiamine having 2 to 12 carbons for linear alkyl groups, 3 to 12 carbons for branched alkyl groups, and 3 to 12 carbons for cyclic alkyl groups. Formula: HR 1 C=CHR 2 or HR 1 C=CH-CR 3 =CHR 4 [In the formula, R 1 , R 2 , R 3 and R 4This includes hydrogen, linear alkyl groups of 1-6 carbon atoms, branched alkyl groups of 3-6 carbon atoms, cyclic alkyl groups of 3-10 carbon atoms, phenyl, methyl, ethyl, OH, CONH2, COOH, and -(CH2). n A neutral olefin monomer comprising COOH, NO2, CN, SO3H, SONH2, pyridyl, O2CR' [wherein R' is an alkyl group of 1 to 3 carbon atoms], vinyl, and phenyl substituted with alkyl vinyl having 1 to 3 carbon atoms in the alkyl group, each independently selected.

[0180] Preferred embodiments of the hydrophilic monomer of the organic polymer include olefinic carboxylic acids and sulfonic acids selected from one or more of the following: (meth)acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, maleic acid, fumaric acid, glutaconic acid, itaconic acid, citraconic acid, mesaconic acid, vinylsulfonic acid, or any combination thereof. More preferred olefinic carboxylic acids include (meth)acrylic acid, crotonic acid, vinylsulfonic acid, maleic acid, fumaric acid, and itaconic acid. Most preferred olefinic carboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, and itaconic acid. Particularly preferred olefinic carboxylic acids include (meth)acrylic acid and crotonic acid.

[0181] Additional preferred embodiments of the hydrophilic monomer of the organic polymer include preferred hydroxyalkyl esters of the preferred acids esterified with C2-C6 diols, including ethylenediol, propylenediol, butylenediol, pentylenediol, or cyclohexanediol, aminoethanol, aminopropanol, and aminobutanol. Particularly preferred hydroxyalkyl esters include more preferred olefinic carboxylic acids esterified with any of these C2-C6 diols. More preferred hydroxyalkyl esters include the most preferred olefinic carboxylic acids having ethylenediol, propylenediol, or butylenediol.

[0182] Additional preferred embodiments of the hydrophilic monomer of the organic polymer include aminoalkyl esters of preferred olefinic carboxylic acids and sulfonic acids esterified with C2-C4 amino alcohols, including aminoethanol, aminopropanol, and aminobutanol. More preferred aminoalkyl esters include more preferred olefinic carboxylic acids esterified with aminoethanol or aminopropanol.

[0183] Additional preferred embodiments of the hydrophilic monomer of the organic polymer include mercaptoalkyl esters of preferred olefinic carboxylic acids and sulfonic acids. Preferred mercapto alcohols for these esters include mercaptoethanol, mercaptopropanol, and mercaptobutanol. More preferred mercaptoalkyl esters include more preferred olefinic carboxylic acids esterified with mercaptoethanol.

[0184] Additional preferred embodiments of the hydrophilic monomers of the organic polymer include polar olefin monomers selected from p-hydroxystyrene, styrene-p-carboxylic acid, o,p-dihydroxystyrene, styrene-p-sulfonic acid, and any combination thereof.

[0185] Preferred embodiments of the hydrophobic monomers of the organic polymer include alkyl esters in which preferred olefin carboxylic acids and sulfonic acids are esterified with C1-C8 alcohols, including methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, isohexanol, ethylhexanol, and cyclohexyl alcohol. More preferred alkyl esters include preferred olefin carboxylic acids esterified with ethanol, propanol, butanol, ethylhexanol, or cyclohexyl alcohol. The most preferred alkyl esters include the most preferred olefin carboxylic acids esterified with ethanol, butanol, ethylhexanol, or cyclohexyl alcohol.

[0186] Additional preferred embodiments of the hydrophobic monomer of the organic polymer include nonpolar olefin monomers selected from ethylene, styrene, methylstyrene, ethylstyrene, propylstyrene, butadiene, 1-phenylbutadiene, isoprene, or any combination thereof.

[0187] Additional organic polymer embodiments may include one or more monomer units containing one or more functional groups selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate, phosphonate groups and mixtures thereof, as a substitute for the olefinic carboxylic acid of the hydrophilic monomer of the organic polymer. These monomer units can be combined with other hydrophilic monomers and the hydrophobic monomers described above to form additional embodiments of the organic polymer. The functional groups can preferably be selected from the group consisting of sulfate, sulfonate, carboxylate groups and mixtures thereof. Furthermore, anionic polymers of such monomer units can be combined with the above organic polymer embodiments to form mixtures of anionic polymers and organic polymers.

[0188] Preferred combinations of the enumerated species of preferred hydrophilic and hydrophobic monomers include any combination of the enumerated preferred nonpolar olefin monomers, the enumerated preferred polar olefin monomers, the enumerated preferred alkyl esters, the enumerated preferred hydroxyalkyl esters, the enumerated preferred aminoalkyl esters, the enumerated preferred mercaptoalkyl esters, and preferred olefin carboxylic acids and sulfonic acids. The selection of any combination of these species means, according to parameters indicating the amounts of hydrophilic and hydrophobic monomers that should be present in the organic polymer, a selection of a first species from the preferred list of olefin carboxylic acids and sulfonic acids, a selection of a first species from the preferred list of hydroxyalkyl esters, a selection of a first species from the preferred list of aminoalkyl esters, a selection of a first species from the preferred list of mercaptoalkyl esters, a selection of a first species from the preferred list of preferred polar olefin monomers, and a selection of a first species from the preferred list of nonpolar olefin monomers, as well as combining any two of the selections, any three of the selections, any four of the selections, any five of the selections, or all six of the selections. Selection can also be made by selecting any species from any of the preferred lists and combining it with any species from any other list or any of the multiple lists to provide all combinations of the selections.

[0189] A particularly preferred organic polymer of this second embodiment of the film-forming composition comprises repeating units of at least one olefinic acid monomer unit and at least one non-acidic olefin monomer unit selected from any one or more of units a), b), c), and d) and any combination thereof. Examples of these non-acidic olefin monomer units include a) olefin carboxylate ester monomer units, b) olefin carboxamide monomer units, c) hydrophilic olefin monomer units, and d) lipophilic olefin monomer units.

[0190] In this embodiment of the preferred organic polymer, the olefinic acid monomer unit is selected from (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, gluconic acid, C5-C10 ethenic acid, or any combination thereof.

[0191] In this embodiment of the preferred organic polymer, the olefin carboxylate ester monomer units of group a) are selected from C1-C30 linear or branched alkyl esters of any or any combination thereof of olefin acid monomer units.

[0192] In this embodiment of the preferred organic polymer, the olefin carboxamide monomer units of group b) are -NH2, -NR of any one or any combination thereof of the olefin acid monomer units. 1 H or -NR 1 R 2 Amide [wherein R 1 and R 2 [Each element is independently selected from C1-C6 linear or branched alkyl groups.]

[0193] In this embodiment of the preferred organic polymer, the hydrophilic olefin monomer of group c) is selected from olefin carboxylic acid monomer units and hydroxyalkyl esters of linear or branched C2-C24 alkyl diols, or olefin carboxylic acid monomer units and aminoalkyl esters of linear or branched amino C2-C24 alkyl alcohols, or any combination thereof.

[0194] In this embodiment of preferred organic polymers, the lipophilic olefin monomer units of group d) are olefin compounds of formula OL2. R 3 HC=CHR 4 formula OL2 Selected from.

[0195] Regarding this lipophilic olefin monomer unit of formula OL2, R 3The group is selected from hydrogen, a linear or branched alkyl group of 1 to 6 carbon atoms, unsubstituted phenyl, or phenyl substituted with a linear or branched alkyl group of 1 to 6 carbon atoms.

[0196] Regarding this lipophilic olefin monomer unit of formula OL2, R 4 This is selected from hydrogen, a linear or branched alkyl group of 1 to 6 carbon atoms, unsubstituted phenyl, or phenyl substituted with a linear or branched alkyl group of 1 to 6 carbon atoms.

[0197] Alternatively, R in formula OL2 4 This is the ethenyl group of formula OL2'. -CH=CHR 5 Expression OL2' Therefore, regarding equation OL2', R 5 This is selected from hydrogen, a linear or branched alkyl group of 1 to 6 carbon atoms, an unsubstituted phenyl or a phenyl group substituted with a linear or branched alkyl group of 1 to 6 carbon atoms, a methyl or ethyl carboxylate, a carboxamide or a hydroxyl group.

[0198] A more particularly preferred organic polymer in this second embodiment of the film-forming composition is an olefinic acid monomer unit selected from (meth)acrylic acid, crotonic acid, maleic acid or fumaric acid and the formula OL2[wherein R 3 and R 4 The polymer comprises repeating units of lipophilic olefin monomer units of formula OL2, where both are hydrogen, i.e., formula OL2 is ethene, also known as ethylene. A more particularly preferred organic polymer of this second embodiment comprises repeating units of (meth)acrylic acid and ethylene, with the acrylic acid version of (meth)acrylic acid being preferred.

[0199] The organic polymer embodiments may generally have an acid value in the range of zero or 0.01 to about 700, preferably about 1 to about 500, more preferably 2 to 250, and most preferably 7 to 90, with a typical acid value of approximately less than about 100. The typical hydroxyl content may be approximately 1 to 20% by weight on average, or approximately 5 to 10% by weight. The organic polymer may have a weight-average molecular weight in the range of about 2 kDa to about 2 MDa, preferably about 2 kDa to about 100 kDa, and more preferably about 2 kDa to about 25 kDa. The organic polymer may have a glass transition temperature of about -125°C to about -40°C.

[0200] Organic polymers may be constructed with a random distribution of different monomer units along the polymer backbone, or they may be block copolymers having blocks of single monomer units, or they may be graft copolymers having some monomer units forming the polymer backbone and different monomer units forming polymer side chains. Different polymer structures provide different interpolymer bonding properties and different polymer properties. Block copolymers can provide regions of rigid polymer properties and flexible polymer properties. Block copolymers can exhibit crystalline and amorphous regions, which can allow for the development of water-soluble and water-resistant regions. Blocks with different electronic and lipophilic properties can impart open-rebound properties to the polymer so as to minimize a tightly packed internal structure. Grafted or segmented polymers allow for entangled conformations and compact molecular dimensions, which enable a tightly packed internal structure.

[0201] Dual polymer Michael film forming composition A third embodiment of the film-forming composition provides that the binder polymer is a dual binder polymer comprising a first component and a second component of the film-forming composition. These first and second components are distinct. The first component may be an organosilicone binder polymer having at least one pendant and / or terminal first binder functional group. The second component of this third embodiment may be a silicone binder polymer having at least one pendant and / or terminal second binder functional group. The first and second binder functional groups of this third embodiment each include a complementary pair of an alkenoyloxy group and an amine or an alkenoyloxy group and a thiol, also known as a Michael adduct.

[0202] More specifically, the first component of this third embodiment comprises a binder organosilicone polymer, and the second component comprises a linker polymer adapted to be bound in situ and crosslinked through aza-Michael addition. The binder polymer comprises a silicone polymer having pendant and / or terminal α,β unsaturated alkenoyloxy groups. The linker polymer comprises a silicone polymer having pendant and / or terminal organoamine groups, as well as optional pendant and / or alkoxysilyl groups. Preferably, the binder and linker polymers are linear and / or branched, more preferably linear.

[0203] The first binder component and the second linker component of this embodiment of the film-forming composition are kept separate until immediately before use. The film-forming composition is prepared for use in application to keratin fibers by combining and mixing these binder and linker components in a medium according to the proportional amounts described below. A film-forming composition containing pigments / colorants can also be formed by combining pigments / colorants containing dispersants as described below.

[0204] The first component of the binder polymer The binder polymer may be a silicone polymer having at least two pendant and / or terminal α,β unsaturated alkenoyloxy groups, preferably at least two of the α,β unsaturated alkenoyloxy groups being terminal groups. The binder polymer may have a linear or branched structure, preferably a linear structure.

[0205] In particular, embodiments of the binder polymer of the film-forming composition include a polydimethylsiloxane-type polymer having at least two or at least three α,β-unsaturated alkenoyloxy groups bonded to the siloxane units of the polymer. The α,β-unsaturated alkenoyloxy groups are represented by the formula EOY: R 1 R 2 C=CR 3 COO-R 4 - EOY Includes. In formula EOY, R 1 and R 2 Each of these can independently be hydrogen or a C1-C6 linear or branched alkyl group. Preferably, R 1 and R 2 At least one of them is hydrogen. 3 The group can be hydrogen or methyl. 4 The group is part of a connector group that bonds the formula EOY to the silicon in the siloxane unit of a polydimethylsiloxane-type silicone polymer. 4 The group may be a C1-C12 linear alkylenyl group, a linear C3-C12 cycloalkylalkyl or cycloalkyl group, a linear C6-C20 arylalkyl group or C6-C20 aryl group, R 4 It may be substituted in the chain by one or more of ether oxygen, thioether sulfur, and / or amine groups, or pendantly by hydroxyl groups. 4 The group is directly bonded to the silicon atom of the siloxane unit of the dimethylsilxane-type silicone polymer. A preferred embodiment of formula EOY is H2C=CR 3 COO-R 4-and a more preferred embodiment is H2C=CHCOO-R 4 - is

[0206] Embodiments of the binder polymer of the film-forming composition may include a silicone polymer composed of linear and / or branched, preferably linear, D and M siloxane monomer units. The branched form may include T units (MeSiO3) in the backbone to form branch junctions of the branched chain having D and M units, but the linear form is preferred. The binder silicone polymer is given by formula I: (X z )SiMe 3-z O-(Me2SiO) x -(XSiMeO) y -(X z )SiOMe 3-z Equation I It includes. For formula I, two or more of the D units and / or M units are modified with X, which is the α,β unsaturated alkenoyloxy group of formula EOY. Each of the siloxane units Me2SiO and Si(X)MeO contains a monomer siloxane D unit, where Me is methyl. Terminal unit (X z )SiMe 3-zThis comprises monomer siloxane M units. Indicator z is zero or 1 so that terminal units may have a single formula EOY group or may be trimethylsiloxane units. Indicator x primarily determines the molecular size of the silicone binder polymer and may be in the range of about 2 to 200,000, preferably about 5 to about 50,000, and more preferably about 5 to about 1,000. Indicator y primarily determines the number of formula EOY groups in the binder and may be in the range of 0 to about 100, preferably about 2 to about 25, and more preferably about 2 to about 20. The sum of indicators y and z must be at least 1, preferably 2, so that formula I has at least one, preferably at least two, formula EOY groups. Indicator x primarily determines the length of the linear silicone polymer and may be an integer in the range of about 3 to about 200,000, preferably up to about 500, and more preferably up to about 200, with an exemplary sum of integers up to about 100. Multiple monomer units of Me2SiO and (X)SiMeO are randomly distributed in formula I.

[0207] A preferred embodiment of formula I is one in which the indicator y is zero and z is 1. These embodiments provide a binder having only terminal formula EOY. An additional preferred embodiment is one in which the indicator x is at least 5, the indicator y is 1 to 5, and z is 1. These embodiments provide a binder having terminal formula EOY and 1 to 5 pendant formula EOYs. Yet another particularly preferred embodiment is one in which the indicator x is at least 10, the indicator y is 2 to 6, and z is zero. These embodiments provide a binder having 2 to 6 pendant formula EOYs and no formula EOY as a terminal. Instead, the binder is terminated with a Me3SiO group.

[0208] Another preferred embodiment of the preferred embodiment of formula I is H2C=CR 3 COO-R 4 - has formula EOY as. These particularly preferred embodiments of formula I (R 1 and R 2 Among the formulas where the indicator is hydrogen (EOY), a more preferable is R 4is a linear C2-C8 alkylenyl group, and more preferably R 4 The base is -CH2CHOH-CH2-O-(CH2) n -[wherein n is an integer from 1 to 6]. Most preferably, all of these embodiments of formula I are, H2C=CR 3 COO-CH2CHOH-CH2-O-(CH2)3- It has the formula EOY as its function.

[0209] A particularly preferred embodiment of the binder polymer of formula I is formula IV: H2C=CHCOOCH2CHOH-CH2-O-(CH2) c -SiMe2O-(SiMe2O) m -[MeSiO-(-(CH2) c -O-CH2-CHOH-CH2OOC-CH=CH2)] g -(Me2SiO) p -OSiMe2-(CH2) c -O-CH2-CHOHCH2OOCCH=CH2 Formula IV This is a particularly preferred embodiment of the binder, which provides the formula EOY as a terminal group and pendant group for a polydimethylsiloxane-type polymer. In this embodiment, indicator c determines the length of the alkylenyl oxo group connecting the α,β-unsaturated alkenoyloxy group to the silicon of the polymer backbone. Indicator c can be an integer from 1 to 6, preferably 3. Indicators m and p establish the size or length of the linear silicone polymer and separate the pendant α,β-unsaturated alkenoyloxy group from the terminal α,β-unsaturated alkenoyloxy group. Indicators m and p can each be independently in the range of about 5 to about 100. Indicator g establishes how many pendant α,β-unsaturated alkenoyloxy groups are present in this embodiment of the binder. Indicator g can be zero, providing a formula IV embodiment which does not have pendant α,β-unsaturated alkenoyloxy groups but has α,β-unsaturated alkenoyloxy groups at each end. Alternatively, the indicator g can be an integer from 1 to about 10. In this embodiment, -O-(CH2) cThe - portion connects formula EOY to the silicone backbone as a carbon-silicon bond. To achieve the bond, a pathway through the alkenyl moiety may be followed. Alkenyl oxoalkyl bromides can be combined with silicon halides using alkyllithium or Grignard reagents to provide Si-alkyloxoalkene moieties. The olefin bond of the alkene group can be epoxidized, and the epoxy group can be combined with an α,β-unsaturated alkene acid such as acrylic acid to form formula EOY.

[0210] A preferred embodiment of formula IV includes one in which g is an integer from 1 to 5, c and c' are integers from 1 to 3, and m and p are each from 10 to 50. This embodiment provides a binder having formula EOY as the terminal and 1 to 5 pendant bases. Another preferred embodiment of formula IV provides g and p as zero and c and c' as integers from 1 to 3. This embodiment provides a binder having only formula EOY as the terminal.

[0211] Second component: Linker polymer Embodiments of the second component linker polymer of the film-forming composition may include a polydimethylsiloxane-type silicone polymer that is linear and / or branched, preferably linear, and comprises a combination of M1, D, and M2 units as formula V: M1-(D) d -M2 Formula V M1 and M2 units constitute the ends of the silicone polymer as shown. D units form the backbone of the silicone polymer as shown. The branched form may include T units (MeSiO3) in the backbone, which form branch junctions of branched chains having D and M units, but the linear form is preferred. M1 and M2 units are selected from Me3SiO units, A-SiMe2O units [wherein A is an organoamine group], and -SiOR3 units (trialkoxysilyl units) [wherein R is ethyl or methyl]. D units are selected from SiMe2O units and A-SiMeO units. For D units, the indicator d indicates the length of the linear silicone polymer and may be in the range of 3 to 30,000, preferably 3 to 25,000, and more preferably 2,000 to 10,000.

[0212] For the D and M units, the A portion, which is an organoamine group, is given by formula OA: H2N-(R 10 -NH) r -R 11 - OA format Includes R 10 The group may be a linear or branched C1-C10 alkylenyl group or a linear or branched C6-C14 alkylallylenyl group, preferably a linear C2-C4 alkylenyl group, more preferably an ethylenyl group. 11 The group may be a linear or branched C1-C10 alkylenyl group or a linear or branched C6-C14 alkylallylenyl group, preferably a linear C2-C5 alkylenyl group, more preferably a propyrenyl or isobutyl group. The indicator r may be zero or an integer from 1 to 3. 11 The group is bonded to the silicon in the siloxane unit, and when the indicator r is zero, it is also bonded to H2N-.

[0213] The first embodiment of the linker may have both M1 and M2 units as A-SiMe2O units. The second embodiment of the linker may have M1 as an A-SiMe2O unit and M2 as an -SiOR3 unit. For these first and second embodiments, D may have multiple SiMe2O units. Alternatively, for these first and second embodiments, D may have 1 to 10 A-SiMeO units and multiple SiMe2O units. The third embodiment of the linker may have both M1 and M2 as -SiOR3 units, and D may have 1 to 10 A-SiMeO units and multiple SiMe2O units. The fourth embodiment of the linker may have both M1 and M2 as Me3SiO units, and D may have 1 to 10 A-SiMeO units and multiple SiMe2O units.

[0214] M1-(D) d A preferred embodiment of the linker as M2 may be selected to provide at least two pendant and / or terminal D units, M1 units and M2 units having a formula OA group and not having a trialkoxysilyl group. A preferred embodiment may also be selected to provide at least one D unit having a formula OA group, as well as one of the M1 and M2 units, and the other of the M1 and M2 units as a trialkoxysilyl group. A preferred embodiment may also be selected to provide at least two D units having a formula OA group, as well as M1 and M2 units together as trialkoxysilyl groups. More preferred versions of these preferred embodiments may also be selected to provide additional D units having 2 to 6 formula OA groups. Particularly preferred versions of these preferred and more preferred embodiments may be selected to provide a formula OA group only in the D unit and trialkoxysilyl groups as both the M1 and M2 units.

[0215] Formula V, preferably as a linear polydimethylsiloxane type polymer linker, can be extended to indicate possible monomer units. Thus, the linker is formed from the following list of monomer units having the M and D designators shown below: TIFF0007862521000011.tif18146 The first three units form the end of the linker (M-T1-M-T2-M-T3). The last two units form the backbone of the linker (D-B1-D-B2), and the majority of the backbone units are dimethylsiloxane units, D-B1. The indicator o of the dimethylsiloxane unit is an integer from 2 to 100. The indicator p of the siloxane backbone group having formula OA can be zero or an integer from 1 to 10.

[0216] The symbol A represents the formula OA shown above. M-T3 and D-B2 have an amine group of formula OA. Unit M-T2 is a trialkylsilyl group. The silicon in the M-T2 unit is bonded at its terminal to the oxygen of the adjacent D-B1 unit in the backbone of the dimethylsiloxane-type polymer that forms the linker polymer.

[0217] As described above, the embodiments of the linker can be ordered according to the characteristics of the terminal groups. In all of these embodiments, the silicone backbone is primarily composed of D-B1 units. The number of D-B1 units in the backbone is calculated to provide a weight-average molecular weight range for the linker, as described below. These embodiments include, but are not limited to, the following: A) Both ends as M-T1 (trimethylsiloxane). In this case, the skeleton has at least one unit of the amine formula OA as D-B2, preferably two or three D-B2 units. B) One end as M-T1 and the other end as M-T2 (alkoxysilyl). In this case, the skeleton has at least one amine formula OA as unit D-B2, preferably two or three D-B2 units. C) One end as M-T1 and the other as M-T3 (the M unit has organoamine formula OA). In this case, the skeleton has at least one amine formula OA as unit D-B2, preferably two or three D-B2 units. D) One end as M-T2 (alkoxysilyl) and the other as M-T3 (the M unit has organoamine formula OA). In this case, the skeleton has at least one amine formula OA as unit D-B2, preferably two or three D-B2 units. E) Both ends as M-T2 (alkoxysilyl). In this case, the skeleton has at least one amine formula IA as unit D-B2, preferably two or three D-B2 units. F) Both ends as M-T3 (the M unit has organoamine formula OA). In this case, the skeleton does not need to have D-B2 units. G) Both ends as M-T3. In this case, the skeleton may have at least one or two D-B2 units.

[0218] Embodiments of the binder polymer of the film-forming composition may have indicators selected to indicate the number of siloxane units that provide a weight-average molecular weight of the binder in the range of about 0.5 kDa to about 10 kDa, preferably about 0.5 kDa to about 5 kDa, more preferably about 1 kDa to about 5 kDa, most preferably about 1 kDa to about 3 kDa, and especially about 1 kDa to about 2 kDa.

[0219] Embodiments of the linker polymer of the film-forming composition may have a number of monomer units selected to provide a weight-average molecular weight of the linker in the range of about 5 kDa to about 50 kDa, preferably about 5 kDa to about 30 kDa, more preferably about 5 kDa to about 20 kDa, most preferably about 8 kDa to about 20 kDa, and particularly about 10 kDa to about 20 kDa. The weight-average molecular weight of the linker is mainly provided by the number of dimethylsiloxane units present in the backbone of the polydimethylsiloxane-type silicone linker.

[0220] The molar concentrations of the binder polymer and linker polymer in the film-forming composition result in a ratio of Michael groups to aza groups. In some embodiments of the film-forming composition, the binder provides a number of α,β-unsaturated alkenoyloxy groups (Michael groups) equal to the number of organoamine groups (aza groups) in the linker. In preferred embodiments of the film-forming composition, the binder provides an excess number of Michael groups relative to the number of aza groups in the linker. This ratio allows for Michael-aza addition of the binder and low molecular weight amine groups of the pretreatment composition. In more preferred embodiments of the film-forming composition, the binder provides at least 2 to 8 Michael groups for every 2 to 6 aza groups in the linker.

[0221] Dual polymer carboxyl-carbodimide film-forming composition A fourth embodiment of the film-forming composition comprises a dual-binder polymer containing different first and second binder components. The first component may be an organosilicon or oganosilicon binder polymer having at least one pendant and / or terminal first binder functional group. The second component of this fourth embodiment may be a low molecular weight, prepolymer, or polymer having at least one pendant and / or terminal second binder functional group. The first and second binder functional groups of this fourth embodiment each contain a complementary pair of a carboxylic acid group and a carbodiimide group.

[0222] The first and second components of this fourth embodiment of the film-forming composition are adapted to be combined in situ and crosslinked through carboxylic acid-carbodiimide (acid-CDI) addition. The first component binder polymer comprises an olefin polymer, silicone polymer, or olefin-silicone block copolymer having at least two pendant and / or terminal carboxylic acid groups. The binder is preferably linear or branched, more preferably linear. The second linker polymer comprises an alkylenyl, aromatic, or alkylenyl aromatic polymer having multiple intrachain segments of carbodiimide; or a polymer of ester, urethane, or urea monomer residue having a pendant alkylenyl single carbodiimide group. The linker is preferably linear or branched, more preferably linear.

[0223] The binder polymer and linker polymer components of the film-forming composition are kept separate until immediately before use. The film-forming composition is prepared for use on keratin fibers by combining and mixing the binder and linker components in a medium according to the proportional amounts described below. A film-forming composition containing pigments / colorants can also be formed by combining pigments / colorants containing dispersants as described below.

[0224] First component: Binder polymer The first component binder polymer may be a homopolymer, copolymer, terpolymer, or multiblock polymer having at least two carboxylic acid groups. Furthermore, the structure of the binder polymer may be an organic polymer, silicone polymer, or organosilicone polymer, each of which is configured to have a linear and / or branched configuration, preferably a linear configuration.

[0225] In particular, embodiments of the first component binder polymer of the film-forming composition include an olefin, silicone, or organosilicone polymer of formula I having at least two carboxylic acid groups. MUE-(MU1) x-(MUX) y -(MU2) z -(MU3) a -(MU3X) b -MUE Equation I

[0226] The symbols MUE, MU1, MUX, MU2, MU3, and MU3X represent monomer units of a carboxylic acid polymer. The binder polymer of formula I may be linear or branched, preferably linear. Monomer units MU1, MUX (where X is acid) and MU2 are hydrophobic, acidic, and hydrophilic olefin monomer units, respectively. MU3 and MU3X are siloxane units having an X siloxane unit with a pendant alkanoic acid group, respectively. MUE (where E is terminal) is the terminal unit of the polymer and may be either an olefin monomer unit or a siloxane unit. The olefin polymer contains either or both MU1 and MU2 in combination with MUX, and the terminal (MUE) of this polymer may be any of these three preceding monomer units. When hydrophilic and hydrophobic units are present in the olefin polymer, these olefin monomer units may be randomly distributed throughout the olefin polymer or may form blocks of hydrophilic and hydrophobic units, with carboxylic acid units preferably located in the hydrophilic blocks. The silicone polymer includes a combination of MU3 and MU3X, with MU3 at its ends. Carboxylic acid units may be randomly distributed throughout the silicone polymer. The organosilicone polymer includes blocks of olefin polymer and silicone polymer. The olefin polymer block may have monomer units arranged similarly to those of the olefin polymer. The acid-containing units may be MUX or MU3X, preferably MUX. The binder, which includes the olefin, silicone, or organosilicone polymer formed from the monomer units, may be linear or branched, preferably linear.

[0227] In particular, these monomer units may be linear or branched, preferably linear, as follows: a) MU1 is a hydrophobic olefin monomer unit containing C2-C10 alkene residues, C4-C12 alkadiene residues, and / or C6-C10 aromatic / alkyl aromatic vinyl residues. b) MU2 is a hydrophilic olefin monomer unit containing vinyl C2-C16 alkanoate ester residues, C1-C14 alkyl or hydroxyalkyl C2-C14 alkenoate ester residues, C2-C10 alkenoamide residues, or N-C1-C4 alkyl substituted versions of amide residues. c) MUX is an acidic olefin monomer unit containing C3-C10 alkenoic acid residues or C4-C10 alkadienoic acid residues. d) MU3 is a dimethylsiloxane monomer unit. e) MU3X is a monomethylsiloxane monomer unit in which at least four carbon atoms are bonded to an alkanoic acid, and one of the alkyl carbons of the alkanoic acid may have a hydroxyl group. f) MUE is a single-terminated monomer unit of MU1, MU2, or MUX when the polymer is an olefin polymer or organosilicon polymer. g) MUE is a single-terminated monomer unit of MU3 with an additional methyl group, i.e., a trimethylsiloxane unit, if the polymer is a silicone polymer.

[0228] Indicators x, y, z, a, and b indicate the number of corresponding monomer units present in the corresponding polymer. Regardless of the type of polymer, its molecular size is the sum of x, y, z, a, and b, which can be an integer from about 3 to a maximum of about 1,000,000, preferably up to about 300,000, more preferably up to about 250,000, and most preferably up to about 200,000. Each of indicators x, y, z, a, and b independently indicates the number of corresponding monomer units that form the linear polymer backbone. Each of x, z, and a can be zero or an integer from 1 to a maximum of about 100,000. Indicators y and b indicate the number of acid units present in the polymer, where y indicates the number of olefinic carboxylic acid units and b indicates the number of siloxaneic carboxylic acid units. Indicators y and b independently can be zero or an integer from 1 to 100, preferably from 1 to 50, more preferably from 1 to 20, provided that at least two carboxylic acid groups are present. Furthermore, if the polymer is a silicone polymer, b is zero and y is an integer. If the polymer is an olefin polymer, b is an integer and y is zero. If the polymer is an organosilicon polymer, one of b and y may be zero and the other may be an integer, or both may be integers.

[0229] A preferred form of formula I includes the following: Formula I is an olefin polymer in which the indicators x and z are each at least 10, the indicator y is at least 3, the indicators a and b are both zero, and the terminal MUE is MUX. Formula I is an organosilicon block copolymer having olefin unit carboxylic acid groups. Formula I is characterized by indicators x, y, and z being zero, indicator a being at least 20, preferably at least 40, indicator b being 1 to 50, and terminal MUE being MU3X or MU3. This is a silicone polymer having terminals as either dimethylsiloxane or trimethylsiloxane units having alkylalkanoic acid groups. Formula I is an organosilicone polymer having carboxylic acid-containing olefin and siloxane units.

[0230] Preferred binder polymers include olefin or organosilicone polymers having three or more pendant and / or terminal carboxylic acid groups, a weight-average molecular weight of about 0.5 kDa to about 10 kDa, preferably about 0.5 kDa to about 5 kDa; and at least one pendant group selected from alkylalkylenyl carboxylate ester groups, alkyl groups, alkylenyloxycarbonylalkyl groups, and hydroxyalkyl groups.

[0231] Preferred binder polymers also include three or more pendant C4-C6 alkanoic acid groups and a silicone polymer having a weight-average molecular weight of about 0.5 kDa to about 10 kDa, preferably about 0.5 kDa to about 5 kDa.

[0232] Another preferred binder polymer of formula I comprises an olefin polymer with 3 to 10, preferably 3 to 5, carboxylic acid groups and a weight-average molecular weight of about 0.5 kDa to about 10 kDa, preferably about 0.5 kDa to about 5 kDa; MU1 is butene, pentene, hexene, styrene, or any combination thereof; MUX is (meth)acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, fumaric acid, maleic acid, itaconic acid, glutaconic acid, citraconic acid, or mesaconic acid, preferably (meth)acrylic acid, maleic acid, Fumaric acid or crotonic acid; MU2 is vinyl acetate, vinyl propanoate, vinyl butanoate, C1-C3 alkyl or hydroxyalkyl (meth)acrylate, C1-C3 alkyl or hydroxylalkyl crotonate, C1-C3 alkyl or hydroxylalkyl pentanoate, C1-C3 diachyl or di-(hydroxylalkyl) fumarate, C1-C3 maleate, or the corresponding primary amide or C1-C3 alkyl secondary amide or any combination thereof.

[0233] Another preferred binder polymer of formula I comprises 3 to 10, preferably 3 to 5, carboxylic acid groups; a silicone polymer with a weight-average molecular weight of about 0.5 kDa to about 10 kDa, preferably about 0.5 kDa to about 5 kDa; and MU3X is MeSiO-(CH2) n The compound is -CHOH-(CH2)2-COOH, where n is an integer from 1 to 6, preferably 2 or 3.

[0234] Another preferred binder polymer of formula I comprises an olefin polymer with 3 to 10, preferably 3 to 5, carboxylic acid groups and a weight-average molecular weight of about 0.5 kDa to about 10 kDa, preferably about 0.5 kDa to about 5, where MU1 is hexene or styrene, MUX is (meth)acrylic acid or crotonic acid, and MU2 is vinyl acetate, vinyl C8-C12 isoalkanoate, methyl, ethyl or isopropyl (meth)acrylate, or the corresponding hydroxymethyl, hydroxyethyl or hydroxyisopropyl analog, methyl, ethyl or isopropyl crotonate, or the corresponding hydroxymethyl, hydroxyethyl or hydroxyisopropyl analog.

[0235] Another preferred binder polymer of formula I is an organosilicon block copolymer having carboxylic acid groups in the olefin block. Indicators of this preferred binder include indicator x as zero, meaning there are no hydrophobic olefin units; indicator b as zero, meaning there are no acid groups pendanting the siloxane units; indicator a as at least 10, meaning at least 10 dimethylsiloxane units; indicator z as at least 10, meaning at least 10 hydrophilic olefin units; and indicator y as 1 to 50, meaning 1 to 50 carboxylic acid olefin units, where MUE is MUX, meaning terminal olefin carboxylic acid units.

[0236] Another preferred binder polymer of formula I is an olefin polymer containing at least monomer units of alkyl (meth)acrylate and / or crotonate, and (meth)acrylic acid and / or crotonic acid. The acid value of this polymer is about 50 to about 600, preferably about 100 to about 400.

[0237] A more preferred binder polymer of formula I is an olefin polymer in which the acid monomer units are about 0.3% to about 75% by weight of (meth)acrylic acid and / or crotonic acid; the hydrophilic units are about 0% to about 20% by weight of hydroxyethyl or hydroxypropyl (meth)acrylate and / or crotonate; and the hydrophobic monomers are about 5% to about 20% by weight of methyl or ethyl (meth)acrylate and / or crotonate, all of which are relative to the total weight of the polymer.

[0238] Examples of olefin polymers used as binder polymers include organic copolymers such as acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymer, sold by BASF under the names Ultrahold 8 and Ultrahold Strong; (meth)acrylic acid / tert-butyl (meth)acrylate and / or isobutyl (meth)acrylate / C1-C4 alkyl (meth)acrylate copolymers, such as acrylic acid / tert-butyl acrylate / ethyl acrylate terpolymer, sold by BASF under the name Luvimer 100P; (meth)acrylic acid / ethyl acrylate / methyl methacrylate terpolymers and tetrapolymers, such as ethyl acrylate / methyl methacrylate / acrylic acid / methacrylic acid copolymer, sold by Amerchol under the name Amerhold DR-25; and Acudyne Examples include methyl methacrylate / butyl or ethyl acrylate / hydroxyethyl or 2-hydroxypropyl acrylate or methacrylate / (meth)acrylic acid tetrapolymer, such as methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylate tetrapolymer, which is sold by Rohm & Haas at 255.

[0239] Additional examples of organic polymers as binder polymers include copolymers of acrylic acid and C1-C4 alkyl methacrylates, as well as terpolymers of vinylpyrrolidone, acrylic acid, and C1-C20 alkyl, such as lauryl methacrylate, for example, sold by ISP under the name Acrylidone M, and copolymers of methacrylic acid and ethyl acrylate sold by BASF under the name Luvimer MAEX.

[0240] Examples of silicone polymers having pendant carboxylic acid groups as binder polymers include double-terminated carboxysilicones such as X-22-162C from Shin Etsu and Silform INX (INCI name: bis-carboxydecyldimethicone) from Momentive; single-terminated carboxysilicones such as X-22-3710 from Shin Etsu; and other carboxysilicones such as Grandsil PCA, such as Grandsil SiW-PCA-10 (INCI name: dimethicone (and) PCA dimethicone (and) butylene glycol (and) decyl glucoside) from Grand Industries.

[0241] Examples of organosilicon polymers used as binder polymers include multiblock carboxysilicone polymer with INCI name: crotonic acid / vinyl C8-12 isoalkyl ester / VA / bis-vinyldimethicone crosspolymer (trade name Belsil (registered trademark P1101)), and similar organosilicon polymers with the trade name crotonic acid / vinyl C8-12 isoalkyl ester / VA / divinyldimethicone crosspolymer manufactured by Wacker Chemie AG.

[0242] Additional exemplary silicone and organosilicone polymers that function as binder polymers include Wacker's HUILE M 642, Wacker's SLM23 000 / 1 and SLM23 000 / 2, General Electric's 176-12057, OSI's FZ 3707, Toray Silicone's BY 16 880, and Noveon's Ultrasil® CA-1 Silicone (Dimethicone PEG-7 Phthalate) and Ultrasil® CA-2 Silicone (Dimethicone PEG-7 Succinate).

[0243] Second component: Linker polymer Embodiments of the second component linker polymer of the film-forming composition include an organic polymer of formula II having intrachain carbodiimide groups, which may be linear or branched, preferably linear. Alternatively, the linker may include an organic polymer of formula X having pendant single carbodiimide groups, which may have a linear or branched skeleton, preferably a linear skeleton. Z-(LN=C=N-) p -Z (Poly) q -(K) s -(Poly) r Formula II Formula X

[0244] For formula II, p is at least an integer of 2. In many examples, L may be an organic group of an organic diisocyanate that is converted to the polycarbodiimide of formula II. In other examples, L may be an oligomer or polymer moiety terminated by an isocyanate group that is converted to a carbodiimide in combination with another isocyanate group, or converted to a uretanyl group in reaction with Z. This formation understanding indicates that L may be an organic linker group containing a saturated aliphatic divalent group, an aromatic divalent group, or an alkyl aromatic divalent group, or a repeating olefin, carbonate, ester, ether, amide, urethane, or polymer or oligomer divalent group having a urea bond. Preferably, L is a saturated aliphatic divalent group, an aromatic divalent group, or an alkyl aromatic divalent group.

[0245] For formula X, each Poly is an organic polymer segment of amide, urea, ester, olefin, or imine monomer residues. Poly can be based on C3-C6 alkanediamines and C4-C10 alkanedicarboxylic acids or C4-C10 alkanediisocyanates, or on C3-C6 alkanediols and ester monomer residues based on C4-C10 alkanedicarboxylic acids, where the indicators q and r are each at least an integer of 2. The K group provides a pendant carbodiimide group, and s is at least an integer of 2. If s is 2 or greater, the resulting multiple K groups are randomly distributed along the Poly backbone, including the terminals. The K group is based on formula XI. Includes TIFF0007862521000012.tif30170.

[0246] Regarding equation XI, R 20 These are C3-C6 alkylenyl residues, and R 21 These are C3-C6 alkylenyl residues.

[0247] For formulas II and XI, Z can be a non-reactive or reactive end group of the polycarbodiimide. In the case of a reactive end group, Z is -(CH2) n-Si(OR)3 [wherein R is methyl or ethyl, and n is an integer from 3 to 6]. In the case of a non-reactive terminal group, Z can be a saturated aliphatic monovalent group, an aromatic monovalent group, or an alkyl aromatic monovalent group.

[0248] The preferred linker polymer is of formula II, where L is a saturated aliphatic divalent group selected from a linear, branched, or cyclic alkylenyl group of 2 to 20 carbon atoms, an aromatic divalent group selected from benzene or diphenyl, or an alkyl aromatic divalent group selected from p-dimethylenylphenyl or methyleneyldiphenyl.

[0249] Another preferred linker polymer is of formula II, where L is a saturated alkylenyl divalent group of 2 to 6 carbon atoms.

[0250] Another preferred linker polymer is of formula II, where L is a residue of toluene, diphenylmethane, phenyl, dicyclohexylmethane, methyl-3,5,5-trimethylcyclohexane, hexane, cyclohexane, or norbornane. These L residues are derived from the corresponding diisocyanate compounds.

[0251] A more preferred linker polymer is formula II, where L is dicyclohexylmethane, methyl-3,5,5-trimethylcyclohexane (isophorone), or hexane.

[0252] For formulas II and X, preferred nonreactive groups for Z are saturated aliphatic monovalent groups selected from linear, branched, or cyclic alkyl groups of 2 to 20 carbon atoms, aromatic monovalent groups selected from benzene or diphenyl, or alkyl aromatic monovalent groups selected from p-dimethylenylphenyl or methyleneyldiphenyl.

[0253] The preferred linker polymer as formula X is polyamide or polyurea, and the number of pendant carbodiimide K groups shown is 2 to 50, preferably 2 to 10, more preferably 2 to 5.

[0254] A more preferred linker polymer is given by formula X, and R 20 and R 21 Z is either butyrenyl or hexylenyl, and Z is either butyl or hexyl.

[0255] For formulas II and X, the preferred nonreactive group of Z is butane or hexane.

[0256] The molecular sizes of the linker polymers of formulas II and X are determined by the number of carbodiimide groups and the size of L for formula II, and by Poly for formula X. For both formulas II and X, the preferred number of carbodiimide groups, indicated by p and k respectively, is 2 to 100, preferably 2 to 50, more preferably 2 to 10, and most preferably 2 to 5. The preferred L groups (non-polymer L groups for formula II) provide the molecular sizes for these preferred versions of formula II. For formula X, the preferred Poly is a polyamide formed from hexanediamine and adipic acid, and the pendant K group is formed from 3-aminopropyl-1,6-hexanediamine. However, based on factors such as the number of L groups, the size of the polyp, and the number of carbodiimide groups, the weight-average molecular weight of the linker may range from 0.5 kDa to about 500 kDa, preferably about 0.5 kDa to about 400 kDa, more preferably about 0.5 kDa to about 10 kDa, and most preferably about 0.5 kDa to about 3 kDa to 5 kDa.

[0257] The molar concentrations of the binder polymer and linker polymer in the film-forming composition, as well as the relative levels of their functional groups, result in a ratio of carboxylic acid groups to carbodiimide groups. In some embodiments of the film-forming composition, the binder provides a number of carboxylic acid groups equal to the number of carbodiimide groups in the linker. In preferred embodiments of the film-forming composition, the linker provides an excess number of carbodiimide groups relative to the number of carboxylic acid groups in the binder. This ratio allows for the addition of carbodiimide to the linker with low molecular weight amine groups in the pretreatment composition. In more preferred embodiments of the film-forming composition, the ratio of linker carbodiimide groups to binder carboxylic acid groups may be in the range of about 50:1 to 1.2:1, preferably about 30:1 to 2:1, more preferably about 25:1 to 2.5:1, particularly more preferably about 20:1 to about 3:1, and most preferably about 20:1 to about 10:1.

[0258] medium When applied to keratin fibers, the media of the embodiments of the film-forming composition and pretreatment composition of the present invention may be organic compounds that can be closely mixed with small amounts of water, or preferably form a solution. Preferred media include embodiments of alcoholic solvents such as alkyl alcohols of 1 to 6 carbon atoms, to which water has not been intentionally added. These include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, neopentanol, isopentanol, and n-hexanol. Preferred organic alcohols include ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, n-butanol, isobutanol, and pentanol. The alcoholic solvent may be intentionally combined with small amounts of water, up to about 10 weight percent, preferably up to about 5 weight percent, more preferably up to about 2 or 3 weight percent, and most preferably less than about 1 weight percent, relative to the total weight of the medium. It is recognized that alcoholic solvents, to which water has not been intentionally added, may contain small amounts of water, as alcoholic solvents absorb water from the atmosphere. Although not limited to the present invention, the presence of water molecules is thought to promote the condensation of alkoxysilyl groups to silyloxysilyl groups in the film-forming composition and the pretreatment composition.

[0259] Furthermore, the medium for the pretreatment composition may contain a small amount of acetic acid, such as about 0.1% to about 2% by weight, preferably about 0.1% to about 1% by weight, and more preferably about 0.1% to about 0.5% by weight, relative to the total weight of the medium. Alternatively, a 90% to 95% alcoholic-aqueous medium containing ethanol and acetic acid may be used for the pretreatment composition. The presence of acetic acid promotes the hydrolysis of alkoxysilyl groups to hydroxysilyl groups, making the low molecular weights of the pretreatment composition water-soluble. When a small amount of acetic acid is present in the aqueous-alcoholic pretreatment composition, the lifespan of the pretreatment composition is only a few hours. As a result, this option for the application of the pretreatment composition is typically carried out in small batches that are mixed and used immediately. The medium for the pretreatment composition may also involve a balance between the amounts of alcohol, water, and acetic acid present relative to the low molecular weight elements present. In some examples, the concentrations of acid and / or water may be higher than others. The appropriate and / or optimal ratios of the concentrations of individual pretreatment components, the selection and amount of the medium, and the determination of the presence and amount of acid or alkali are within the scope of the normal experimental capabilities and skills of the laboratory technician. The guidelines include pretreatment component concentrations that provide a viscosity that allows for a free-flowing liquid that does not easily leach out of the keratin fibers upon application, and water is intentionally omitted or included in very small amounts if necessary to promote condensation.

[0260] The pretreatment composition, the first and second components or unitary film-forming components (disintegrated first and second components having the same functional binder groups), and other reactive or catalytic components of the film-forming composition are kept separately until use. Packaging each in separate containers is suitable for this purpose. Each component of the film-forming composition and the pretreatment composition may be kept in a medium that does not interact with the reactive groups. Suitable media are, but are not limited to, the alcohols mentioned above, preferably isopropanol and isobutanol, or non-aqueous organic solvents such as liquid hydrocarbons or silicone solvents. The medium for keeping these components separate should not contain water or any agents that hydrolyze or react with the functional binder groups. Typically, the pretreatment components and film-forming components may be formulated at ready-to-use concentrations, or may be concentrates diluted in a suitable medium for preparation for use, or may be at concentrations ready for application to keratin fibers.

[0261] When film-forming compositions and pretreatment compositions are prepared for application to keratin fibers, they may be formulated using a single-phase alcohol or alcohol medium as described above, or as a two-phase aqueous medium containing water or water-alcohol as a continuous phase and water or water-alcohol immiscible organic liquid as a discontinuous phase. The continuous phase may contain water-soluble components, while the discontinuous phase may contain components of the film-forming composition and components of the pretreatment composition such as PTH alkoxysilane that react with water. The discontinuous non-aqueous phase tends to isolate such compounds from decomposition by water. Preferably, water is part of the medium, but in situations where one or more components of the film-forming composition and pretreatment composition are water-sensitive, the film-forming composition and pretreatment composition are maintained in a non-aqueous environment until they are ready to be dressed onto the keratin fibers. During the application stage, single-phase or two-phase media may be prepared as needed.

[0262] The polarity and proton properties of the medium are important for controlling several reactions that occur when the components of the film-forming composition and pretreatment composition are combined. These reactions include alkoxysilyl group condensation, as well as complementary pairs of a first functional binder group and a second functional binder group, including Michael complementary pairs and carboxylic acid-carbodiimide pairs. Preferably, the medium for applying the film-forming composition and pretreatment composition is polar and can support condensation and addition reactions. For both the film-forming composition and pretreatment composition, isopropanol or isobutanol with a small amount of water as described above is suitable. The application medium can be combined with binders, catalysts and low molecular weight concentrates stored separately, and the medium of the stored concentrates is preferably at least partially to substantially miscible with the application medium.

[0263] The medium may be present independently in each of the film-forming composition and the pre-treatment composition in an amount ranging from about 0.1% to about 99% by weight, for example, from about 1% to about 98% by weight, or for example, from 50% to 95% by weight, relative to the total weight of the film-forming composition and the pre-treatment composition. The concentrations of the components of the pre-treatment composition and the film-forming composition are discussed in the following sections.

[0264] Viscosity, composition component concentration The viscosity of the film-forming composition and pretreatment composition functions to hold them in place on the keratin fibers while the coating, preferably a color coating, is being formed. The viscosity substantially avoids free translational flow of these compositions, which would cause the composition to flow rapidly and drip off the surface of the hair. Nevertheless, the viscosity is not so high that it does not undergo self-leveling to coat the keratin fibers substantially uniformly. The appropriate viscosity of the composition is the result of the interaction of the various components of the film-forming composition and pretreatment composition, their concentrations, pigment microparticles, and, if necessary, any viscosity control agents, any suspending agents, and any thickening agents. Nevertheless, a viscosity approximating that of a fluid liquid such as ethanol or isopropanol is appropriate when applied in a suitable application apparatus, although it is not limited to these.

[0265] Generally, the viscosity of film-forming compositions and pre-treatment compositions is approximately 0.001 to approximately 2000 Pa / sec. -1 The range may be as follows. Viscosity measurements are performed using a controlled stress rheometer, for example, an AR2000 model from TA Instruments, or an equivalent instrument. A 6 cm flat acrylic crosshatch parallel plate shape (TA item 518600.901) and a stainless steel crosshatch base plate (TA item 570011.001) are used. The rheometer is prepared for flow measurements according to standard manufacturer procedures. The shape gap of the parallel plate is set to 1000 microns. The flow procedure is programmed into the rheometer under the following conditions: a continuous stress gradient of 0.1 to 300 Pa over 2 minutes at 25°C, including 250 measurement points in linear mode. The product is loaded into the shape according to standard procedures, and measurements are started 5 minutes after mixture preparation. 10 seconds from the shear stress versus shear rate curve. -1 The shear stress value at the shear rate is obtained, and the corresponding viscosity is calculated by dividing the obtained shear stress by 10.

[0266] The concentrations of the unitary components of the film-forming composition, specifically the concentrations of the first and second components of the film-forming composition and the concentration of the PTH alkoxysilane component in the pretreatment composition, can each be independently in the range of about 0.1% to about 90% by weight, preferably about 1% to about 40% by weight, more preferably about 2% to about 30% by weight, most preferably about 2% to about 15% by weight, and most preferably about 1% to about 10% by weight, relative to the total weight of the composition. As discussed above, the viscosity is controlled so that the film-forming composition and pretreatment composition do not easily flow off the surface of the hair, but level to substantially coat these surfaces and flow relatively freely. The development of appropriate viscosity by partially controlling the concentrations of the components of the film-forming composition and pretreatment composition can be experimentally determined by routine methods such as blending several samples of components at different concentrations in these compositions, coating these samples onto hair strands, and observing the flow, spreading, and leveling of the compositions on the hair.

[0267] The film-forming composition and pretreatment composition can be applied simultaneously, sequentially, or in a pre-combined form to keratin fibers such as hair strands using the coloring procedure described later herein. The upper part of the hair being bonded together is fixed so that the hair is aligned vertically downward. After a residence time of 5 minutes, the amount of product that has dripped from the hair strands, if any, is observed. The results obtained from several samples can be plotted against the flow time and leveling time to determine the appropriate concentration or concentration range of the components of the film-forming composition and pretreatment composition.

[0268] The degree of in situ bonding between the reactive components of the film-forming composition and the pretreatment composition can be controlled by manipulating ratios, amounts, and concentrations, as well as by the physical means described herein, so as to maintain the mechanical and chemical properties of the coating, preferably the color coating. These properties include the ability to adhere to hair, the ability to maintain the flexibility and free-flow properties of hair, the ability to provide persistence, the avoidance of stickiness, and the avoidance of aggregation.

[0269] The glass transition temperature of the polymer produced by the molecules of the film-forming composition and pretreatment composition partially contributes to the flexibility, strength, hardness, and similar qualities of the coating on the keratin fiber surface, preferably the color coating. The glass transition temperature of these embodiments is preferably much lower than the normal minimum ambient temperature, such as -100°C to +100°C. g This determines the solid-solid transition of a polymer from a hard, glassy material to a soft, rubbery material. For the purpose of coating on keratin fibers, preferably a color coating, a soft, rubbery, elastic state is to be achieved. This is an undesirable result. The coating should be soft, flexible, elastic, inconspicuous to the touch and inconspicuous to the eye, but should not peel off, decompose, or otherwise fall off from the keratin fibers, especially anagenic hair, when stroked with a hand or brushed with a brush. The Tg of the coating, preferably a color coating, can be measured using ASTM D7426-08 (2008).

[0270] solute content Embodiments of film-forming compositions and pretreatment compositions are combinations of media containing liquids and solids, and these compositions generally contain a solvent and a solute. The solvent is a volatile medium under ambient conditions; in other words, the medium is a liquid and functions as a liquid in which the solvent and / or solute are dissolved and / or dispersed. The solute includes all components and substances other than the medium, such as at least the liquid, gel, and solid components of these compositions that remain after the medium has been removed. The solute includes at least the polymers, oligomers, pretreatment compounds, associated catalyst / promoter materials (if present), as well as pigment microparticles and colorants of these compositions. Optional components include plasticizers, dispersants, surface treatment agents, crosslinking agents, and other materials that may be added to the medium. These optional components are included in the solute content insofar as they remain, if present, along with the polymers, oligomers, pretreatment compounds, reactants, and pigment microparticles after the application and setting of the color and pretreatment compositions as coatings on human hair. This includes all substances of the pretreatment and film-forming compositions that are typically considered liquids, gels, and / or solids because they remain in the coating on the hair.

[0271] The solute content of the film-forming composition and the pretreatment composition may range from about 0.1% to about 50% by weight relative to the total weight of each composition. A preferred solute content is in the range of about 0.1% to about 20% by weight relative to the total weight of the composition, and a more preferred solute content is in the range of about 0.2% to about 12% by weight. A particularly preferred solute content range is about 0.3% to about 11% by weight, with content of about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, and about 8% by weight being particularly preferred.

[0272] Since the solute of the pretreatment composition is a pretreatment molecule, the solute content also indicates the concentration of the pretreatment molecule in the pretreatment composition medium, and a particularly preferred range of solute content is a preferred concentration of the pretreatment molecule in the pretreatment composition medium.

[0273] When the film-forming composition is ready to be applied to keratin fibers, it comprises first and second components or unitary components, additives, and pigments or colorants. Except for the pigments, these components may be liquid, gel, or solid depending on the individual properties of each component, and each constitutes part of the total solute content of the film-forming composition ready for use. When the film-forming composition is maintained separately as a binder and medium, a catalyst and medium, and a pigment and medium, the particularly preferred solute content ranges shown above are preferred concentrations of the first and second components or unitary components of the film-forming composition in the medium when stored in separate containers. The concentrations of dispersants in separate containers and pigments in the medium are typically much higher, and in preparation for combination into the film-forming composition, several different pigments are combined and diluted as described herein to form the colorants of the film-forming composition. Catalysts, if present, are also present in the lower solute concentration ranges mentioned above during storage. Catalysts are typically combined with the binder in the medium immediately before application to keratin fibers.

[0274] When applying the pretreatment composition and film-forming composition to keratin fibers, the ratio of the concentrations of the first and second components or unitary component binders to the PTH alkoxysilane compound (pretreatment compound) and any other additives is adjusted to provide at least equal molar equivalents of alkoxysilyl groups and / or other interacting groups, ensuring that the components of the pretreatment composition and film-forming composition condense and / or react not only with themselves but also with each other. Preferably, the molar equivalent of the PTH alkoxysilane compound is 2% to 20%, preferably 3% to 10%, more preferably about 5% to about 10%, higher than the molar equivalent of the film-forming component. The concentrations and molar equivalents designed to yield a molar equivalent excess of the pretreatment compound in the pretreatment composition and the components in the film-forming composition, preferably the binder, at concentrations of 2% to 4% by weight, are calculated and measured in the delivery containers to obtain the desired result of internal condensation of the binder and pretreatment molecules by applying the measuring container of the pretreatment composition to a portion of the hair, followed by applying the measuring container of the film-forming composition to the same portion of the hair.

[0275] plasticizer If the glass transition temperature of the components of a coating, preferably a color coating, and / or film-forming composition and pretreatment composition is too high for the desired application, but other properties, such as color and persistence, are satisfactory, then one or more plasticizers may be used to change the T of the components. gThe plasticizer can be combined with components of the film-forming composition and pretreatment composition embodiments to reduce the plasticizer and provide suitable tactile and visual properties for the coating, preferably a color coating. The plasticizer can be directly incorporated into one or both of the film-forming composition and the pretreatment composition, or applied to the hair after the formation of the color composition on the keratin fibers of the combined film-forming composition and pretreatment composition, thereby substantially curing the color composition to form a coating, preferably a color coating, on the keratin fibers. The plasticizer can be selected from plasticizers typically used in the application field. Appropriate selection includes selecting a plasticizer that does not interfere with or compete with alkoxysilyl condensation or complementary reactions.

[0276] The plasticizer may have a molecular mass of 5,000 g / mol or less, for example, 2,000 g / mol or less, for example, 1,000 g / mol or less, for example, 900 g / mol or less. In at least one embodiment, the plasticizer has a molecular mass of, for example, 40 g / mol or more.

[0277] Therefore, the film-forming composition and pretreatment composition may also contain at least one plasticizer. Examples include, but are not limited to, common plasticizers such as glycols and their derivatives, silicones, silicone polyethers, polyester polyols; adipic acid esters (such as diisodecyl adipate), trimellitic acid esters, sebacate acid esters, and azelaic acid esters, either alone or in mixtures; but are not limited to, examples of glycol derivatives include diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether or diethylene glycol hexyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, or ethylene glycol hexyl ether; polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymers, and mixtures thereof, for example, high molecular weight polypropylene glycols having a molecular weight in the range of 500 to 15,000, such as glycol esters; and propylene glycol derivatives, such as propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, diethylene glycol methyl ether, and dipropylene glycol butyl ether. Such compounds are marketed by Dow Chemical under the names DOWANOL PPH and DOWANOL DPnB; acid esters, such as carboxylic acid esters including triacids, citrates, phthalates, adipates, carbonates, tartrates, phosphates, and sebacates; formula R 11 COOH monocarboxylic acids and formula HOR 12 OH diol [wherein R 11 and R 12Esters derived from the reaction of [which may be the same or different, selected from linear, branched or cyclic saturated or unsaturated hydrocarbon chains containing 3 to 15 carbon atoms], for example, monoesters resulting from the reaction of isobutyric acid with octanediol, for example, 2,2,4-trimethyl-1,3-pentanediol, for example, the product sold by Eastman Chemical Company under the reference TEXANOL ESTER ALCOHOL; oxyethylene derivatives, for example, oxyethylene oils, for example, vegetable oils such as castor oil; mixtures thereof.

[0278] Among tricarboxylic acid esters, the triacid is formula TIFF0007862521000013.tif20170 [wherein R is a -H, -OH, or -OCOR' group, and R' is an alkyl group containing 1 to 6 carbon atoms] Examples of esters of triacids that correspond to this are listed. For example, R may be an -OCOCH3 group. Esterifying alcohols for such tricarboxylic acids may be those described above for monocarboxylic acid esters.

[0279] The plasticizer may be present in either or both the film-forming composition and the pretreatment composition in an amount of approximately 0.01% to 20%.

[0280] pigment Embodiments of the film-forming compositions and pretreatment compositions of the present invention enable obtaining a preferred colored coating without substantially modifying keratin fibers. As used herein, colorants include the terms “pigments and colorants”. The term pigment generally refers to any particulate colorant or amorphous insoluble color material / colorant that has or contains a pigment material that imparts colors including black and white to keratin fibers, such as titanium dioxide which imparts only white to keratin fibers. Pigments are substantially water-insoluble. Colorants generally refer to partially soluble to soluble color materials such as soluble dyes, henna, indigo, anthocyanines, and other similar soluble color compounds. Pigments are also called pigment microparticles or pigment particles to distinguish them from dyes presented in molecular form. The terms pigment microparticles and pigment particles are synonymous and are used interchangeably herein. Pigments may be organic, inorganic, or a combination of both. Pigments may be in pure form or coated with, for example, a polymer or dispersant.

[0281] The selection, multiple types, and various forms of pigment microparticles described in the following section can be incorporated into any of the first, second, and third components of the multicomponent composition, or into any two or all three of these components. Preferably, the pigment microparticles can be incorporated into either or both of the first and second components. More preferably, the pigment particles can be incorporated into the first component.

[0282] At least one pigment that can be used can be selected from organic and / or mineral pigments known in the art, such as those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry. The pigment contained in the microparticles containing at least one pigment does not substantially diffuse or dissolve in the keratin fibers. Instead, the pigment contained in the microparticles containing at least one pigment remains substantially separate from the keratin fibers but adheres to them.

[0283] At least one pigment may be in the form of a powder or pigment paste. It may be coated or uncoated. The at least one pigment can be selected from, for example, mineral pigments, organic pigments, metal elements and their oxides, as well as pigments with special effects such as other metal modifications, lakes, mother-of-pearl or glitter flakes, and mixtures thereof.

[0284] Pigment shape Pigment microparticles can have any suitable shape, including substantially spherical. However, pigment microparticles can also be oval, elliptical, tubular, irregular, or a uniform combination of various shapes. In addition, pigment microparticles can have two dimensions of similar size: length and width / diameter. Furthermore, pigment microparticles can be microplatelets, i.e., they can have a thickness substantially smaller than their planar dimensions. For example, the thickness may be 5, 10, or even 20 times smaller than the planar dimensions. In one embodiment having any of the reactive components of the present invention, the pigment may be surface-treated, surface-coated, or encapsulated.

[0285] Pigment size The pigment can be present in the composition in an undissolved form. Depending on its shape, the pigment can have a D50 [volume] particle diameter of 0.001 microns to 1 micron.

[0286] According to one embodiment, the particle size distribution of pigment microparticles with respect to either the number of particles or the volume may be at least bimodal. A bimodal particle size distribution has two distinct peaks that are relatively spaced apart, and a trimodal particle size distribution has three distinct peaks. The term “peak” refers to the local maximum value of the distribution curve. The “distance” between the two peaks expressed with respect to particle size may be at least 0.05 microns, preferably at least 0.1 microns, for example, at least 0.2 microns. By providing at least a bimodal particle size distribution, it becomes possible to adjust the optical appearance of colored hair. For example, scattering properties vary with particle size, so particles of different diameters scatter light in different directions.

[0287] Pigments made from metals and metal-like materials that can conduct electricity, absorb light, and re-emit light from the metal to give a highly reflective appearance. While we do not wish to be bound by a specific theory, it is thought that absorbed light induces an alternating current on the metal surface, and this current immediately re-emits light from the metal. Such pigment microparticles may be platelets, for example, having a thickness substantially smaller than their planar dimensions. For example, the thickness may be about 5 times, about 10 times, or even about 400 times smaller than the plane. Such platelets may have a planar dimension of less than about 30 nm but a thickness of less than about 10 microns in width. This includes ratios of 10000 to 30, or 333. Larger platelets, such as 50 microns, are also available at this thickness of 10 microns, and therefore the ratio can even reach up to 2000.

[0288] Pigment microparticles can be composites formed from two different types of pigment microparticles. Examples include composites of two-dimensional microparticles and at least one microsphere, composites of different microspheres, and composites of different two-dimensional particles. Composite particles formed from two-dimensional microparticles to which microspheres adhere offer an attractive alternative to pure mixtures of two-dimensional microparticles and microspheres. For example, metallic two-dimensional microparticles may have one or more microspheres, such as one or more organic microspheres. The microspheres attached to or bonded to the two-dimensional microparticles can be formed from the same pigment material or from different pigment materials. Composite microparticles formed from two-dimensional microparticles and microspheres can provide multiple functionalities in a single particle, such as (metallic) reflectivity and dielectric scattering, reflectivity, and absorption.

[0289] Pigment microparticles can exhibit both light scattering and light absorption for visible light wavelengths. While we do not wish to be bound by any particular theory, it is thought that such pigments can provide a visual effect of lightening hair. Such pigment microparticles can have D50 values ​​between approximately 50 nm and 750 nm, between approximately 100 nm and 500 nm, or between approximately 150 nm and 400 nm. Such materials have refractive indices greater than approximately 1.5, greater than approximately 1.7, or greater than approximately 2.0.

[0290] According to one embodiment, different pigment microparticles are combined to provide the reflective, transmissive, and refractive properties of hair colored with the color compositions described herein. The microparticle combination may be a material composite in which pigment microparticles are formed using at least two different pigment materials. In addition to, or instead of, the microparticle combination may be used to obtain the desired reflective, transmissive, and refractive properties by using a mixture of different types of distinct pigment microparticles.

[0291] Compound pigments, pigment combinations, and mixtures of pigment microparticles eliminate, or at least significantly reduce, light transmission and scattering through hair, thus eliminating the perception of pigment in natural hair color changes.

[0292] Pigment concentration The film-forming composition for coloring hair fibers according to this disclosure comprises fine particles containing at least one pigment. The film-forming composition contains the pigment in an amount of about 0.01% to about 40% by weight, about 0.05% to about 35% by weight, about 0.1% to about 25% by weight, or about 0.15% to about 20% by weight of the film-forming composition.

[0293] Pigment materials The material of the pigment microparticles can be inorganic or organic. Inorganic-organic mixed pigments are also possible.

[0294] According to one embodiment, inorganic pigments may be used. The advantage of inorganic pigments is their excellent resistance to light, weather, and temperature. Inorganic pigments may be of natural origin and may be derived from materials selected from the group consisting of, for example, chalk, ochre, amber, green earth, burnt sienna, and graphite. The pigment may preferably be a white pigment such as titanium dioxide or zinc oxide. The pigment may also be a coloring pigment such as, for example, ultramarine or red iron oxide, luminous pigments, metal effect pigments, pearlescent pigments, and fluorescent or phosphorescent pigments. The pigment may be selected from the group consisting of metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates, alloys, and the metal itself. Pigments can be selected from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), reddish-brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), Prussian blue (ferric ferrocyanide, CI 77510), carmine (cochineal), zinc sulfide, barium sulfate, zinc oxide, derivatized titanium dioxide, derivatized zinc sulfide, derivatized zinc oxide, and mixtures thereof. Pigments can be selected from the group consisting of iron oxide, titanium dioxide, mica, borosilicates, and combinations thereof. Pigments may include iron oxide (Fe2O3) pigments. Pigments may include combinations of mica and titanium dioxide.

[0295] The pigments can be pearlescent pigments and coloring pigments, and are preferably based on mica coated with metal oxides or metal oxychlorides such as titanium dioxide or bismuth oxychloride, and optionally with further colorants such as iron oxide, Prussian blue, ultramarine, and carmine. The color exhibited by the pigment can be adjusted by varying the thickness of the layer. Such pigments are sold under trade names such as Rona®, Colorona®, Dichrona®, RonaFlair®, Ronastar®, Xirona®, and Timiron®, all of which are available from Merck in Darmstadt, Germany. For example, Xirona® is a brand of color travel pigments that exhibit a color-changing effect depending on the viewing angle and is based on either natural mica, SiO2, or calcium aluminum borosilicate flakes coated with various layers of TiO2. Pigments from the KTZ® line manufactured by Kobo Products, Inc., located at 3474 South Clinton Boulevard, South Plainfield, USA, particularly Kobo's Surface Treatable KTZ® pearlescent pigments, are also useful herein. KTZ® FINE WHITE (mica and TiO2) and KTZ® CELESTIAL LUSTER (mica and TiO2, 10–60 microns), as well as KTZ® CLASSIC WHITE (mica and TiO2, 10–60 microns), with D50 particle diameters of 5–25 microns, are especially useful. SynCrystal Sapphire from Eckart Effect Pigments, a blue powder containing platelets of synthetic fluorophlogopite coated with titanium dioxide, ferric ferrocyanide, and a small amount of tin oxide, is also useful. Synchronized almonds from Eckart are also useful, as they are beige powders with copper reflectivity, composed of plateslets of synthetic fluorophlogopite, and coated with titanium dioxide and iron oxide.BASF's Duocrome® RV 524C is also useful, as its composition of mica, titanium dioxide, and carmine provides a two-tone appearance via glossy red powder and purple reflective powder. The coloring pigment can be a light, bright coloring pigment, and can be a white variation in particular.

[0296] Pigments can be organic pigments. At least one pigment can be an organic pigment. As used herein, the term “organic pigment” means any pigment that satisfies the definition in the chapter on organic pigments in the Encyclopædia Ullman. For example, at least one organic pigment is nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, copper phthalocyanine, copper hexadecachlorophthalocyanine, 2-[(2-methoxy-4-nitrophenyl)azo]-N-(2-methoxyphenyl)-3-oxobutyramide, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmeta The following can be selected: dimethylquinacridone and quinophthalone compounds, azo dyes, nonionic azo dyes, anionic azo dyes, cationic azo dyes, complex-forming azo dyes, azaanurene dyes, aza analogs of diarylmethane dyes, azaanurene dyes, nitro dyes and their pigments, carbonyl dyes and their pigments (e.g., anthraquinone dyes, indigo), sulfur dyes, fluorescent dyes, anthracenes, or insoluble alkali or earth metal acid dyes. Alternatively, the pigment may be uncolored and UV absorbent.

[0297] Organic pigments can be selected from the group consisting of natural pigments such as sepia, oryzae, bone char, Cassel brown, indigo, chlorophyll, and other plant pigments. Synthetic organic pigments can be selected from the group consisting of azo pigments, anthraquinoids, indigoids, dioxazines, quinacridones, phthalocyanines, isoindolinones, perylenes and perinones, metal complexes, alkali blues, diketopyrrolopyrrole pigments, and combinations thereof. A particularly preferred pigment is 7-bis(1,3-dichloropropane-2-yl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone.

[0298] The pigments used in the color composition may include at least two different pigments selected from the above group of pigments, or at least three different pigments selected from the above group of pigments. According to one embodiment, the pigments used in the color composition may include at least one yellow pigment selected from the group of yellow pigments consisting of Pigment Yellow 83 (CI21108), CAS No. 5567-15-7, Pigment Yellow 155 (CI200310), (CAS: 68516-73-4), and Pigment Yellow 180 (CI21290), (CAS: 77804-81-0).

[0299] In addition to, or instead of, at least one yellow pigment, the pigment used in the color composition may include at least one red pigment selected from the group of red pigments consisting of Pigment Red 5 (CI 12490), (CAS No. 6410-41-9), Pigment Red 112 (CI 12370), (CAS No. 6535-46-2), and Pigment Red 122 (CI 73915), (CAS No. 980-26-7).

[0300] In addition to or instead of at least one yellow pigment and / or at least one red pigment, the pigments used in the color composition may include at least one green pigment selected from the group of green pigments consisting of Pigment Green 36, (CI 74265), (CAS: 14302-13-7).

[0301] In addition to, or instead of, at least one yellow pigment and / or at least one red pigment and / or at least one green pigment, the pigments used in the color composition may include at least one blue pigment selected from the group of blue pigments consisting of Pigment Blue 16 (CAS: 424827-05-4), Pigment Blue 60 (CI 69800) (CAS: 81-77-6), Pigment Blue 66 (CI 73000) (CAS: 482-89-3).

[0302] In addition to, or instead of, at least one yellow pigment and / or at least one red pigment and / or at least one green pigment and / or at least one blue pigment, the pigments used in the color composition may include at least one black pigment selected from the group of black pigments consisting of Pigment Black 6 (CI 77266), (CAS 1333-86-4) and Pigment Black 7 (CI 77266), (CAS 1333-86-4). Additional combinations may include aluminum flakes having red, blue, green, yellow, or any combination thereof.

[0303] The pigment may have a surface zeta potential of ±15 Mv or higher, preferably ±20 Mv or higher, and more preferably ±25 Mv or higher. The surface zeta potential can be measured using a zetasizer, for example, a zetasizer 3000HS. Surface zeta potential measurement is performed, for example, according to ISO 13099.

[0304] For example, white or colored organic pigments can be selected from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments coded in color index references CI 42090, 69800, 69825, 73000, 74100, and 74160, and yellow pigments coded in color index references CI 11680, 11710, 15985, 19140, 20040, 21090, 21100, 21108, 47000, 47005, and 77492.

[0305] Green pigment coded in color index references CI 61565, 61570, 74265, and 74260; orange pigment coded in color index references CI 11725, 12075, 15510, 45370, and 71105; references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, and 1558 Red pigments coded in the color index as 0, 15585, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 45430, 58000, 73360, 73915, 75470, and 77491, as well as pigments obtained by oxidative polymerization of indole or phenol derivatives.

[0306] Similarly, non-limiting examples that can be cited include those by Hoechst, such as: JAUNE COSMENYL IOG: Pigment Yellow 3 (CI11710); JAUNE COSMENYL G: Pigment Yellow 1 (CI11680); ORANGE COSMENYL GR: Pigment Orange 43 (CI71105); ROUGE COSMENYL R: Pigment Red 4 (CI12085); CARMINE COSMENYL FB: Pigment Red 5 (CI12490); VIOLET COSMENYL RL: Pigment Violet 23 (CI51319); BLEU COSMENYL A2R: Pigment Blue 15.1 (CI74160); VERT COSMENYL GG: Pigment Green 7 (CI74260); and NOIR COSMENYL Examples include organic pigment pastes such as those sold under the name R: Pigment Black 7 (CI77266).

[0307] At least one pigment according to this disclosure may also be in the form of at least one composite pigment described in European Patent Publication No. 184426. These composite pigments may be compounds of particles comprising, for example, a mineral core, at least one binder to ensure the binding of an organic pigment to the core, and at least one organic pigment that at least partially covers the core.

[0308] At least one of the pigments of this disclosure may be in the form of small, undissolved microparticles that deposit on the outer wall of keratin fibers rather than diffuse into the hair color. Suitable color pigments may be of organic and / or inorganic origin. However, given their excellent lightfastness, weather resistance and / or temperature resistance, the pigments may also be inorganic color pigments.

[0309] Inorganic pigments, whether of natural or synthetic origin, include, for example, those produced from chalk, ochre, umbra, green earth, burnt sienna, or graphite. Furthermore, black pigments such as iron(II,III) oxide, color pigments such as ultramarine or red iron oxide, and fluorescent or phosphorescent pigments can be used as inorganic color pigments.

[0310] Colored metal oxides, metal hydroxides and metal oxide hydrates, mixed-phase pigments, sulfur silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, metal chromates and / or metal molybdates are particularly suitable. Particularly preferred color pigments are black iron oxide (Cl77499), yellow iron oxide (Cl77492), reddish-brown iron oxide (Cl77491), manganese violet (Cl77742), ultramarine (sodium aluminum sulfosilicate, Cl77007, Pigment Blue 29), chromium oxide hydrate (Cl77289), iron blue (ferric ferrocyanide, Cl77510) and / or carmine (cochineal).

[0311] At least one pigment may also be a colored pearlescent pigment. These are typically mica-based and can be coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), reddish-brown iron oxide (Cl 77491, CI 77499), manganese violet (Cl 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288), and / or iron blue (ferric ferrocyanide, CI 77510).

[0312] Mica forms part of phyllosilicates, which include muscovite, phlogopite, paragonite, biotite, lepidolite, and margalite. To produce pearlescent pigments in combination with metal oxides, mica, mainly muscovite or phlogopite, is coated with metal oxides.

[0313] At least one pigment may also be at least one mica-based coloring pigment coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (Cl 77491, CI 77499), manganese violet (Cl 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288), and / or iron blue (ferric ferrocyanide, CI 77510).

[0314] At least one pigment may also be a color pigment commercially available from Merck under trade names Rona®, Colorona®, Dichrona®, and Timiron®, from Sensient under trade names Ariabel® and Unipure®, from Eckart Cosmetic Colors under trade name Prestige®, and from Sunstar under trade name Sunshine®.

[0315] At least one pigment may also be: Color pigments bearing the trade name Colorona® include, for example: Colorona Copper, Merck, mica, Cl77491 (iron oxide); Colorona Passion Orange, Merck, mica, Cl77491 (iron oxide), alumina; Colorona Patina Silver, Merck, mica, Cl77499 (iron oxide), Cl77891 (titanium dioxide); Colorona RY, Merck, Cl77891 (titanium dioxide), mica, Cl75470 (carmine); Colorona Oriental Beige, Merck, mica, Cl77891 (titanium dioxide), Cl77491 (iron oxide); Colorona Dark Blue, Merck, mica, titanium dioxide, ferric ferrocyanide; Colorona Chameleon, Merck, Cl77491 (iron oxide), mica; Colorona Aborigine Amber, Merck, mica, Cl77499 (iron oxide), Cl77891 (titanium dioxide); Colorona Blackstar Blue, Merck, Cl77499 (iron oxide), mica; Colorona Patagonian Purple, Merck, mica, Cl77491 (iron oxide), Cl77891 (titanium dioxide), Cl77510 (ferric ferrocyanide); Colorona Red Brown, Merck, mica, Cl77491 (iron oxide), Cl77891 (titanium dioxide); Colorona Russet, Merck, Cl77491 (titanium dioxide), mica, Cl77891 (iron oxide); Colorona Imperial Red, Merck, mica, titanium dioxide (Cl77891), D&C RED NO.30 (Cl73360); Colorona Majestic Green, Merck, Cl77891 (titanium dioxide), mica, Cl77288 (chromium oxide green); Colorona Light Blue, Merck, mica, titanium dioxide (Cl77891), ferric ferrocyanide (Cl77510); Colorona Red Gold, Merck, mica, Cl77891 (titanium dioxide), Cl77491 (iron);Colorona Gold Plus MP 25, Merck, mica, titanium dioxide (Cl77891), iron oxide (Cl77491); Colorona Carmine Red, Merck, mica, titanium dioxide, carmine; Colorona Blackstar Green, Merck, mica, Cl77499 (iron oxide); Colorona Bordeaux, Merck, mica, Cl77491 (iron oxide); Colorona Bronze, Merck, mica, Cl77491 (iron oxide); Colorona Bronze Fine, Merck, mica, Cl77491 (iron oxide); Colorona Fine Gold MP 20, Merck, mica, Cl77891 (titanium dioxide), Cl77491 (iron oxide); Colorona Sienna Fine, Merck, Cl77491 (iron oxide), mica; Colorona Sienna, Merck, mica, Cl77491 (iron oxide); Colorona Precious Color pigments with the trade name Unipure® include, for example: Gold, Merck, mica, Cl77891 (titanium dioxide), silica, Cl77491 (iron oxide), tin oxide; Colorona Sun Gold Sparkle MP 29, Merck, mica, titanium dioxide, iron oxide, mica, Cl77891, Cl77491 (EU); Colorona Mica Black, Merck, Cl77499 (iron oxide), mica, Cl77891 (titanium dioxide); Colorona Bright Gold, Merck, mica, Cl77891 (titanium dioxide), Cl77491 (iron oxide); Colorona Blackstar Gold, Merck, mica, Cl77499 (iron oxide); Color pigments with the trade name Unipure® include, for example: Unipure Red LC 381 EM, Sensient Cl77491 (iron oxide), silica; Unipure Black LC 989 EM, Sensient, Cl77499 (iron oxide), silica; Unipure Yellow LC 182 is EM, Sensient, Cl77492 (iron oxide), silica.

[0316] Among dyes, cochineal carmine can be referred to non-limitingly. Dye known by the following names can also be referred to non-limitingly: D&C Red 21 (CI45 380), D&C Orange 5 (CI45 370), D&C Red 27 (CI45 410), D&C Orange 10 (CI45 425), D&C Red 3 (CI45 430), D&C Red 4 (CI15 510), D&C Red 33 (CI17 200), D&C Yellow 5 (CI19 140), D&C Yellow 6 (CI15 985), D&C Green (CI61 570), D&C Yellow 10 (CI77 002), D&C Green 3 (CI42 053), and D&C Blue 1 (CI42 090). A non-exclusive example of rake that can be mentioned is the product known as D&C Red 7 (CI15 850:1).

[0317] Pigment blend color gamut CIE L*a*b* (CIELAB) is a color space designated by the International Commission on Illumination. It describes all colors visible to the human eye and serves as a device-independent model used as a reference.

[0318] The three coordinates of CIELAB represent the lightness of a color (L*=0 results in black, L*100 indicates diffuse white; specular white can be higher), the position between red / magenta and green (a*, negative values ​​indicate green, positive values ​​indicate magenta), and the position between yellow and blue (b*, negative values ​​indicate blue, positive values ​​indicate yellow).

[0319] The L*a*b* model is a three-dimensional model and can only be properly represented in three-dimensional space. A two-dimensional representation would include a chromaticity diagram: a section of the color solid with fixed lightness values.

[0320] Since the opposing channels, red-green and yellow-blue, are calculated as the difference in lightness conversion of the (estimated) cone response, CIELAB is a color value color space.

[0321] In this invention, the color gamut is determined by preparing samples of the film-forming composition without pigments and adding each pigment to be tested to individual samples of the film-forming composition. Samples containing pigments are prepared and applied to the Tress substrate. The samples are cured and then tested for coloring such that the resulting CIELAB lightness or L* value of the colored hair is 60±2. The required level of pigment depends on the pigment being tested. For example, using a sample of the film-forming composition applied alone as described in this invention, HairTress (Kerling, Natural White Special Quality) can be prepared as described. Using a Minolta spectrophotometer CM-2600d, the color of the cured and dried HairTress can be measured at 5 points on both the front and back, and the average value. The D65 L*a*b value can be calculated. The color gamut can be calculated if at least three pigments are measured such that the resulting color is within a target L* value of 60±2. First, the lengths of each side of the triangle resulting from each combination of the three pigments in the a*b plane are calculated using the following formula. To calculate the distance between pigment 1 and pigment 2, use the following formula: Side length SL 12 =((a 顔料1 -a 顔料2 ) 2 +(b 顔料1 -b 顔料2 ) 2 ) 0.5 . This is calculated for each pair of pigments. Then, the calculation is performed for the series of three pigments.

[0322] The resulting color gamut is calculated using the following formula: Color gamut=(S(S-SL 12 )(S-SL 13 )(S-SL 23 )) 0.5 [In the formula, SL 12 , SL 13 , and SL 23 s = (SL) are the lengths of the three sides of a triangle in the a*b plane, where S = (SL) 12 +SL 13 +SL23 ) / 2]. When using four or more pigments, this calculation can be performed for each combination of three of the four or more pigments used, and the widest color gamut is selected.

[0323] Preferred color coating embodiments of the present invention may also have a color gamut of more than 250, more than 500, more than 750, more than 800, more than 900, more than 1100, or even more than 1250.

[0324] Experiments conducted on color gamut Using the above formula, the color gamut with a nominal L value of 60 was calculated for each of the three possible pigment combinations shown in Color Gamut Table 1 below. Color gamut table 1 TIFF0007862521000014.tif140170

[0325] These were formulated using appropriate levels of the first, second, and third compositions within the exemplary formulations described later.

[0326] In one embodiment, a color composition (e.g., a set of film-forming and pre-treatment compositions applied sequentially, simultaneously, or in a premixture to keratin fibers) can be applied sequentially to the hair. For example, a first set containing pigment microparticles that substantially scatter and / or reflect light to produce a visual effect that makes the hair appear lighter in color may be applied to the hair, followed by a second set containing pigment microparticles that substantially absorb light and provide color to the hair, and the combination of sequential addition of the first and second sets of color compositions may provide the final hair color. For example, the first color composition may contain metallic flakes, and the second color composition may contain organic pigment microparticles. Furthermore, to achieve the desired color result, more than the first and second color compositions may be applied to the hair, and three or more color compositions may be applied.

[0327] pH Embodiments of the film-forming composition and pretreatment composition according to the present invention may have pH adjustments associated with application to keratin fibers such that the pH at application may be in the range of about 4 to about 10, preferably about 5 to about 9. The pH is preferably dynamically controlled to control the reaction rate of the reactive components of the film-forming composition and pretreatment composition. By maintaining a slightly basic pH during the mixing and pre-application stages involving these compositions, alkoxysilyl condensation under certain conditions is controlled. Condensation may be initiated by returning the acidic pH to a state suitable for the reaction.

[0328] Dispersant It will be apparent to those skilled in the art that careful and selective selection of dispersants can help maximize performance in terms of maximizing the amount of color produced from the immobilized film, maximizing persistence or washability, and enabling color removal.

[0329] The electrostatic, ionic, and functional properties of the dispersant are selected to be compatible with and not interfere with the reactive components of the film-forming composition and the pretreatment composition. More preferably, the dispersant is selected to be compatible with and miscible with the other components of the medium-containing and non-medium-containing compositions.

[0330] By following the principle of selecting a dispersant that is chemically similar to the binder polymer of the film-forming composition, maximum compatibility can be ensured.

[0331] Similar to the suitability described above, another criterion for selecting a dispersant is its ability to allow the pigment to be dispersed down to the primary particle size, preferably with the minimum amount of mechanical energy input. Those skilled in the art will recognize that the concentration of the dispersant is also a factor. Generally, a minimum amount is usually required for dispersion activity; below this level, the composition will not be completely dispersed, or the dispersant will act as a flocculant.

[0332] These two considerations are used together to define the preferred materials and their respective concentrations.

[0333] Furthermore, depending on the type of binder polymer used, the binder itself may also act as a dispersant. In such cases, it may be possible to avoid the need for additional dispersion additives.

[0334] The combination of the dispersed pigment mixture and the film-forming composition can be carried out in any manner. In this combination, the dispersed pigment mixture is delivered on top of the pretreatment layer together with the film-forming composition layer. At least a portion of the dispersed pigment mixture remains on top of the pretreatment layer while the layers are mixed to a slight, moderate, or essentially complete degree. This arrangement of the coating allows for at least partial removal of the coating when the “off” technique described below is employed.

[0335] Dispersants, types, properties, and chemistry Dispersants are amphiphilic or amphiphatic, meaning they are chemical compounds that possess both hydrophilic (water-loving, polar) and lipophilic (favoring fat) properties. Dispersants are surface-active polymers that enable the uniform distribution and stabilization of pigments in solids, such as liquid media, by reducing the interfacial tension between two components. As a result, aggregates are broken down into primary particles and protected from re-aggregation by a protective dispersant envelope.

[0336] Dispersants are based on their stabilization mechanism. 1. Dispersant for electrostatic stabilization a. Anionic dispersion additives i. Polyacrylate ii. Polyphosphate b. Neutral dispersion additives, such as nonionic surfactants. c. Cationic dispersion additives, such as quaternary ammonium organic and / or silicone polymers. 2. Dispersant for stereostabilization It can be further subdivided.

[0337] Electrostatic stabilization The pigment surface is occupied by additives that have an ionic charge. All pigment particles become equally charged. The mutual repulsion due to the charges is greater than the attractive force between the pigment particles. Electrostatic stabilization is mainly relevant in aqueous paint compositions. • Polyanionic dispersion additives: Polycarboxylates (mainly salts of polyacrylic acid), polyphosphates which can be divided into linear polyphosphates and cyclic metaphosphates, and polyacrylates. • Preferably used as cations are salts of polyacrylic acid, sodium, and ammonium. These polyacrylates are water-soluble, and the technical product has a molecular weight in the range of 2,000 to 20,000 g / mol, with an optimal value of approximately 8,000 g / mol. • Sodium and ammonium salts of homopolymers or copolymers of acrylic acid, methacrylic acid, or maleic acid

[0338] Steric stabilization The attractive forces between pigment particles are only effective over relatively short distances from each other. The proximity of two particles to each other can be prevented by molecules that are firmly fixed to the pigment surface, have groups extending from the surface, and can reduce the likelihood of the pigments coming into contact with each other. Sufficiently long chain lengths can prevent agglomeration. Furthermore, substances added to avoid agglomeration and other undesirable pigment particle interactions are preferably selected to minimize or avoid interaction with the reactive polymer of the color composition.

[0339] Incorporation of pigments into dispersants The pigments described herein can be selected and / or modified to be sufficiently similar so that a single dispersant can be used. In other examples, two or more different dispersants can be used if the pigments are different but compatible. Due to the extremely small size of the pigment microparticles and their affinity, the formation of a substantially homogeneous dispersion that can be combined with the pigment microparticles and dispersants and subsequently modified and / or diluted as desired is achieved before combining with any or all of the film-forming compositions.

[0340] Pigment microparticles can be dispersed and stabilized in a medium by one or more dispersants whose properties and types are described above. Dispersants can be added to the medium or precursor medium, or a coating can be formed on the microparticles to promote dispersion. It is also possible to provide a coating of dispersant material to the microparticles and further provide additional dispersants to the medium or precursor medium used to form the final medium.

[0341] Dispersants added to a medium or provided as a coating facilitate wetting of fine particles, dispersion of fine particles in the medium, and stabilization of fine particles in the medium.

[0342] Wetting involves replacing materials such as air adsorbed on the surface of pigment microparticles and within aggregates of microparticles with a medium. Typically, complete wetting of individual microparticles is desired to separate the particles and break up aggregates formed by microparticles that adhere to each other.

[0343] After wetting, the fine particles can be subjected to a deaggregation and decomposition process, generally called a dispersion process. The dispersion process typically involves the application of mechanical forces, such as shear, to break down the fine particles into single particles. In addition to shear for single-particle breakdown, the fine particles can be further broken down into smaller particles using, for example, roller mills, high-speed mixers, and bead mills. Typical practices involve substantially uniform dispersion of the pigment in the dispersant through the use of high-shear mixing, for example, through the use of a suitable ball mill, an ultra-high-pressure homogenizer, or other compositions known to those skilled in the art of pigment dispersion.

[0344] During wetting and dispersion, the total exposed surface area of ​​the fine particles wetted by the dispersant increases. The amount of dispersant can be gradually increased during dispersion, taking into account the increase in surface area.

[0345] Dispersants also function as de-agglomerants, keeping dispersed fine particles dispersed and preventing them from agglomerating and forming loose aggregates. This stabilization is also necessary for long-term storage purposes. Different types of stabilization are possible, such as electrostatic stabilization and steric stabilization, and the type of dispersant is selected considering the material of the medium and fine particles.

[0346] A dispersant may be added to the dry powder of pigment particles when the particles are ground to a desired size. During grinding, or during any other suitable technique for singling out the pigment particles or breaking them down into smaller parts, the dispersant comes into contact with and adheres to the surface of the microparticles. Since the surface of the newly generated microparticles during grinding is coated with the dispersant, after grinding, microparticles having a coating formed by the dispersant are provided.

[0347] Coating with a dispersant can also be performed in a liquid carrier medium to which the dispersant is added. Fine particles can also be pulverized in a liquid carrier.

[0348] In some cases, pigment microparticles may be coated with low molecular weight from a pretreatment composition. A portion of the pretreatment composition can be combined with pre-ground pigment particles following the procedure described above for wetting and dispersing the microparticles with a dispersant. After the wetting and dispersion procedures, the treated microparticles can be separated from the excess pretreatment composition to produce microparticles coated with low molecular weight. During this procedure, the low molecular weight coating is thought to begin condensing, resulting in a coating that is at least partially condensed into a net of silicone coating the individual microparticles. The coated microparticles can then be wetting and dispersed in a dispersant as described above for the wetting and dispersion procedures.

[0349] Additive ingredients Additive components for film-forming compositions include suspending agents, leveling agents, and viscosity modifiers. Suspending agents help maintain pigment particles in a dispersed state and minimize or counteract their aggregation. Examples of suspending agents include fatty acid esters of polyols such as polyethylene glycol and polypropylene glycol. These are similar to plasticizers and function in a similar manner to allow pigment particles to "pass each other" without delayed or binding interactions. They act as grease in this way. Furthermore, suspending agents are partially involved in promoting stable dispersion of pigment particles and avoiding sedimentation. Polymers in film-forming compositions are also involved through their solubilization or interaction with pigment particles and the medium. Suspending agents provide another factor for maintaining a stable dispersion. They not only provide a "grease" to promote Brownian motion but also partially stabilize pigment particles in the medium through interaction as emulsifiers. Any components should also be selected so that they do not interfere with, or only minimally interfere with, reactive polymer coupling reactions.

[0350] Embodiments of the film-forming composition according to the present invention may also optionally include, for example, reducing agents, fatty substances, softeners, defoaming agents, humectants, UV screening agents, mineral colloids, peptides, solubilizers, fragrances, anionic, cationic, nonionic, or amphoteric surfactants, proteins, vitamins, propellants, oxyethylene- or nonoxyethylene-treated waxes, paraffin, stearic acid, or lauric acid. 10 ~C 30 Fatty acids, and C such as lauric acid diethanolamide. 10 ~C 30 It may contain at least one adjuvant selected from fatty acid amides.

[0351] Embodiments of the film-forming composition according to the present invention are further, however, optional, of antioxidants (e.g., phenolic acids, secondary amines, phosphites, thioesters, and combinations thereof), non-reactive diluents (e.g., ethylene glycol, di(ethylene glycol), tetra(ethylene glycol), glycerol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, triethylene glycol monomethyl ether, 2-ethoxyethanol, solketal, benzonitrile, hexamethylphosphoramide, 2-N-methylpyrrolidinone, and N,N-dimethylformamide); dyes, fillers (e.g., silica; carbon black; clay; titanium dioxide; silicates of aluminum, magnesium, calcium, sodium, potassium, and mixtures thereof; carbonates of calcium, magnesium, and mixtures thereof; oxides of silicon, calcium, zinc, iron, titanium, and aluminum; sulfates of calcium, barium, and lead; alumina trihydrate; magnesium hydroxide, and mixtures thereof), plasticizers (e.g., ASTM Petroleum such as D2226 aromatic oils; paraffin oils and naphthenic oils; polyalkylbenzene oils; organic acid monoesters such as alkyl and alkoxyalkyl oleates and stearates; organic acid diesters such as dialkyl, dialkoxyalkyl, and alkylaryl phthalates, terephthalate, sebacate, adipate, and glutarate; glycol diesters such as tri-, tetra-, and polyethylene glycol dialkanoates; trialkyl trimellitates; trialkyl, trialkoxyalkyl, alkyldiaryl, and triaryl phosphates; chlorinated paraffin oils; coumarone-indene resins; pine resin; vegetable oils such as castor oil, tall oil, rapeseed oil, and soybean oil, and their esters and epoxidized derivatives; esters of monohydric alcohols with dibasic acids (or their anhydrides) such as o-phthalates, adipates, and benzoates;The product may contain one or more additives including (and combinations thereof), processing aids, UV stabilizers (e.g., hindered amines, o-hydroxyphenylbenzotriazole, 2-hydroxy-4-alkoxybenzophenone, salicylates, cyanoacrylates, nickel chelates, benzylidene malonate, oxalanilide, and combinations thereof), and combinations thereof.

[0352] Additional additives may include tactile hair modifiers. These may include, but are not limited to, softening and / or lubricating and / or antistatic and / or hair alignment and / or anti-frizzy effects on keratin fibers.

[0353] Additional additives include, but are not limited to, uncolored materials having a particle size of approximately 2 nm to 500 nm; polymer chains or nanoparticles composed of polyolefins such as polyethylene, polypropylene, polybutene, and combinations thereof; and filler materials such as clay and mineralite materials such as smectite, kaolin, illite, chlorite, attapulgite, and intercalated aluminosilicate materials, as well as refined forms (formed) of these and combinations thereof. Additional mineral microparticles may consist of inorganic metal oxides selected from the group consisting of silica, titanium dioxide, zirconium dioxide, aluminum dioxide, magnesium dioxide, boehmite alumina, and hydrotalcite. Further filler materials include, but are not limited to, carbon nanotube micrographite materials such as nanofillers of graphite oxide mixed polymers, microbucky balls, clathrates, and crown composites of organic and mineral complexes. Furthermore, the filler may combine, complex, contain, or incorporate a polymer that contains one of the members of a complementary reaction pair related to the first and second components of the reactive polymer composition.

[0354] Additives are not limited to these, but may also include UV filters and UV blocking materials such as avobenzone, bemotoridinol octocrylene, benzophenone-4, ethylhexyl methoxycinnamate, PABA, padimate O, PBSA, cinoxate, dioxybenzone, homosalate, menthyl anthranylate, octyl salicylate, Parsol Max, thinosolve S and A2B, ubinal, amioxate, polyvinylidene fluoride and other similar conjugated organic compounds, radical scavengers, triplet formation inhibitors, and metal compounds incorporating oxides and similar forms of chromium, titanium, zinc, nickel, manganese, iron, niobium, silver, gold, aluminum, hafnium, tantalum, etc. (metal compounds absorb or reflect UV light).

[0355] Top coat A topcoat composition is a post-dressing composition that can be applied later by a person (hereinafter referred to as the user) whose hair has been dressed with a coating, preferably a color coating. The topcoat composition can also be applied to the user's hair by a salon professional who has previously dressed the user's hair with a coating, preferably a color coating, or who is in the process of dressing the user's hair. The topcoat typically contains an aqueous alcohol mixture combined with a water-repellent compound, a hair setting compound that may be removable by shampoo and / or rinse with water, or a hair setting compound that may be slowly removed by a cationic shampoo but not by a rinse with water or by a typical anionic shampoo that is typically used as a shampoo for washing hair at home.

[0356] Examples of water-repellent compounds for inclusion in the topcoat composition include waxes, silicones, and organofluoride compounds. Among these water-repellents, carnauba wax, beeswax, olefin waxes, and paraffin are preferred. Polyurethanes, polyureas, polyesters, polysilicones, and combinations thereof can also constitute components of the topcoat composition. Preferably, these polymers have a considerable number of non-reactive functional groups distributed as pendant groups throughout their polymer chains, so as to generate hydrogen bonds, dipole interactions, and ionic interactions with the base film on the hair. The presence of such polymers adds water-repellent, glossy, and reasonable buoyancy properties to the hair.

[0357] Hair setting compounds for inclusion in topcoat compositions may be easily removed by normal shampooing, or they may be long-lasting in that multiple shampooings slowly remove the hair setting compounds. Hair setting compounds enable the retention of specific sets or hairstyles under typical environmental conditions such as rain, humidity, and wind. Nevertheless, they can be removed by shampooing with commercially available shampoo formulations. Useful hair setting compounds for inclusion in topcoat compositions may be copolymers of acidic vinyl monomers such as (meth)acrylic acid, hydrophobic nonionic vinyl monomers such as alkyl (meth)acrylates, and first and second associative monomers such as polyoxyalkienyl fumaric acid or similar unsaturated dicarboxylic acids. Compounds may include polyvinylpyrrolidone (PVP), copolymers of PVP and vinyl acetate (VA), copolymers of acrylates and hydroxyalkyl acrylates, CARBOPOL (polyacrylic acid), CARBOPOL ETD polymers, xanthan gum, and hydrophobic modified cellulose. Further substances useful as hair setting compounds and water-repellent compounds for topcoats are based on (meth)acrylic esters of C6-C20 alkyl groups and (meth)acrylic copolymers of (meth)acrylic esters of hydrophilic monomers such as unsaturated alcohols and (meth)acrylic acid. Copolymers of this formulation have unsaturated moieties as films applied to hair. Short UV irradiation of copolymers such as films allows crosslinking, imparting wind, rain, and shampoo resistance to topcoat compositions. Block copolymers of olefin monomers such as (meth)acrylic acid, crotonic acid, alkyl (meth)acrylates, and small amounts of styrene provide topcoats with retention, low tackiness, and high moisture resistance qualities while simultaneously allowing for easy removal by shampooing. Incorporation of non-tacky pressure-sensitive adhesives into topcoats, such as copolymers of butyl acrylate and methacrylic acid, with trace amounts of methacrylic acid (around 2-4% by weight), also promotes retention and setting.In some cases, a topcoat formulated with a (meth)acrylate copolymer that is not easily removed by shampooing and exhibits thermoplastic properties at temperatures at least approximately 20°C higher than human body temperature may be useful for resetting hairstyles. This version of the topcoat can be heated with a hot air hairdryer to reset the hair into a new style. By cooling the reset hair, the thermoplastic polymer retains the shape provided by the reset, thus providing the reset hairstyle.

[0358] The topcoat composition may contain polymer compounds as fine particles dispersed in a medium, or it may be dissolved in a solution with the medium. The topcoat can be applied as a liquid composition using a brush, sponge, or other similar applicator to coat individual hairs. Alternatively, the topcoat composition can be incorporated into a spray pump container and applied to hair as an aerosol. Topcoat compositions applied as a spray are preferably formulated so that gentle brushing transfers the liquid to the entire hair, leaving the liquid on the hair for a sufficient amount of time to allow all the hair to be coated. If hair styling is part of the topcoat process, the hair may be set with a mechanical device, or set by heat and mechanical operations as described above.

[0359] Post-care composition To maintain the shine, color durability, and properties of hair coatings, preferably color coatings, post-care compositions may be applied periodically by the user. Post-care compositions incorporate components that provide lubrication, texture modification, and a sacrificial semi-fluid film to the hair. These include nonionic surfactants, cationic surfactants such as long-chain quaternary ammonium compounds, amosilicone conditioners, fatty acid amide conditioners, fatty alcohols betaine and sultaine, and non-penetrating surfactants having a molecular volume greater than approximately 450 cc per mole. Post-care compositions may be formulated in a medium such as an aqueous or aqueous alcohol medium that is volatile over a short period, such as 1 to 5 minutes. Post-care compositions may be applied to keratin fibers as a spray or liquid. Similarly useful as post-care compositions are protective compositions that can be applied as a mask to the user's skin and areas not treated with the compositions described herein. The protective compositions form a thin film mask on the skin and are easily removed by peeling. Adhesion to the skin is minimal so that peeling does not damage the skin. The compounds in the aqueous alcohol solution provide a mask film as the medium evaporates. Compounds such as polymers and copolymers of high Mw organic hydroxy acids, including lactic acid and glycolic acid, provide useful peelable masks. Post-care compositions can be designed to specifically care for the coating on the surface, rather than the surface itself. For example, in the context of a coating on the surface of hair, instead of using a regular product designed to clean and condition the hair surface, a post-care composition is formulated to care for and maintain the coating on the hair surface.

[0360] Testing the flexibility of the coating Since the coating, preferably a color coating, is prepared on a peelable substrate and isolated as an independent polymer film, it can be tested for optical density to confirm that the polymer film itself does not significantly alter the appearance of the hair.

[0361] Furthermore, preferably, the polymer film can be tested as described above to determine its glass transition temperature (Tg), thereby preventing damage or cracking of the colored coating and ensuring cleanability and friction resistance.

[0362] The coating, preferably a color coating, has a density of approximately 20 to 50 mN m -1 It can have a surface energy between [a certain value].

[0363] Limit elongation. The term limit elongation refers to the amount of elongation a given material can experience under a specific test method before failure occurs and the material breaks into two or more pieces. This is calculated by multiplying the separation at fracture by the initial separation in the test by 100 to obtain the percentage limit elongation.

[0364] Young's modulus. Young's modulus is a mechanical property that measures the stiffness of a solid material. It defines the relationship between stress (force per unit area) and strain (proportional deformation) of a material in a linear elastic regime of uniaxial deformation. This is the stress / strain ratio in this region.

[0365] Extreme compression. The term extreme compression refers to the amount of compression that a given material can experience under a specific test method before failure occurs and the material breaks.

[0366] Mean repeated elongation before failure. This refers to the number of elongation cycles that can be performed on a test material to reach a certain level of elongation before failure occurs and the material breaks into two or more fragments.

[0367] The mechanical properties of elastomers (Young's modulus, intrinsic elongation, intrinsic compression, and mean repeated elongation before failure) are measured using a Texture Analyzer TA.XT.Plus (Stable Micro Compositions) by known methods.

[0368] For Young's modulus and ultimate elongation, the elastomer is prepared as a continuous film, for example, 10 mils thick, on a release layer (e.g., cooking sheet) using a BYK square applicator or a Bird-type film applicator (e.g., 5570 single bar 6'', 10 mil or 5357 or square frame 4'', 5-50 mil). If the elastomer is manufactured as a diluted composition, those skilled in the art will select an appropriate thickness for the drawdown film to produce a film suitable for testing. The film is cured at 25°C for at least 24 hours. The elastomer is removed from the release layer and cut into 30 mm × 10 mm rectangular sections using a scalpel. The thickness is then measured using a caliper to account for shrinkage or solvent loss during curing. The rectangular film is then mounted in a TA instrument within an initial separation of 12 mm using an A / MTG mini tensile grip (Stable Micro Systems). The sample is then stretched at a rate of 0.5 mm sec⁻¹ until the elastomer sample breaks. Young's modulus is defined as the initial slope of the linear portion of the elastic region of the force-elongation curve that occurs immediately after an initial force of 5g is applied. Since the initial cross-sectional area is known, the force is converted to MPa and Young's modulus is calculated. The ultimate elongation is expressed as a percentage, i.e., elongation distance at fracture / initial distance * 100. To evaluate the average repeated elongation before fracture, the ultimate elongation of the sample is first measured. The sample and TA instrument are positioned in the same manner as when evaluating the ultimate elongation. The sample is then stretched at a rate of 0.5 mm-sec⁻¹ to a fixed elongation of 60% of the measured ultimate elongation. The sample is then returned to its original state at a rate of 0.5 mm-sec⁻¹, and the cycle is repeated until the sample fractures, or up to 2000 repeated cycles.

[0369] For extreme compression, the elastomer is prepared as a continuous 3 mm film on a release layer. The film is cured at 25°C for at least 24 hours. The elastomer is removed from the release layer, and a series of cylindrical discs are punched out from the film to a diameter of 3.5 mm. The thickness is then measured using a caliper to account for shrinkage or solvent loss during curing. The rectangular film is then mounted on a TA apparatus using an A / MTG mini tensile grip (Stable Micro Systems) in a compression cycle. The sample is compressed at a rate of 0.05 mm-sec⁻¹ until the sample breaks. This is observed as a rapid deflection in the stress-strain graph during the compression cycle and will be apparent to those skilled in the art.

[0370] For all of the above mechanical property measurements, the results shown are the average of at least seven measurements.

[0371] Kit and container Film-forming compositions and pretreatment compositions may be maintained in separate storage compartments or in separate kit forms, especially if they react together without special activation. Furthermore, complementary components of the film-forming composition and compounds having PTH alkoxysilyl groups may be maintained separately to avoid reactions between the PTH group and the complementary group, interactions between the alkoxysilyl groups, and reactions between the complementary groups. Convenient storage means such as plastic squeeze tubes, plastic bottles, glass containers, sachets, multi-compartment containers, totors, spottles syringes, and plunger-operated dispensing devices can be utilized. Unit amounts for combination can be formulated so that the entire contents of the film-forming composition unit can be combined with the entire contents of the catalyst / promoter for application to keratin fibers. Alternatively, measuring or calibrating dispensing containers with any brush and / or sponge pads for dispensing measured amounts of components as indicated by printed instructions can be provided. In some embodiments, these components can be pre-combined for storage and handling, provided that substantial components causing in situ bonding are maintained in separate compartments.

[0372] The use of the aforementioned delivery means enables the preparation of embodiments for carrying out the method of the present invention. This embodiment may involve applying the pretreatment composition and the film-forming composition sequentially, simultaneously, or pre-mixed to keratin fibers. Pigment microparticles may be incorporated into the film-forming composition. This aspect of the present application provides a lower layer of the pretreatment composition and an upper layer of the film-forming composition on keratin fibers. By controlling the removal of the medium, the temperature of the applied composition, and the use of an activator (if present), the polymers of these compositions can interact in situ to convert into a finished coating, preferably a color coating, which is covalently, hydrogenally, electrostatically, coordinationally, ionically, dipole-like, and entangled. In the case of the film-forming composition, self-reactive or complementary reactive groups are chemically reactive, so that covalent and / or coordination bonds are formed between these components. Preferably, the components of the film-forming composition are also combined with the PTH alkoxysilane compound of the pretreatment composition so that the components of the film-forming composition and the pretreatment composition interact covalently to bond all components together. In this embodiment, the resulting coating on the keratin fibers, preferably a color coating, provides good persistence against repeated shampooing, rinsing, and contact with mild detergents, soaps, and similar cleaning substances.

[0373] Kit forms for pretreatment compositions and film-forming compositions may also include one or more containers or packaging units for materials and / or apparatus for carrying out the Praeparatur and Fundamenta technologies. Packaging units for the Praeparatur technology may include one or more containers of anionic surfactants of various concentrations and types, as well as containers for additives such as pH adjusters and carbonate solutions. Instructions may also be included, including an instruction packet, on when to use the types of anionic surfactants, how to dilute them, how to massage and / or act on the surfactant composition over the entire anagenic hair, and how to rinse and dry the anagenic hair after the Praeparatur treatment. Packaging units for the Fundamenta technology may include one or more containers containing PETT formulations of various concentrations and carbonate base additives for preparing PETT formulations for use. Fundamenta packaging units may also include a low-temperature plasma pen with associated electronics and accompanying cleansing and rinsing compositions. Instructions may also be included, including an instruction packet, on how to use the PETT and / or low-temperature plasma pen. Furthermore, packaging units for acidic oxidation may include instructions on the addition of hydrogen peroxide and adjustment of pH and concentration.

[0374] Application of the PRAEPARATUR procedure and the FUNDAMENTA procedure According to the present invention, one or both of the Praeparatur procedure and the Fundamenta procedure can be applied to keratin fibers such as anogenic hair. These may be applied separately, to different segments of the keratin fibers, sequentially, and / or simultaneously. Typically, the Praeparatur procedure can be applied first to the anogenic hair, and the Fundamenta procedure can be applied as needed.

[0375] The Praeparatur procedure typically initiates the formulation of an aqueous-alcoholic surfactant, with the preferred surfactant being an anionic sulfate surfactant. Using a high-shear mixing procedure and appropriate dilution steps, sodium lauryl sulfate and lauryl ether (PEG) are combined. 10 Approximately 10-40 ml of concentrated anionic surfactant mixture of sodium sulfate can be combined with approximately 150-200 ml of distilled water. A sample prepared as described in the Experiment section can be immersed in the cleansing surfactant and vigorously stirred with a fine-toothed comb for several minutes. If a live salon hair model is to be the subject of the Praeparatur procedure, it may be asked to place its head over the salon's washbasin. The salon operator can then first wet the model's hair with water, then apply the surfactant solution to the hair, and massage and lather the Praeparatur composition into the hair and scalp. After a certain period, the salon operator can rinse the product from the hair and, if necessary, repeat this process once more. Depending on the visual inspection and feel of the hair by the salon operator or laboratory technician, the salon operator / technician may also use a fine-toothed comb or pass a portable ultrasonic device through the segments of hair that have been treated with the cleansing solution. This process is continued with any increase in the concentration of anionic surfactant and any pH adjustments until the operator / technician's visual inspection and the feel of the hair indicate that sebum, grime, and minerals have been removed, exposing the bare hair shaft.

[0376] The Fundamenta procedure can be applied independently and separately from the Praeparatur procedure, or the two can be combined in any order. In the case of a typical combined procedure, the Fundamenta procedure can be applied after the Praeparatur procedure.

[0377] To achieve the Plasma Fundamenta procedure, sections of salon model hair or imitation traces can be exposed to a device that generates low-temperature (room temperature) plasma, such as a Revlon PZ2 plasma pen. Typical low-temperature plasma generators pass a stream of air, nitrogen, or oxygen through a high-energy RF or EMF field to generate ions, along with ozone, from the air and oxygen. A stream of partially ionized gas can be directed onto the hair. The result is a "low-temperature plasma" of partially ionized gas on the keratin fibers. The "low-temperature plasma" can be spread over the Praeparatured segments of hair to deeply cleanse the hair surface. The low-temperature plasma is applied at an appropriate distance for a period of 1 to 5 minutes, preferably 1 to 3 minutes, to provide the desired deep-cleaning effect.

[0378] In another Fundamenta procedure, an aqueous solution of polyalkylammonium bromide, such as trimethylcetylammonium bromide (PETT) or trimethylstearylammonium bromide (STAB), with an alkali pH of about 10 or a thiol pH above 7 is applied to a hair section of a simulant hair rest or salon model, and massaged over the entire rest or hair section for a period of about 5 to 30 minutes, preferably 5 to 10 minutes. The treatment is then rinsed off with shampoo at an acidic pH (by acetic acid) until the PETT or STAB is removed.

[0379] In an alternative Fundamenta procedure, a composition containing 1.9–12% hydrogen peroxide is mixed with a persulfate decolorizing composition, which may be in powder form. The mixed composition is applied to the hair for a period of about 1 minute to 120 minutes, more preferably 3–40 minutes, and then rinsed thoroughly from the hair. In an additional alternative Fundamenta procedure, a composition containing 1.9–12% hydrogen peroxide is mixed with a composition containing an alkaline agent between 0.1–10% selected from monoethanolamine or ammonia and ammonium hydroxide. The mixed composition is applied to the hair for a period of about 1 minute to 120 minutes, more preferably 3–40 minutes, and then rinsed thoroughly from the hair.

[0380] In another Fundamenta procedure, an acidic oxidizing agent composition is prepared by combining 12% hydrogen peroxide solution with an acetic acid solution with a pH of 3.5–4 to produce a hydrogen peroxide concentration of approximately 0.5%–2.5. The acidic oxidizing agent composition is applied to the hair for a period of approximately 1–10 minutes, more preferably 3–6 minutes, and then rinsed thoroughly from the hair.

[0381] In another Fundamenta procedure, a reducing composition, such as Wella Creatine(N) Perm Emulsion, available from Wella Professionals, is applied to the hair for a period of about 1 to 20 minutes, more preferably 2 to 15 minutes, and then rinsed thoroughly from the hair.

[0382] After performing the Fundamenta procedure alone or in combination with the Praeparatur procedure, the hair of a imitation sample or salon model is ready for the pretreatment steps according to the present invention.

[0383] Application of pretreatment composition According to the present invention, the application of a pretreatment composition to keratin fibers as a pretreatment after the application of the Praeparatur and Fundamenta procedures and before the application of the film-forming composition is at least partially a factor in achieving the quality and properties of the coating, preferably a color coating, on the keratin fibers. According to this embodiment of the method, the pretreatment is applied to at least a portion, preferably the entire keratin fiber.

[0384] Pretreatment with a pretreatment composition may be performed before application of the color composition. Pretreatment may be performed immediately before application of the color composition, or at least 1 hour before application of the color composition, or at least 24 hours before application of the film-forming composition, or at least 10 days before application of the film-forming composition, or at least 1 month before application of the film-forming composition. Preferably, pretreatment may be performed immediately before application of the film-forming composition or within a few minutes to a maximum of 1 hour before. Typically, the pretreatment composition is at least partially dried with any heat to remove or eliminate at least substantially its medium. For example, excess medium can be removed from the pretreatment composition on the hair by bringing damp coated hair into contact with an absorbent cloth, or damp coated hair can be partially dried by heating with a hairdryer. Preferably, substantial removal of the medium of the pretreatment composition is achieved before application of the color composition.

[0385] In one embodiment, two or more pretreatment compositions may be applied to the hair. Two different pretreatment compositions may be applied sequentially to provide a cumulative benefit to the subsequent film-forming composition applied, or two different pretreatment compositions and optionally two different film-forming compositions may be applied to substantially different parts of the hair. Such cases may occur when applying to hair that has properties very different from natural hair, for example, parts that have been pre-bleached or have color, or root vs. tip hair. In such cases, different pretreatments may be required to prepare the entire hair for the subsequent film-forming composition. Such different pretreatments are directed towards different parts of the hair, but there is at least some slight mixing, and it is likely that some areas of the hair will receive both pretreatment compositions. A third case may be applying a pretreatment composition to a part of the hair, for example the roots, and then applying a second different pretreatment composition over the entire hair.

[0386] Application of film-forming composition after pretreatment As described above, one or more film-forming compositions can be applied to keratin fibers in combination with the pretreatment using a pretreatment composition. Embodiments of the film-forming compositions as a first binder component and a second binder component having complementary binder functional groups can be maintained separately until use. Application of one or more film-forming compositions to pretreated keratin fibers can preferably be achieved by sequential application to segments of hair. Once all segments are coated with one or more wet film-forming compositions, the one or more film-forming compositions can be dried and / or cured to form an overlay coating layer on the keratin fibers. Alternatively, the application and subsequent drying and / or curing can be carried out section by section across the head. Typically, the condensation rate and drying rate of the film-forming composition can be pre-adjusted through medium control, optionally pH adjustment, concentration, steric interaction, temperature, and similar factors controlling the reaction and / or drying rate so that the premix of the binder components of the film-forming composition preferably does not substantially interact before the premix is ​​applied to the keratin fibers. In the pretreatment embodiment, this step involves first introducing the film-forming composition onto the low-molecular-weight pretreatment layer on the keratin fibers. Since the film-forming composition is in a medium, penetration, combination, mixing, and / or fusion of the film-forming composition into the pretreatment layer are achieved at least partially. The penetration is thought to enable bonding between the binder polymer of the film-forming composition, the low-molecular-weight components of the pretreatment composition, and the keratin fibers. Drying and curing of these compositions preferably occur after all compositions have been applied. In this way, fusion between all layers is best achieved.

[0387] The application of one or more film-forming compositions to keratin fibers pre-treated with a pre-treatment composition is preferably performed after the pre-treatment. This sequence may be performed immediately after the pre-treatment, or at least one hour after the pre-treatment, or at least 24 hours after the pre-treatment, or at least 10 days after the pre-treatment, or at least one month after the pre-treatment.

[0388] The sequential, simultaneous, or premixed application of the film-forming composition may be applied to at least a portion of the keratin fibers, or to the entire keratin fiber. A portion of the film-forming composition may be applied sequentially to all keratin fibers, simultaneously in a single application, or applied stepwise to the keratin fibers. Applying the film-forming composition stepwise as described above helps ensure that the treatable portion of the keratin fibers is saturated with the combined film-forming composition and pretreatment composition, thus potentially providing better coating of the keratin fibers.

[0389] Operational techniques for application After the application of the pretreatment composition and one or more film-forming compositions is achieved, the wet coated keratin fibers, e.g., treated keratin fibers, may be rinsed, after which the treated keratin fibers begin to harden. Heating the treated keratin fibers using a high temperature can accelerate the condensation hardening and complementary reactions from alkoxysilyl groups to siloxanyl groups. The temperature of the keratin fibers can be raised to a high temperature above room temperature, e.g., 40°C or higher, for example, using a hair dryer. While the keratin fibers are being heated, some form of fitting device can be used to separate some of the keratin fibers, in particular to separate hair from each other. Examples of fitting devices include combs or brushes. The keratin fibers can be combed or brushed until touch-dry while being heated with a hair dryer. Alternatively, keratin fibers such as hair can be heated and separated simultaneously by other means. For example, a combination of air movement and vibration can be used to achieve the distribution of a multi-component composition throughout the hair.

[0390] Instructions for coating hair By applying embodiments of the operating method of the present invention to keratin fibers, a coating of a pretreatment composition, a film-forming composition, and an optional topcoat composition can be formed. This embodiment of the present invention relates to a method for coloring keratin fibers and includes applying embodiments of one or more pretreatment compositions and film-forming compositions for a sufficient time to deposit an effective coating, preferably a color coating, on each keratin fiber or keratin fiber such as hair. This results in a somewhat to substantially overall distribution of the coating over the length and circumference of each fiber.

[0391] To achieve this embodiment, the Praeparatur and Fundamenta procedures for preparing keratin fibers may be performed before, overlapping with, or concurrently with the application of the pretreatment. Depending on the order of the activation and pretreatment steps, embodiments of the pretreatment composition and film-forming composition may be applied sequentially, overlappingly, or concurrently to keratin fibers such as hair by coating the keratin fibers with the embodiments using brushing, painting, spraying, atomizing, squeezing, printing, friction, massage, or any other method, in accordance with the above order. After applying embodiments of the composition to keratin fibers such as hair, the composition is set, cured, linked, adjusted, and / or fused by preferably heating with blow-drying hot air from a hairdryer or similarly, thereby removing the medium and initiating in situ bonding of alkoxysilyl groups and complementary bonds between film-forming polymers, as well as hydrogen bonding, molecular entanglement, and polar interactions, thereby initiating an in situ-forming silicone network formed from the pretreatment composition and keratin fibers. This set leaves substantial to essentially complete overall bonding and binding between these substantial components of the coating, preferably a color coating, on the keratin fiber.

[0392] The rate at which film-forming compositions and pretreatment compositions cure and bond internally and to each other, or the reaction rate, is the rate at which reactants are converted into products. In the context of film-forming compositions and pretreatment compositions forming adhesive colored coatings, rate refers to the rate at which covalent and non-covalent bonding occurs. In one embodiment, it is preferable that the reaction / drying rate is not fast enough for the resulting elastomer to form before wetting and diffusion on the keratin surface can occur. If the reaction / drying rate is too fast, the resulting elastomer may not be able to subsequently wet and diffuse onto the hair surface, resulting in poor coating of hair and low resistance to washing. Conversely, an extremely slow reaction / drying rate will not yield practical results within the typical time of a salon coloring treatment. In a preferred embodiment, the reaction / drying rate is slow enough for the film-forming compositions and pretreatment compositions to wet and diffuse onto the keratin surface, but fast enough for a macroscopic continuous film to form on the keratin surface as the film bonds covalently / non-covalently. A typical period for achieving continuous film formation is preferably less than 48 hours, more preferably less than 24 hours, even more preferably less than 12 hours, most preferably less than 6 hours, and most preferably less than 30 minutes, after completion of application and under normal room temperature conditions.

[0393] The bonding and binding of substantial components of the applied pretreatment composition and one or more film-forming compositions to keratin fibers provides a coating, preferably a color coating, that resists removal by washing with a diluted mixture of soap and water or shampoo and water. The coating is not substantially removed by washing with a dilute soap aqueous solution or a dilute shampoo aqueous solution, but color persistence is developed so that the coating can be easily removed by using a conversion trigger. The properties of the coating include persistence, flexibility, adhesion, abrasion resistance, and resilience, which are at least partially attributable to the bonding and binding properties of the substantial coating components, including at least intermolecular entanglement, ionic and electrostatic intermolecular interactions, covalent and / or non-covalent bonds, hydrogen bonds, dipole interactions, and lipophilic interactions.

[0394] The pretreatment compositions and film-forming compositions and any topcoats according to this disclosure may have a viscosity that can be controlled to allow the product to be applied to the hair using either a brush and a bowl or a bottle, but may have sufficient rheology so as not to drip from the hair to the face or body.

[0395] Alternatively, low-viscosity formulations can be applied to the hair via an appropriate application device to prevent them from dripping onto the face and body.

[0396] The pretreatment composition, film-forming composition, and any topcoat can be used in concentrated or sequentially diluted form to provide a color result that is substantially consistent along the entire length of the keratin fiber.

[0397] As described above, the embodiment of coloring keratin fibers with a pretreatment composition, a film-forming composition, and an optional topcoat includes a method for this coloring. This method is (i) Applying the above pretreatment composition and film-forming composition to keratin fibers to obtain an effective deposition amount of a color composition containing pigment fine particles and any additional components; (ii) Setting the pretreatment composition and the film-forming composition by removing or eliminating the medium (for example, by drying the composition); (iii) Initiating in situ bonding between these groups sets up the interaction between the reactive components of the film-forming composition and the pretreatment composition. Includes.

[0398] During the setting / drying process, color distribution can be facilitated by simultaneously moving and / or stroking the hair with a fitting device. Examples of fitting devices include combs or brushes. The fitting device needs to be pulled substantially along the hair from root to tip. This is approximately 0.1 cm. -1 ~50cm seconds -1 Speed ​​or 0.5 cm / second -1 ~20cm seconds -1 It can be pulled out at a speed between [speeds].

[0399] The pretreatment composition and film-forming composition, as well as any topcoat, are applied to the keratin fibers by any suitable method, including spraying the pretreatment composition and film-forming composition, applying the pretreatment composition and film-forming composition to the hands, and then massaging the keratin fibers by hand, or by combing, brushing, or other methods to apply the pretreatment composition and film-forming composition to the entire keratin fiber.

[0400] The methods for applying the pretreatment compositions and film-forming compositions, as well as any topcoat compositions described herein, can be modified so that the user can apply the product to one area of ​​hair and then apply a diluted version to another area of ​​hair. The diluted formulations are specially selected to be compatible with the colorant formulations and maintain the lifespan of the color result while reducing the color intensity. This can effectively result in a “blank” formulation containing nearly the same materials as the colorant formulation, but with low or no pigment. When diluted, the ratio of diluent to colorant may be between about 10:1 and about 1:10, about 8:1 and about 1:2, or about 5:1 and about 1:1.

[0401] Alternatively, the amounts of the applied pretreatment composition, film-forming composition, and any topcoat composition can be varied in different areas of the hair. For example, applying half the amount of product to the length of the hair will result in a less colorful finish. The difference between the amount applied to one area of ​​hair and the amount applied to another area may be between approximately 4:1 and 1:4 or approximately 2:1 and 1:2.

[0402] Alternatively, a combination of these techniques can be used to produce target color variations.

[0403] If the aforementioned technique is not feasible, it may be possible to apply two or more hair colors to different areas of the hair, rather than applying a single hair color. When doing so, the different hair colors preferably provide complementary colors to produce an attractive result. The differences in usable colors are as follows, based on the final result of hair treatment (described later - untreated hair treatment): as explained within the CIELCh color space: Color 1 (LCh) vs. Color 2 (LCh) Color 1L-15<Color 2L<Color 1L+15 0 or color 1C - 10 < color 2C < color 1C + 10 Color 1h-45<Color 2h<Color 1h+45

[0404] Those skilled in the field of color measurement will know how to interpret the difference in h when the hue angle extends from a low positive value to a value close to 360 degrees, due to the periodic cyclical nature of the hue angle.

[0405] The pretreatment composition and film-forming composition, as well as any topcoat composition according to the present invention, can be used for any suitable period of time. The application period may be approximately 0 to 30 minutes, but in any case, it may be long enough to allow the coating of pigment microparticles to coat and adhere to or bond to each individual keratin fiber substantially along the entire length of each keratin fiber. As a result, keratin fibers are obtained that have at least the same color and persistence as those produced from oxidative hair color, except under much milder conditions.

[0406] The pretreatment compositions and film-forming compositions described herein may be prepared by the manufacturer as primary colors, for example, ready for application to hair, and then shipped to the user in separate units. The user may need to re-blend the pretreatment and film-forming compositions before application to ensure that the pretreatment and color compositions provide optimal performance. Such re-blending may require shaking the pretreatment and film-forming compositions for about 1 to about 120 seconds, or about 3 to about 60 seconds. Re-blending may also be carried out by stirring the pretreatment and film-forming compositions before use. This may be done for about 1 to about 120 seconds, or about 3 to about 60 seconds. Although the pretreatment and film-forming compositions according to the present invention are designed to provide a stable suspension of pigment particles, re-blending is desirable to stir the fine particles and resuspend them in a substantially uniform distribution.

[0407] Multiple compositions containing different pigments can be blended together before application to keratin fibers. Such blends can be made in a manner that applies multiple complementary surface colors to the keratin fibers. Typically, a large group of different pigments, concentrated in a dispersant medium and having low molecular weight coatings, is provided as a premix for combination with a film-forming composition. The color selection program described above determines which selection of different pigment concentrates will provide the desired color result for the customer's hair. The premix is ​​metered into the film-forming composition at a concentration ready for application to an anagenic hair.

[0408] The pretreatment composition and film-forming composition may include multiple layers, with at least multiple applications of the film-forming composition following the pretreatment composition and film-forming composition. Periodic reapplication of a third component may also be beneficial. Techniques for applying multiple layers follow the techniques described above for the application of a single pretreatment and color composition.

[0409] Coatings of pigment microparticles containing at least one pigment in the coating of substantial components of pretreatment compositions and film-forming compositions can be adhered to treatable materials such as hair, utilizing a coating having a total thickness of less than about 5 μm, preferably less than about 2 μm, at any given point along the hair fiber, as measured using a scanning electron microscope (SEM). To perform such measurements, a coated hair sample can be embedded in a suitable resin, and then sections can be made from root to tip using techniques known to those skilled in the art of scanning electron microscopy. The thickness of the layer on the surface can then be evaluated along the cuticle line over a length of at least 100 μm. The layer thickness is determined by averaging 10 points evenly distributed across the sectio...

Claims

1. A method for creating a coating on hair, An activation step comprising contacting hair with a Fundamenta procedure, or both a Praeparatur procedure and a Fundamenta procedure, to form modified hair; A pretreatment step comprising applying a pretreatment composition to modified hair to form pre-coated hair; The process includes applying a film-forming composition to pre-coated hair to form a composite film of the film-forming composition and the pre-treatment composition on the hair, wherein the composite film can be converted into a coating through a binder process; The activation process and the pretreatment process are performed simultaneously or sequentially. Includes, The Praeparature procedure includes the cleaning process; Fundamenta procedures include acidic oxidation processes, basic oxidation processes, plasma processes, alkali phase-transfer tenside processes, reduction processes, or any combination thereof; The pretreatment composition is a medium, a PTH-organo-alkoxysilane having at least one PTH group and at least one alkoxysilane group, and / or a PTH-organo-multidimethylsiloxane alkoxysilane having at least one PTH group and at least one alkoxysilane group [wherein PTH is R ３ S-, OHC-, H ２ C=CR １０ -CO ２ - or HO - including R １０ is hydrogen or C1-C6 alkyl, R ３ [containing a hydrogen or sulfur protecting group]; and / or further comprising a disulfide dimer of a PTH-alkoxysilane compound [wherein PTH is a thiol] and / or a tetrasulfide dimer of a PTH-alkoxysilane compound [wherein PTH is a thiol]; The film-forming composition comprises a medium and a binder polymer, the binder polymer comprising a unitary binder polymer having binder functional groups, or a dual binder polymer comprising a first organosilicone or organosilicone component and a second organosilicone or organosilicone component, wherein the first and second components have complementary binder functional groups. method.

2. The method according to claim 1 for producing a color coating, comprising combining at least one colorant with a pretreatment composition and / or a film-forming composition.

3. The method according to claim 1 or 2, wherein the pretreatment composition further comprises a PTH organic compound and / or an aminoorganoalkoxysilane compound.

4. The method according to any one of claims 1 to 3, wherein a pretreatment step comprising an activation step comprising at least one of the processes of the Fundamenta procedure and a pretreatment step comprising applying a pretreatment composition comprising at least one PTH alkoxysilane compound produces a colored coating having color persistence that lasts longer than that of a colored coating produced without performing the activation step comprising at least one of the processes of the Fundamenta procedure and without performing the pretreatment step comprising applying a PTH alkoxysilane compound, the persistence being determined according to a full root simulation color persistence test.

5. The method according to claim 4, wherein a PTH alkoxysilane compound reacts with hair.

6. The method according to any one of claims 1 to 5, wherein the pretreatment composition comprises a PTH organo-alkoxysiloxane compound of formula IIIA, a PTH organo-multi-dimethylsiloxanyl alkoxysilane of formula IIIB, a disulfide or tetrasulfide dimer of formula IIIA having PTH as a thiol, a disulfide or tetrasulfide dimer of formula IIIB having PTH as a thiol, and a PTH alkoxysilane compound comprising at least one of any combination thereof: (PTH-(CH ２ ) ｋ -(Y) ｌ ) ｄ -(ORG) ｍ -SiR １ ３－ｎ (OR) ｎ Formula IIIA PTH-(CH ２ ) ｋ -(Si(Me) ２ O) ｏ -SiR １ ３－ｎ (OR) ｎ Formula IIIB [In the formula, The indicator k is an integer between 1 and 20; The indicator l is either zero or one; The indicator d is an integer of 1, 2, or 3; The indicator m is zero or an integer from 1 to 6; The indicator n is an integer between 1 and 3; The indicator o is an integer between 1 and 20; PTH is R ３ S-, OHC-, H ２ C=CR １０ -CO ２ -, including HO-; R ３ It comprises hydrogen, cyano, 2-10 carbon alkanoyl, phenyl group, heteroaromatic group, phenylalkyl group or heteroaromatic alkyl group, the heteroaromatic group is pyridyl, pyrimidinyl, pyrrolyl or thiophenyl, and the alkyl group is C1-C4 alkyl group, R １０ can be hydrogen or methyl, resulting in R ３ S- can be a thiol group (HS-) or a protected thiol group; R1 contains C1-C3 alkyl; R includes C1-C4 alkyl groups; Y includes -COO-, -OOC- (carboxyl, oxycarbonyl), ether oxygen, ether thiol, -NMe-NH-, -NHCO-, -CONH-; The ORG group is (i) an alkyldithioalkyl, alkyldiazoalkyl, alkyluretanylalkyl, alkylureidoalkyl, alkylcarboxylalkyl, alkylamidealkyl, alkylesteralkyl, or divalent organic group containing alkyl [each alkyl is independently a C1-C20 linear or branched alkyl in each case, and as a result ORG is the left (PTH-(CH) of formula III] ２ ) ｋ - (Y) ｌ ) ｄ Part and right-SiR １ ３－ｎ (OR ２ ) ｎ [to connect parts]; or (ii) Expressions having f as zero or an integer from 1 to 19 polyvalent C1-C20 alkylenyl groups (PTH-(CH ２ ) ｋ - (Y) ｌ ) ｄ - (ORG) ｍ The part of formula IIIA that includes formula A (In the formula, two or three (PTH - (CH ２ ) ｋ - (Y) ｌ ) ｄ The part is connected as D, however, two Ds are (PTH-(CH ２ ) ｋ - (Y) ｌ ) ｄ If it is a part, the third D in formula A can be hydrogen or a C1-C6 alkyl; (CH ２ ) ｆ The dangling valency of - is the right-hand -SiR in formula IIIA. １ ３－ｎ (OR ２ ) ｎ (Joined to a part) This is the result.

7. In formulas IIIA and IIIB, The indicator k is an integer from 1 to 6, and / or R1 contains methyl and / or R contains methyl or ethyl, and / or Each alkyl group of the divalent organic ORG group (i) includes a linear C1-C3 alkyl group and / or The method according to claim 6, wherein the third D in formula A is methyl.

8. The pretreatment composition comprises at least a polycondensate of a PTH alkoxysilane of formula IIIA and / or formula IIIB having PTH as a thiol or protective thiol, wherein the thioalkoxysilane of formula IIIA and / or formula IIIB is itself and / or the alkylalkoxysilane of formula B [wherein R ８ [A linear or branched alkyl group consists of 1 to 10 carbon atoms]: R ８ -SiR １ ３－ｎ (OR) ｎ Formula B It undergoes at least partial polycondensation to produce a linear or branched oligomeric silicone polycondensate having a silicone chain of combinations of M, D, and T groups, wherein the polycondensate has a pendant alkoxy group, a pendant thioalkyl group and / or a pendant alkyl group, and the polycondensate has M of 350 to 3500 Da ｗ and functional group equivalents M of thiols and / or protected thiols from 100 to 900 ｗ (FEM ｗ ) and FEM for 50-900 alkoxy groups ｗ The method according to claim 6, having the following characteristics.

9. The method according to claim 8, wherein only formula IIIA undergoes at least partial polycondensation to form a linear or branched oligomeric silicone polycondensate.

10. The method according to any one of claims 1 to 9, wherein PTH is a thiol (HS-).

11. The PTH organoalkoxysilane compound is of the formula OSSI [wherein k is an integer from 1 to 20, and multiple CH ２ The chain can be linear or branched, n is an integer from 1 to 3, and R １ is methyl, R ２ [It is methyl or ethyl.] HS-(CH ２ ) ｋ -SiR １ ３－ｎ (OR2) ｎ OSSI formula The method according to any one of claims 1 to 10, which describes a pretreatment composition including the following:

12. The method according to claim 11, wherein k is an integer from 1 to 6.

13. The OSSI formula is HS- (CH ２ ) ｋ - Si (OME) ３ またはHS-(CH ２ ) ｋ - Si (Oet) ３ [In the formula, k is an integer between 1 and 6.] The method according to claim 11, including the method described in claim 11.

14. The pretreatment composition is a thiol organic compound of formula V. [In the formula, D is defined above (PTH-(CH ２ ) ｋ - (Y) ｌ ) ｄ And; Each of the indicator g is independently either zero or one; The E group can be a bond or a C1-C6 alkylenyl group; The Ak group is the carbon atom Ak0 or structure Ak1, Ak2, Ak3, Ak4 shown below, and the dangling valence of the central carbon of Ak0, Ak1, Ak2, and Ak3 is bonded to E-D, CH ２ The valence is bonded to D; all dangling valences of Ak4 are bonded to E-D: PHY is an oligomer of 2 to 10 units of a C3-C8 α,ω-hydroxyalkanoic acid ester having an -O-(CH ２ ), ｈ -O- at its carboxyl terminus and a -(CH ２ ), ｉ -O- group at its hydroxyl terminus, where the -O-(CH ２ ), ｈ -O- group and the -(CH ２ ), ｉ -O- group are each bonded to a CH group, the indicator h is an integer from 2 to 4, and the indicator i is an integer from 1 to 3] The method according to any one of claims 1 to 13, further comprising:

15. The method according to claim 14, wherein PTH is a thiol (-SH).

16. The pretreatment composition is formula VI: H ２ N-(CH ２ ) ｍ -(NH-R １４ -) ｎ -[RO ｔ Me ３－ｔ Si-O] ｂ -(-SiMe ２ -O) ｐ -[(-SiMe ２－ｒ [(CH ２ ) ｍ’ -NH ２ ] ｒ -O] ｓ -[A] ｃ -[(-SiMe ２ -O] ｕ -(SiMe ３－ｔ OR ｔ ) Formula VI [In the formula, R １４ Each example is independently a C1-C6 alkylenyl group; R can be methyl or ethyl; The indicators m and m' can be integers from 1 to 3; Indicators b, r, s, and c can be zero or one; The indicator n can be zero or an integer from 1 to 6; The indicator t can be 1 to 3; The indicators p and u can be zero or integers from 1 to 12; Group A may be a divalent group containing dithio, diazo, uretanyl, ureido, carboxyl, amide, ester, or aminoethyloxycarbonyl, or a C1-C20 alkylenyl group, connecting the left and right portions of the aminoorgano-alkoxysiloxane compound; or Group A can be a polyvalent C1-C20 alkylenyl group connecting two or three left portions and one right portion of an aminoorganoalkoxysiloxane compound, where a is 2 or 3 and b, p, and s are zero; or Group A can be a linear or branched polyethyleneimine moiety of 2 to 2000 ethyleneimine units, in which case b, p, s and u are all zero; or The A group is a C2-C8 alkylenyl (meth)acrylate or -(CH ２ ) ｎ -O-CH ２ - CHOHCH ２ -O ２ C(R) = CH ２ [In the formula, R is H or CH] ３ [where n is an integer between 2 and 8] and can be a terminal group. The method according to any one of claims 1 to 15, further comprising an aminoorganoalkoxysilane compound containing the above.

17. Group A is -(SiMe ３－ｔ OR ｔ ) The base is -NH ２ The method according to claim 16, wherein the linear or branched polyethyleneimine portion is 2 to 2,000 ethyleneimine units replaced by

18. Equation VI is Equation OASI H ２ N-(CH ２ ) ｍ -(NH-R １４ -) ｎ -(SiMe ２ O) ｐ -A ｃ -(-SiMe ２ -O) ｕ SiMe ３－ｔ OR ｔ formula OASI [In the formula, m is an integer from 1 to 6; n is zero or an integer between 1 and 3; p and u are each independently zero or integers from 1 to 3; c is either zero or one; t is an integer between 1 and 3; A is a C1-C6 alkylenyl; R is either methyl or ethyl. The method according to claim 16, including the method described in claim 16.

19. The formula OASI is H ２ N-(CH ２ ) ｍ -Si (OR) ３ or H ２ N-(CH ２ ) ｍ - (NH-R １４ ) ｎ -NH-R １４’ -Si (OR) ３ or H ２ N-(CH ２ ) ｍ -NH-R １４ -Si (OR) ３ [wherein m is 2 or 3, n is 1 or 2, and R is methyl or ethyl, R １４ Each example is independently ethyl, propyl, or isobutyl, and R １４’ [These are propyl, butyl, or isobutyl.] The method according to claim 18.

20. The method according to any one of claims 1 to 19, wherein the pretreatment step and the binder step are performed simultaneously.

21. The method according to any one of claims 1 to 20, wherein the pretreatment step and the binder step are carried out sequentially.

22. The method according to any one of claims 1 to 21, wherein the hair is an anogenic hair.

23. The method according to claim 22, wherein the hair is from a human scalp.

24. The method according to any one of claims 1 to 23, wherein no coloring agent is present.

25. The method according to any one of claims 1 to 24, wherein the curing of the composite coating includes a step selected from drying, heating, heat drying, and addition of a catalyst to accelerate the curing rate.

26. The method according to any one of claims 1 to 25, wherein a coloring agent is present and comprises a pigment or a coating pigment.

27. The method according to any one of claims 1 to 26, wherein the Fundamenta procedure is combined with a pretreatment step.

28. The method according to any one of claims 1 to 27, wherein the Fundamenta procedure is a reduction process followed by an acidic oxidation process.

29. The method according to any one of claims 1 to 28, wherein the Fundamenta procedure is an acidic oxidation process.

30. The method according to any one of claims 1 to 29, wherein the activation step includes a Praeparatur procedure.

31. The method according to claim 30, wherein the Praeparatur procedure and the Fundamenta procedure are combined.

32. The method according to any one of claims 1 to 29, wherein the activation step comprises at least one of the processes of the Fundamenta procedure, but does not comprise the Praeparatur procedure.

33. The method according to any one of claims 1 to 32, wherein the film-forming composition comprises a unitary binder polymer comprising an organic binder polymer of one or more monomer units selected from olefin carboxylate ester units, olefin carboxamide units, carbon-hydrogen olefin units, ester monomer units, amide monomer units, urethane monomer units, and urea monomer units, and the organic polymer has at least one pendant and / or terminal binder-functional monogroup comprising an alkoxysilyl group.

34. The organic binder polymer is a compound of at least formula I. X ３ Si-R １ -Ct-[Poly] ｙ -Ct-R １ -Si-X ３ Formula IA [In the formula, X is a hydroxyl or alkoxy of 1 to 3 carbon atoms; R １ These are C1-C8 alkylenyl groups; Ct is X ３ Si-R １ Formula II-U that combines - with Poly １ -R ２ -U ２ - is a connector base, U １ is R １ It is covalently bonded to U ２ It is covalently bonded to Poly; U １ and U ２ Each of them is independently a urea or urethane group; R ２ These are C2-C12 alkylenyl groups, C6-C16 alkylcycloalkyl groups, or C6-C14 aromatic or alkylaromatic groups; Poly is a polymer of monomer units of an organic ester, urethane, urea, amide, or polyol, or any combination thereof, where y indicates the number of monomer units of Poly that form the polymer backbone, where y is an integer from 2 to approximately 1 million, and Poly is linear or branched; Organic ester monomer units are formed from C2-C20 alkanediols or C6-C10 aromatic diols and C3-C10 alkanediic acids or C8-C10 aromatic dicarboxylic acids, or units are formed from C3-C10 hydroxyalkanoic acids or C8-C10 aromatic hydroxycarboxylic acids; Organic urethane monomer units are C2-C10 alkanediols and R ３ - Formed from diisocyanates; The organourea monomer unit consists of C2-C10 alkanediamines and R ３ - Formed from diisocyanates; Organic amide monomer units are formed from C2-C10 alkanediamines and C3-C10 alkanediic acids or C8-C10 aromatic dicarboxylic acids; Polyol monomer units are formed from ethylene oxide or propylene oxide; R ３ These are linear or branched C2-C12 alkylenyl groups, C6-C16 alkylcycloalkyl groups, or C6-C14 aromatic or alkylaromatic groups; however, When Poly is an ester monomer unit, U ２ It is a urethane group, U １ It is a urea group; When Poly is a urethane monomer unit, U ２ It is a urethane group, U １ It is a urea group; If Poly is a urea monomer unit, then U ２ It is a urea group, U １ It is a urea group; When Poly is an amide monomer unit, U ２ and U １ Both are urea groups; When Poly is a polyol monomer unit, U ２ It is a urethane group, U １ It is a urea group; Or, U １ [This can be a urethane group for each of the following conditions: Polyester, Polyurethane, Polyurea, Polyamide, and Polyol] The method according to claim 33, including the method described in claim 33.

35. The method according to any one of claims 1 to 32, wherein the film-forming composition comprises a unitary binder polymer containing an organic polymer of one or more monomer units selected from olefin carboxylate units, olefin carboxamide units, carbon-hydrogen olefin units, ester monomer units, amide monomer units, urethane monomer units, and urea monomer units, and the organic polymer has at least one pendant and / or terminal binder functional monogroup containing at least one pendant and / or terminal carboxylic acid group.

36. The method according to claim 35, wherein the pretreatment composition comprises a PTH alkoxysilane compound and an aminoorganoalkoxysiloxane compound, and an organic polymer having at least one carboxylic acid binder-functional monogroup is capable of non-covalent interaction with the pretreatment compound.

37. The binder polymer comprises an organic polymer comprising repeating units of at least one olefinic acid monomer unit and at least one non-acidic olefin monomer unit selected from olefin carboxylate ester monomer units, olefin carboxamide monomer units, hydrophilic olefin monomer units, lipophilic olefin monomer units, and any combination thereof. The olefinic acid monomer unit is selected from (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, gluconic acid, C5-C10 ethenic acid, or any combination thereof; The olefin carboxylate ester monomer unit is selected from C1-C30 linear or branched alkyl esters of any or any combination thereof of olefin acid monomer units; The olefin carboxamide monomer unit is -NH of any one or any combination thereof of the olefin acid monomer units. ２ , -NR １ H or -NR １ R ２ amide [wherein R １ and R ２ [Each is independently selected from C1-C6 linear or branched alkyl groups; The hydrophilic olefin monomer is a hydroxyalkyl ester of an olefin carboxylic acid monomer unit and a linear or branched C2-C24 alkyldiol, or an aminoalkyl ester of an olefin carboxylic acid monomer unit and a linear or branched amino C2-C24 alkyl alcohol, or any combination thereof; Lipophilic olefin monomer units, formula R ３ HC=CHR ４ [In the formula, R ３ R is selected from hydrogen, a linear or branched alkyl group of 1 to 6 carbon atoms, an unsubstituted phenyl or a phenyl group substituted with a linear or branched alkyl group of 1 to 6 carbon atoms, a methyl or ethyl carboxylate, a carboxamide or a hydroxyl, ４ This includes hydrogen, a linear or branched alkyl group of 1 to 6 carbon atoms, unsubstituted phenyl or phenyl substituted with a linear or branched alkyl group of 1 to 6 carbon atoms, methyl or ethyl carboxylate, carboxamide or hydroxyl, or the formula -CH=CHR. ５ (In the formula, R ５ [Selected from hydrogen, a linear or branched alkyl group of 1 to 6 carbon atoms, an unsubstituted phenyl or a phenyl substituted with a linear or branched alkyl group of 1 to 6 carbon atoms, a methyl or ethyl carboxylate, a carboxamide or hydroxyl group, or an ethenyl group] Selected from the olefin compounds, The method according to claim 35 or 36.

38. The film-forming composition comprises a dual binder polymer comprising a first component containing a silicone or organosilicone polymer having at least one pendant and / or terminal first binder functional group, and a second component containing a low molecular weight, prepolymer or polymer having at least one pendant and / or terminal second binder functional group; The first binder functional group and the second binder functional group are complementary pairs selected from the group consisting of (i) an alkenoyloxy and an amine or (ii) an alkenoyloxy and a thiol. The method according to any one of claims 1 to 32.

39. The first component is a silicone polymer of formula I. X ｚ -SiM% ３－ｚ Oh- (Me) ２ (SiO) ｘ -(Si(-X)MeO) ｙ -SiOM% ３－ｚ -X ｚ Equation I [In the formula, Me ２ Each of SiO and Si(-X)MeO contains monomer siloxane D units, X ｚ SiMe ３－ｚ O contains monomer siloxane M units; X is R １ R ２ C=CR ３ COO-R ４ - including; R １ and R ２ Each of them is independently hydrogen or a C1-C6 alkyl group, however R １ and R ２ At least one of them is hydrogen; R ３ is hydrogen or methyl; R ４ R is a C1-C12 alkylenyl group, a C3-C12 cycloalkylalkyl or cycloalkyl group, a C6-C20 arylalkyl group or C6-C20 aryl group, ４ It is bonded to monomer D and / or M units of silicon; Each of the indicators x and y independently indicates the number of monomer Dsiloxane units that form the corresponding linear polymer silicone backbone, where x is an integer from 1 to approximately 100,000, and indicator y is zero or an integer from 1 to 10; X ｚ SiMe ３－ｚ For each of the O units, the indicator z is either zero or 1, and as a result X ｚ SiMe ３－ｚ The O unit may have a terminal X group, or it may be an M-type trimethylsiloxy group; The sum of x and y is an integer between approximately 3 and a maximum of approximately 200,000, with exemplary sums being between 10 and 50 and between 10 and 20; Me ２ Multiple monomer units of SiO and Si(-X)MeO are randomly distributed in formula I. Including; The second component is given by equation V M1-(D) ｄ -M2 Formula V [In the formula, M1 and M2 are the ends of the second component, Me ３ SiO units, A-SiMe ２ O units and -Si(OR) ３ The units can be selected from, where R is methyl or ethyl, and A is an organoamine or organothiol group of formula OA. Y-(R １０ -NH) ｒ -R １１ - OA format (In the formula, Y is -NH) ２ or -SH; R １０ R is a linear or branched C1-C10 alkyl group or a linear or branched C6-C14 alkylaryl group; １１ is a linear or branched C1-C10 alkyl group or a linear or branched C6-C14 alkylaryl group; the indicator r is zero or an integer from 1 to 3, and if r is not zero, R １１ It is bonded to silicon, and when r is zero, R １１ (It is bonded to silicon, and if Y is -SH, then r is zero.) And; The D unit forms the backbone of the polydimethylsiloxane-type second component, and the indicator d is an integer between 3 and 20,000 indicating the magnitude of the second component. The D unit is SiMe ２ [Selected from O units (dimethylsiloxane units) and A-SiMeO units] Including; The second component contains at least one A-SiMeO unit. The method according to claim 38.

40. R ４ The method according to claim 39, wherein one or all of the groups are substituted in the chain by one or more ether oxygen, thioether sulfur and / or amine groups, and / or pendanted by hydroxyl groups.

41. The film-forming composition comprises a dual binder polymer comprising a first component containing an organosilicone or organosilicone polymer having at least one pendant and / or terminal first binder functional group, and a second component containing a low molecular weight, prepolymer or polymer having at least one pendant and / or terminal second binder functional group; The first and second binder functional groups are complementary, containing a carboxylic acid and a carbodiimide. The method according to any one of claims 1 to 32.

42. The first component is an olefin, silicone, or organosilicone polymer of formula I. *||||) ｘ (**) ｙ (**) ｚ (**) ａ (*|3) ｂ _||| Equation I [In the formula, MU1 comprises a hydrophobic olefin monomer unit containing linear C2-C10 alkene residues, linear C4-C12 alkadiene residues and / or C6-C10 aromatic / alkyl aromatic vinyl residues; MUX comprises acidic olefin monomer units containing linear C3-C10 alkenoic acid residues or C4-C10 alkadienoic acid residues; MU2 comprises hydrophilic olefin monomer units including vinyl linear C2-C16 alkanoate ester residues, C1-C14 linear alkyl or hydroxyalkyl linear C2-C14 alkenoate ester residues, linear C2-C10 alkenoamide residues, or N-C1-C4 alkyl-substituted versions of amide residues; MU3 contains a dimethylsiloxane residue; MU3X contains monomethylsiloxane residues bonded to at least four carbon alkanoic acids; MUE comprises single-terminated monomer units of MU1, MU2, MU3, MUX, or MU3X; Each of the indicators x, y, z, a, and b independently indicates the number of corresponding monomer units that form a linear polymer backbone, where each of x, z, and a is an integer from zero or 1 to approximately 100,000, and each of y and b is an integer from zero or 1 to 100; If b is an integer, then y can be zero or an integer; if b is zero, then y is an integer; The sum of x, y, z, a, and b is an integer ranging from approximately 3 to a maximum of approximately 1,000,000; Multiple monomer units of MU1, MU2, and MU3 are randomly distributed or form blocks in Formula I, and multiple carboxylic acid monomer units MUX and MU3X are randomly distributed among the MU1, MU2, and MU3 units. Including; The first component is either linear or branched; The second component is an organic polymer of formula II, a polymer having an intrachain carbodiimide group or formula X, or a polymer having a pendant single carbodiimide group. Z-(L-N=C=N-) ｐ - Z (Poly) ｑ -(K) ｓ -(Poly) ｒ Formula II Formula X (In the formula, For formula II, p is at least an integer of 2; L is a second organic component group comprising a saturated aliphatic divalent group, an aromatic divalent group or an alkyl aromatic divalent group, or a repeating olefin, carbonate, ester, ether, amide, imine, urethane, or a polymer or oligomer divalent group having a urea bond; For formula X, each Poly is an organic polymer segment of an amide, imine, olefin, caronate, ester, ether, urethane, or urea monomer residue, where the indicators q and r are each at least an integer of 2; K is a pendant carbodiimide group of formula XI, where s is at least an integer of 2. [In the formula, R ２０ These are C3-C6 alkylenyl residues, and R ２１ These are C3-C6 alkylenyl residues. For formulas II and XI, Z is a non-reactive or reactive terminal group of the polycarbodiimide; multiple Ks are randomly distributed along the Poly backbone; and the second component L or Poly is linear or branched. [including] The method according to claim 41, including the method described in claim 41.

43. The method according to any one of claims 1 to 42, wherein a colorant is combined with a film-forming composition.

44. The method according to any one of claims 1 to 43, wherein the coloring agent is a pigment and / or a coating pigment.

45. The method according to any one of claims 1 to 44, wherein all components of the pretreatment composition and the film-forming composition in the compatible medium are kept in separate containers until use.

46. The method according to any one of claims 1 to 45, comprising combining separate amounts of the first component and the second component in a compatible medium before applying them to hair to form a film-forming composition.

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