HK1188948A

HK1188948A - Method for chemically modifying the internal region of a hair shaft

Info

Publication number: HK1188948A
Application number: HK14102089.2A
Authority: HK
Inventors: A.弗洛尔
Original assignee: 宝洁公司
Priority date: 2011-01-19
Filing date: 2012-01-19
Publication date: 2014-05-23

Description

Method for chemically modifying the internal region of a hair shaft

Technical Field

In a first aspect, the present invention provides a method for chemically modifying the internal region of a hair shaft. The method comprises applying an oxidising formulation to the hair; removing moisture from the hair; applying a monomer composition to hair, wherein the monomer composition comprises an alkenyl monomer having a molecular weight of 500g/mol or less and a cosmetically acceptable carrier. In a second aspect, the present invention provides a kit comprising instructions for use comprising the method and monomer composition according to the first aspect.

Background

Retention of the hairstyle has traditionally been achieved by using styling products comprising polymers and other components that at least partially coat the hair and act on the surface of the hair fibres. Several disadvantages accompany this approach. Loss of hair style due to time lapse, increased ambient humidity, excessive movement, etc., can cause the consumer to feel the need to style the hair throughout the day. This often requires the application of additional styling products. Traditional styling products may also have a reduced benefit when applied to hair to which the conditioning agent has been applied. Furthermore, applying materials to the surface of hair can impair the natural feel and appearance of the hair and result in a dull appearance and/or stiffness, or otherwise unpleasant feel. Furthermore, for certain hair types it may simply not be possible to achieve the desired hairstyle with conventional styling products and treatments.

Consumers with damaged, thinner, poorer, or softer hair need to increase their hair volume and fullness, especially consumers who use hairdryers. These consumers seek hair styles, treatments and products that allow others to perceive and speculate as having thicker hair (i.e., increased hair volume, elasticity and greater fullness). It is also a strong desire of these consumers to improve hair direction and style. Accordingly, there remains a desire to enable consumers to achieve both increased volume and better hair feel, mobility, texture, healthy appearance, as well as increased control over their hairstyle. There is a need to enable these consumers to achieve such benefits without the need for reverse combing, extensive blow drying, mousse products and/or hair sprays.

And for consumers with curly and/or non-compliant and/or curly hair, especially consumers with hair straighteners, there is also a need to obtain better control of their hair. These consumers seek hair styles, treatments and products that allow others to perceive and presume that they have smooth hair and/or increased curl definition. In other words, all the hair is in place and the appearance of the hair is very well defined, shiny and looks healthy. These consumers may seek reduced volume and straightening of the hair shaft, which results in a more perfect well-defined appearance. These consumers may often rely on the use of conventional methods such as the application of styling gels and/or styling mousses. Thus, there is a need to enable such consumers to achieve such benefits without having such consumers rely on such conventional methods.

Methods for chemically modifying the internal region of a hair shaft and compositions thereof are known in the art. See, e.g., US2008/0210253a 1. The method may comprise the steps of: a first composition comprising specific monomers is applied to the hair and a second composition comprising an initiator is applied to the hair. The method may result in increased stiffness of the hair shaft, reduced negative effects of moisture and/or humidity (i.e., resulting in a less frizzy condition or fluffy moisture resistance) after multiple washes and/or wettings of the hair, and may require less styling product to be applied and/or may hold the hairstyle for a longer period of time.

While such methods provide satisfactory results to the hair shaft, there is a continuing need to provide methods that result in further improved performance, efficacy and/or efficiency. In view of the improved performance concerns, there is a particular need to provide improved desired style retention and style durability. In terms of efficiency of interest, there is a need to improve penetration of the monomer into the hair shaft and/or to improve polymerization of the monomer, for example, to increase the length of the polymeric chains within the internal structure of the hair shaft. Furthermore, there is a need to improve the durability of the treatment so that the beneficial effect lasts longer. There is also a need to enhance the efficacy, e.g. so that less active and/or composition/formulation/step is needed to achieve similar performance. Furthermore, there is a need to simplify the application process so that it can be carried out by a trained hairdresser or by a consumer at home on their own hair. Furthermore, there is a need to better ensure that the results are more predictable and to reduce the variability of the final results between consumers with different hair types.

Disclosure of Invention

In a first aspect, the present invention relates to a method for chemically modifying the internal region of a hair shaft, wherein said method comprises:

(i) applying an oxidizing formulation to the hair;

(ii) removing moisture from the hair;

(iii) applying a monomer composition to hair, wherein the monomer composition comprises an alkenyl monomer having a molecular weight of 500g/mol or less and a cosmetically acceptable carrier.

In a second aspect, the present invention relates to a kit comprising:

(a) instructions for use comprising the method according to the first aspect;

(b) a monomer composition.

Drawings

FIG. 1: showing the disappearance of the monomer over time, e.g. from proton NMR spectrum: (¹H-NMR).

FIG. 2: shows that when Al is contained in the alloy³⁺Molecular weight of the polymer formed when cationic monomer composition is used, and when Sr containing monomer is used²⁺The molecular weight of the polymer formed when the monomer composition is cationic, as measured by Gel Permeation Chromatography (GPC).

Fig. 3A to 3E: detection of hair bundle by autoradiography¹⁴C-3-SPA。

Fig. 4A to 4D: detection of hair bundle by autoradiography¹⁴C-3-SPA。

Detailed Description

In all examples of the present invention, all percentages are by weight of the total composition, unless otherwise specifically indicated. All ratios are by weight unless otherwise specifically indicated. All ranges are inclusive and combinable. The number of significant figures does not represent a limitation on the indicated amount nor on the accuracy of the measurement.

Unless otherwise specifically stated, all numerical values should be understood as being modified by the word "about". Unless otherwise indicated, all measurements are understood to be made at 25 ℃ and at ambient conditions, where "ambient conditions" refers to conditions at about one atmosphere of pressure and at about 50% relative humidity. All such weights as they pertain to listed ingredients are based on the active level and do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.

Herein, "comprising" means that other steps and other ingredients which do not affect the end result can be added. The term includes the terms "consisting of …" and "consisting essentially of …". The compositions, methods, uses, kits, and processes of the present invention can comprise, consist of, and consist essentially of the inventive components and limitations described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein.

As used herein, the term "substantially free" or "substantially free" means less than about 1%, preferably less than about 0.8%, more preferably less than about 0.5%, still more preferably less than about 0.3%, and most preferably about 0%, by total weight of the composition or formulation.

As used herein, "hair" refers to mammalian hair, including scalp, facial and body hair, more preferably hair on the head and scalp of a human. "shaft" refers to an individual hair strand, and is used interchangeably with the term "hair".

As used herein, "hair shaft interior region" refers to any non-surface portion of the hair shaft, including the interior of the epidermis and beneath the epidermis. "non-surface portion" may be understood to mean a portion of the hair that is not in direct contact with the external environment.

As used herein, "adjacent the scalp" refers to that portion of an extended or substantially straight hair shaft that is closer in distance to the scalp than to the hair ends. Thus, about 50% of the hair will be considered proximal to the scalp and about 50% of the hair will be distal to the scalp. "z cm adjacent to the scalp" refers to the distance "z" along the hair, where one end point is on or directly adjacent to the scalp and the second end point is measured as "z" centimeters along the length of the stretched or substantially straight hair.

As used herein, "cosmetically acceptable" means that the composition, formulation, or component is suitable for use in contact with human keratinous tissue without undue toxicity, incompatibility, instability, allergic response, and the like. All compositions and formulations described herein that are intended for direct application to keratinous tissue are limited to those that are cosmetically acceptable.

As used herein, "derivatives" include, but are not limited to, amide, ether, ester, amino, carboxyl, acetyl, and/or alcohol derivatives of the specified compounds.

As used herein, "monomer" refers to a discrete unpolymerized chemical moiety capable of undergoing polymerization in the presence of an initiator.

As used herein, "alkenyl monomer" refers to a chemical species that contains an olefinic carbon-carbon double bond (C = C) and is capable of undergoing a polymerization reaction in the presence of an initiator.

As used herein, "polymer" refers to a polymer that is chemically formed from the polymerization of two or more monomers. As used herein, the term "polymer" shall include all materials made by polymerization of monomers as well as natural polymers. Polymers made from only one type of monomer are referred to as homopolymers. The polymer comprises at least two monomers. Polymers made from two or more different types of monomers are known as copolymers. The distribution of different monomers can be calculated statistically or in blocks-both possibilities are applicable to the present invention. As used herein, unless otherwise indicated, the term "polymer" includes any type of polymer, including homopolymers and copolymers.

As used herein, the term "hair styling polymer" refers to a hair fixative polymer that forms a film on a surface. In the context of hair, the surface is the surface of an individual hair fiber or a plurality thereof. The polymers cause them to glue together to build a fusion, which is a cross-link that provides a retention benefit. Consistently, these fusions form a "hair net" to provide hair retention and volume benefits to the user. When effectively forming a fused network, the retentive and volume beneficial effect can last throughout the day or provide good resistance to ambient humidity.

As used herein, the term "molecular weight" or "m.wt." refers to number average molecular weight, unless otherwise indicated.

All percentages are by weight unless otherwise indicated.

As used herein, "chemically modified" or grammatical equivalents thereof means that a chemical moiety, such as a monomer and/or crosslinker and/or polymer, is stably attached to a second chemical moiety, e.g., keratin, another component of the hair, and/or another monomer or crosslinker or polymer.

As used herein, "separately packaged" refers to any form of packaging that avoids physical contact or mixing of one composition or formulation with a second composition or formulation. "separately packaged" may mean that the individual compositions/formulations are packaged in separate containers, or packaged in separate single containers such that the individual compositions/formulations are not in direct physical contact.

As used herein, "relative humidity" refers to the amount of water vapor carried in the hair. Herein, "high relative humidity" means a relative humidity that is higher than ambient conditions, i.e., at least about 70%. As used herein, "ambient humidity" refers to the relative humidity to which a consumer may be exposed once the method of the present invention has been completed. Examples of ambient humidity are due to weather conditions. As used herein, "resistance to ambient humidity" refers to the ability of hair to better withstand the negative consequences of ambient humidity.

As used herein, "multivalent cation" refers to an element having a net ionic charge of 2+ to 7 +.

"stably attached" is understood to include chemical bonds in both covalent and non-covalent forms that, once formed, remain unchanged upon wetting, washing, styling and other types of hair treatment. Generally, the stabilizing adjunct chemical moiety cannot be removed from the hair without damaging or substantially destroying the hair.

As used herein, "enhanced style retention and/or durability" refers to the retention of the formed, shaped, and/or obtained hair style for a longer period of time after application of the composition of the present invention to the hair relative to the same hair without application of the composition.

As used herein, "increased apparent volume" means that the hair exhibits an apparently significantly greater volume, i.e., the distance between the scalp and the outermost layer of the hairstyle and/or the distance between individual hairs, after application of the composition of the present invention relative to before application of the composition.

As used herein, "enhanced moisture resistance" means that the hair exhibits no visually significant effects, such as volume reduction, loss of hairstyle, increased kinking, etc., after exposure to water vapor (i.e., relative humidity greater than about 50%) after application of the composition of the present invention relative to prior to application of the composition.

As used herein, "kit" refers to a packaging unit comprising a plurality of components. Examples of kits are, for example, a first composition and a separately packaged second composition. Another kit may comprise a first composition and an energy delivery device. Different kits may contain three different types of separately packaged compositions and hair styling tools. Other kits may contain instructions for the use of the methods and compositions/formulations.

As used herein, "separately packaged" refers to any form of packaging that prevents direct contact or mixing of a first composition with a second composition. "separately packaged" may mean that the individual compositions are packaged in separate containers, or packaged in separate single containers such that the compositions are not in direct contact.

As used herein, "implement" refers to a device used to aid in applying a composition to hair and/or manipulating hair. Examples of implements include, but are not limited to, combs, directional delivery means (e.g., applicators or tubes), coverings for hair (e.g., plastic bags, shower caps, etc.), and combinations thereof.

As used herein, "energy delivery device" refers to any device used to deliver energy to keratinous tissue, including hair and scalp. By "energy delivery" is meant that the surface of the keratinous tissue is exposed to energy emitted from an energy delivery device, wherein the energy can penetrate to a desired layer of tissue, including the hair shaft and/or hair follicle. Energy includes, but is not limited to, energy in the form of light, heat, sound (including ultrasonic waves), electrical energy, magnetic energy, electromagnetic energy (including radio frequency waves and microwaves), and combinations thereof.

(i) applying an oxidizing formulation to the hair;

(ii) removing moisture from the hair;

(iii) applying a monomer composition to hair, wherein the monomer composition comprises an alkenyl monomer having a molecular weight of about 500g/mol or less and a cosmetically acceptable carrier.

The present inventors have responded to the above-mentioned need by carefully selecting a specific combination of mutually compatible features such that their interaction results in a method for chemically modifying the internal region of a hair shaft having improved properties. Specific important beneficial effects of the invention include: reducing the variability of the efficacy of the invention between consumers with different hair types and simplifying the method of applying the invention.

Without being bound by theory, it is believed that there is a wide range of hair types among consumers, for example consumers may have highly damaged hair or undamaged hair. In addition, it is believed that different hair types also contain different levels of redox active materials that catalyze the decay of the initiator required to initiate free radical polymerization of ethylenically unsaturated monomers. Such redox-active substances may for example be residual amounts of metals (e.g. Fe, Co) present in the hair (e.g. from tap water), or cysteine, amino acids present in keratin, proteins forming the hair shaft. The content of those redox-active substances present in human hair varies between different consumers depending on the degree of damage to their hair. It is well accepted in polymer science that the molecular weight of polymers made by free radical polymerization is inversely proportional to the square root of the initial radical concentration. Thus, it is believed that changes in the concentration of redox active in consumer hair result in changes in the molecular weight of the polymer produced within the hair, which correlates with its wash fastness. Higher concentrations of redox active materials will result in lower molecular weight polymers inside the hair, resulting in less wash fastness, and vice versa. While professional stylists can judge the level of macroscopic damage to hair, which may have some correlation with the amount of such damage, it is neither effective nor cost effective to provide methods and compositions tailored for each consumer hair type. Thus, as exemplified in the present invention, the present inventors have surprisingly found that applying an oxidising formulation to the hair prior to applying the monomer composition results in improved performance. It is believed that this oxidation step results in the normalization of the concentration of redox active substances between hair types. The reduction step may also reduce the variability of different hair types, but at the same time will also require a significant reduction in initiator concentration to maintain a lower initial free radical concentration. However, it is necessary to keep the initiator concentration down to a level at which it cannot be handled under practical use conditions.

The inventors have also surprisingly found that it is not required to have a reduction step prior to application of the monomer composition, as is often conventionally taught, to reduce disulfide bonds and exploit the epidermis. When hair is treated according to the present invention without the use of a reducing step prior to application of the monomer composition, excellent benefits are obtained.

It has also been found that the monomer composition can be provided to the consumer and/or stylist in a ready-to-use form. In other words, the monomer composition need not be mixed with at least one other formulation/composition, such as a composition comprising an initiator, salt, oxidant, acid, base or catalyst, prior to application to the hair. This represents a significant improvement in the method for applying the present invention to hair from the standpoint of reduced application time, delivery time, carbon footprint, and cost effectiveness.

The present invention relates to compositions and methods for chemically modifying the interior region of a hair shaft, and more preferably for forming a polymer in the interior region of a hair shaft. Without being bound by theory, it is believed that the polymer on the outer surface of the hair shaft should be washed away more easily, whereas the polymer inside the hair shaft, e.g. under the cuticle, will be better protected and thus substantially more durable. As described in detail herein, fig. 1 and 2 show polymers formed from active materials used in the present invention.

Features and other related components of the methods according to the first and other aspects are described in detail below.

The methods of the invention include, as described herein, (i), (ii), and (iii), which indicate a specific order, i.e., (i) then (ii) then (iii).

The method of the present invention comprises applying an oxidizing formulation to the hair. The oxidizing agent includes an oxidizing agent. The oxidizing agent may be selected from: peroxides, preferably hydrogen peroxide; persulfates, preferably potassium persulfate or sodium persulfate; and mixtures thereof. The other composition or formulation, or a plurality thereof, may comprise at least one oxidizing agent, as described herein. In one embodiment, the monomer composition does not comprise an oxidizing agent. In one embodiment, the oxidizing formulation is substantially free of hair colorant, or substantially free of oxidative and/or direct dyes.

The amount of the oxidizing agent may be from about 0.01% to about 15% by total weight of the composition/formulation. When a persulfate oxidizer is used, it may be in powder form and mixed as a liquid immediately prior to application to the hair. The final level of persulfate in the composition/formulation may be from about 0.5% to about 2%, more preferably from about 0.8% to about 1.2%, by total weight of the composition/formulation. When the oxidizing agent is a peroxide, the amount of the peroxide may be from about 0.5% to about 5%, preferably from about 1% to about 4%, more preferably from about 1.3% to about 3%, most preferably from about 1.5% to about 3%, by total weight of the composition or formulation.

In one embodiment, the oxidizing formulation is allowed to remain on the hair for a period of time y after application of the oxidizing formulation to the hair but before dewetting the hair, wherein the period of time y is from about 1min to about 120min, preferably from about 2min to about 45min, more preferably from about 3min to about 20min, and most preferably from about 4min to about 10 min.

When the oxidizing formulation comprises a peroxide, the oxidizing formulation may comprise a buffer system to stabilize the pH. Suitable buffers may also function as chelating agents. The chelation of transition metals, such as copper or iron from pipes, which may be present in tap water in trace amounts, is important because peroxides are readily cleaved by transition metals. In the absence of a buffer system, the transition metal can cleave the peroxide, deactivating it.

Typical buffer systems comprise a strong acid and its weak conjugate base or a weak base and its conjugate acid. Examples of suitable buffer systems are phosphoric acid and disodium phosphate. Another example of a suitable buffer system is citric acid and sodium hydroxide. In one embodiment, the monomer composition comprises a buffer system.

The method of the present invention comprises dewetting hair. In one embodiment, dewetting hair comprises applying an absorbent material to hair such that moisture is transferred from the hair to the absorbent material and wherein the moisture comprises a cosmetically acceptable carrier. The absorbent material may be selected from: towels, absorbent paper, and combinations thereof. In one embodiment, dewetting hair comprises allowing moisture to evaporate from the hair, wherein the moisture comprises a cosmetically acceptable carrier. In one embodiment, dewetting the hair includes towel drying the hair so that the oxidizing formulation no longer drips from the hair. In one embodiment, dewetting hair includes removing surface oxidizing agents from the hair. In one embodiment, dewetting the hair does not include rinsing the oxidizing formulation from the hair. The hair may be dewetted for a time z, wherein time z is from about 1min to about 120min, preferably from about 2min to about 45min, more preferably from about 3min to about 20min, most preferably from about 4min to about 10 min.

The method of the present invention comprises applying the monomer composition to the hair. The monomer composition includes an ethylenic monomer having a molecular weight of about 500g/mol or less. In one embodiment, the ethylenic monomer is selected from: mesaconic acid, 2-pentenoic acid, tiglic acid ester, furan-3-acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, maleamic acid, 3-aminocrotonic acid, crotonate, itaconic anhydride, trimethylsilyl acrylate, poly (ethylene glycol) acrylate, N-vinylacetamide, 2-acetamidoacrylic acid, vinylsulfonic acid, tetrahydrofurfuryl acrylate, N-methyl-N-vinylacetamide, vinyl propionate, vinylanisole, vinyl crotonate, methyl 3-hydroxy-2-methylenebutyrate, methacryloyl-L-lysine, N- (2-hydroxypropyl) methacrylamide, 2-acrylamidodiglycolic acid, methacrylic acid, maleic acid ester, 3-aminocrotonic acid ester, itaconic anhydride, trimethylsilyl acrylate, poly (ethylene glycol) acrylate, N-vinylacetamide, 2-acetamidoacrylic acid, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, N-isopropyl methacrylamide, 2-aminoethyl methacrylate, 2-bromoethyl acrylate, propyl 3- (dimethylamino) acrylate, (3-acrylamidopropyl) trimethylammonium salt, [2- (acryloyloxy) ethyl ] -trimethylammonium salt, alkyl acetamidoacrylate, sulfoalkyl (meth) acrylate, 3-sulfopropyl methacrylate, and salts, isomers, derivatives and mixtures thereof. In one embodiment, the monomer composition comprises at least one ethylenic monomer selected from the above-exemplified as the sole ethylenic monomer. In one embodiment, the ethylenic monomer is selected from the group consisting of 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and salts, derivatives, and mixtures thereof. In one embodiment, the only ethylenic monomer present is selected from the group consisting of 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and salts, derivatives, and mixtures thereof. In one embodiment, the only ethylenic monomer is 3-sulfopropyl acrylate. In one embodiment, the ethylenic monomer is 3-sulfopropyl acrylate, which is added to the composition as the potassium salt of 3-sulfopropyl acrylate.

In another embodiment, the ethylenic monomer is selected from: acrylic acid, sodium acrylate, potassium acrylate, calcium acrylate, monoethanolamine acrylate, 3-hydroxypropyl acrylate, 2, 5-butylaminoethyl acrylate, methacrylic acid, sodium methacrylate, potassium methacrylate, calcium methacrylate, monoethanolamine methacrylate, 2-N, N-dimethylaminoethyl acrylate, glycidyl methacrylate, 2-dimethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2, 4-dihydroxybutyl methacrylate, 2, 3-epoxybutyl methacrylate, 2-tert-butylaminoethyl methacrylate, 2- (2-diethylamino) ethyl methacrylate, ethylene glycol monomethacrylate, ethylene glycol, Itaconic acid (and salts thereof), vinylpyridine, resorcinol, and mixtures thereof.

The molecular weight of the ethylenic monomer is important because it is desirable for the monomer to penetrate into the hair shaft prior to polymerization. Large and/or bulky monomers will be less likely to penetrate into the hair shaft. In one embodiment, the ethylenic monomer has a molecular weight of about 50g/mol to about 500g/mol, preferably about 75g/mol to about 400g/mol, more preferably about 100g/mol to about 400g/mol, and even more preferably about 150g/mol to about 300 g/mol. In one embodiment, the ethylenic monomer does not have a molecular weight of less than about 50g/mol, preferably less than about 75g/mol, more preferably less than about 100g/mol, even more preferably less than about 150g/mol, nor more than about 500g/mol, preferably also not more than about 400g/mol, even more preferably also not more than about 300 g/mol.

The amount of the ethylenic monomer may be from about 0.1% to about 20%, preferably from about 1% to about 15%, more preferably from about 5% to about 14%, even more preferably from about 7% to about 13%, and most preferably from about 11% to about 12.5%, by total weight of the monomer composition.

In one embodiment, two or more different ethylenic monomers are present in the monomer composition. The resulting polymer may be a copolymer.

In one embodiment, the monomer composition is substantially free of oxidizing agents and/or initiators. In another embodiment, the monomer composition is substantially free of an oxidizing agent selected from the group consisting of: peroxides, preferably hydrogen peroxide; persulfates, preferably potassium persulfate or sodium persulfate; and mixtures thereof. In another embodiment, the monomer composition is substantially free of α -methylene lactone compounds.

In another embodiment, the monomer composition is in a ready-to-use form, which means that no pre-mixing is required prior to application to the hair. In another embodiment, the monomer composition is substantially free of at least one of: reducing agent and transition metal.

According to the first aspect, the method may further comprise one or more of the following steps: allowing the monomer composition to remain on the hair for a time x, wherein the time x is from about 1min to about 120 min; rinsing the hair; the hair is washed. The time x may be from about 5min to about 100min, more preferably from about 10min to about 90min, most preferably from about 20 to about 60 min.

A composition or formulation as described herein, or a plurality thereof, comprising a cosmetically acceptable carrier. The composition or formulation, e.g., a monomeric composition or an oxidative formulation, may comprise from about 60% to about 99.9%, alternatively from about 70% to about 95%, alternatively from about 80% to about 90%, of a cosmetically acceptable carrier, based on the total weight of the composition or formulation. Suitable cosmetically acceptable carriers include, for example, those used in the preparation of tonics and gels. Cosmetically acceptable carrierMay comprise water; silicones such as volatile silicones, amino or non-amino silicone gums; organic compounds such as C_2-C₁₀Alkanes, acetone, methyl ethyl ketone, volatile organic C₁-C₁₂Alcohol, C₁-C₂₀Acid with C₁-C₈Esters of alcohols such as methyl acetate, butyl acetate, ethyl acetate and isopropyl myristate, dimethoxyethane, diethoxyethane, C₁₀-C₃₀Fatty alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol; c₁₀-C₃₀Fatty acids such as lauric acid and stearic acid; c₁₀-C₃₀Fatty amides such as lauric acid diethanolamide; c₁₀-C₃₀Fatty alkyl esters such as C₁₀-C₃₀Fatty alkyl benzoates; hydroxypropyl cellulose, and mixtures thereof. In one embodiment, the carrier comprises water, fatty alcohols, volatile organic alcohols, and mixtures thereof. In a most preferred embodiment, the carrier is water.

The monomer composition may also include a cross-linking agent having a molecular weight suitable for penetrating the hair shaft. The purpose of the cross-linking agent is to covalently bond the monomer to the hair, the monomer to other monomers, and the polymer to other polymers.

The molecular weight of the crosslinking agent can be about 500g/mol or less, preferably about 100g/mol to about 500g/mol, more preferably about 100g/mol to about 400g/mol, and even more preferably about 150g/mol to about 400 g/mol.

The cross-linking agent may be selected from: 1, 4-bisacrylpiperazine, methylenebisacrylamide, vinylbisacrylamide, divinylbenzene, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bis [2- (methacryloyloxy) ethyl ] phosphoric acid, N' -bis (acryloyl) cystamine, N-diallylacrylamide, triallyl cyanurate, 3- (acryloyloxy) -2-hydroxypropyl methacrylate, and mixtures thereof.

In one embodiment, the ratio of the weight percent of the ethylenic monomer to the weight percent of the crosslinker (i.e., ethylenic monomer: crosslinker) is from about 50:1 to about 10:1, alternatively from about 40:1 to about 10:1, alternatively from about 20:1 to about 10: 1.

The present invention relates to compositions for chemically modifying the internal region of a hair shaft. In one embodiment, the chemical modification is selected from: forming a polymer in the interior region of the hair shaft; modifying the internal region of the hair shaft with a polymer; and combinations thereof. In one embodiment, the polymerization that occurs is a free radical polymerization.

In one embodiment, the at least one performance benefit as described herein provided by the present invention remains significant to at least about 40% of consumers, preferably to at least 45% of consumers, more preferably to at least 50% of consumers, even more preferably to at least 55% of consumers, most preferably to at least 60% of consumers, optimally to at least 65% of consumers, even more optimally to at least 70% of consumers after about 15 washes. In one embodiment, the consumer is selected from: consumers who regularly style their hair and have thin and/or soft hair, and consumers who regularly style their hair and have thick and/or non-compliant hair.

The composition or formulation as described herein, or a plurality thereof, may further comprise a monomer which does not penetrate into the interior region of the hair shaft, which will be referred to hereinafter as an impermeable monomer. Reasons for non-penetration include hydrophobicity, insolubility, too large a molecular weight, i.e., greater than about 500g/mol, and highly reactive monomers that may polymerize before reaching the hair shaft. It thus implies that such impermeable monomers cannot chemically modify the internal region of the hair shaft. However, the impermeable monomer may be able to chemically modify the outer surface of the hair shaft and such modification may be able to withstand multiple washes and shampoos. Such external modification may enhance the benefits of the present invention. Impermeable monomers include those of cyano-acrylate chemistries and reactive siloxanes. Such impermeable monomers include those disclosed in US7357921B2, US7780742, US 7740664.

The compositions and formulations as described herein, or a plurality thereof, may further comprise a viscosity-increasing means selected from viscosity-increasing agents and viscosity-increasing systems. The viscosity is important when the composition is in the form of a gel, cream, lotion, emulsion, etc., as it prevents the composition from falling off the hair. However, the lower viscosity allows the active substance to penetrate/diffuse into the interior region of the hair shaft. Viscosity of the composition when it is in gel form: preferably from about 500 mPas to about 7000 mPas, more preferably from about 1000 mPas to about 5000 mPas, even more preferably from about 1500 mPas to about 4500 mPas, most preferably from about 1900 mPas to about 4000 mPas, as measured at 25 ℃ and 1rpm with a Brookfield viscometer RVDV III Ultra CP 52.

The viscosifying agent may be selected from the group consisting of nonionic, cationic, anionic, zwitterionic, and mixtures thereof; nonionic thickeners, anionic thickeners, and mixtures thereof are preferred. The tackifier may be present in the composition in an amount of from about 0.1% to about 10%, preferably from about 0.2% to about 5.0%, by total weight of the composition.

Due to the typical anionic chemistry of the polymerized ethylenic monomer, nonionic or anionic thickeners (or mixtures thereof) are preferred for the monomer composition. Nonionic or anionic thickeners are less prone to interact directly with the polymer formed and are thus also less prone to form insoluble complexes or precipitates. The viscosity building means is also preferably stable at the desired pH and does not substantially affect the level of activity of the ethylenic monomer. The adhesion promoter may be a crosslinked or non-crosslinked polymer.

In one embodiment, the tackifier is a hydrophobically modified polyacrylate polymer. Such hydrophobically modified polyacrylate polymers are particularly suitable when the composition/formulation is produced by addition of at least one salt. The monomer composition may comprise from about 0.5% to about 1.5% of the hydrophobically modified polyacrylate polymer, by total weight of the monomer composition. Suitable hydrophobically modified polyacrylate polymers include: acrylate/C10-C30 alkyl acrylate copolymers, e.g. from LubrizolAnd from LubrizolAcrylate/behenyl polyether-25 methacrylate copolymers, e.g. from Rohm&Of Haasacrylate/Hexadecylethenoxy ether-20 itaconate copolymers, e.g. from Akzo Nobel3001 or 2001.

In one embodiment, the viscosifier is a non-crosslinked associative thickening polymer. The monomer composition may comprise from about 0.5% to about 3% of the non-crosslinked associative thickening polymer, by total weight of the monomer composition. Suitable associative thickeners include polyurethane-based polymers such as polyurethane-30, e.g., available from BASF. And EO-PO block copolymers, e.g. from BASF, may also be used

In one embodiment, the viscosifier comprises at least one polysaccharide, preferably at least one heteropolysaccharide. The total polysaccharide amount in the monomer composition may be from about 0.2% to about 5%, more preferably from about 0.5% to about 4%, by total weight of the monomer composition. Suitable polysaccharides and heteropolysaccharides include starch and its derivatives, such as mono-or diesters of phosphoric acid, cellulosics and their derivatives, xanthan gum, carrageenan. Preferred heteropolysaccharides include xanthan gums such as those available from KelcoT, and from Herkules250 HHR. In one embodiment, the polysaccharide is selected from the group consisting of hydroxyethylcellulose, hydroxypropylcellulose, xanthan gum, carrageenan, and mixtures thereof. The amount of xanthan gum and its derivatives is from about 0.2% to about 1.5%, more preferably from about 0.5% to about 0.9%, by total weight of the monomer composition. The amount of starch and its derivatives is from about 3% to about 4% by total weight of the monomer composition. A preferred Starch is hydroxypropyl Starch phosphate, e.g., available from National StarchXL. In one embodiment, the monomer composition comprises two different heteropolysaccharide tackifiers.

In one embodiment, a viscosity increasing system is used. The tackifying system may use a tackifier as defined above. Alternatively or additionally, the viscosifying system comprises a non-polymeric system that provides internal structure to the product. The non-polymeric system is selected from: preferably a surfactant system comprising lauryl ether sulfate plus sodium chloride; liquid crystal systems such as cationic conditioners made from fatty alcohols plus cationic surfactants; water-in-oil (w/o) type emulsions; oil-in-water (o/w) type emulsions; inorganic thickening systems such as bentonite, montmorillonite. In another embodiment, the viscosifying system is free of polymeric viscosifying agents or polymeric thickeners.

In one embodiment, a composition or formulation as described herein, or a plurality thereof, may comprise a cation, wherein the cation is selected from inorganic cations having a charge density of about 0.05 charge/pm or greater, preferably about 0.052 charge/pm. In one embodiment, the inorganic cation is a metal. In one embodiment, the cations may not be selected from inorganic cations having a charge density of about 0.04 charge/picometer or less, preferably less than about 0.05 charge/picometer. In one embodiment, the cations are selected from inorganic cations having a charge density of from about 0.050 to about 0.090, preferably from about 0.052 to about 0.080, more preferably to about 0.070, even more preferably to about 0.060, and most preferably to about 0.053 charges per picometer.

The presence of inorganic cations having a charge density of about 0.05 charge/picometer or greater in the monomer composition and/or oxidizing formulation of the present invention results in superior performance. Without being bound by theory, it is believed that the inorganic cation is capable of binding to the plurality of anionic ethylenic monomers due to its positive charge when the ethylenic monomer is a unit of a polymer, either when it is not polymerized or when it is polymerized. For example, the inorganic cation can be bound to two or more different polymer chains simultaneously carrying an anionic charge. The beneficial effects of this combination include: the increased sequestration of the ethylenic monomer and the closer proximity of the polymers to each other results in longer polymer chains and/or ionic crosslinking of adjacent polymer segments after polymerization. Inorganic cations with higher charge density are able to bind and compete with any other cations with lower charge density for negatively charged binding sites.

The charge density of an ion is calculated by dividing the charge by the radius of the ion, which yields the charge density in units of charge per picometer. For example, Sr²⁺Has an ionic radius of 127pm, and a charge of 2. Thus, the charge is 0.0157 charges/pm per picometer. A table of ionic radii can be found in common textbooks of inorganic Chemistry, such as Atkins p.w., Physical Chemistry, 6 th edition, 2001. The ionic radii of commonly used metals can be found in table I.

TABLE I

Metal	Electric charge	Picometer (pm) per charge	Charge Density (Charge/pm)	Radius of ion (pm)
					K(I)	1+	133.00	0.0075	133
Cd(I)	1+	114.00	0.0088	114
					Na(I)	1+	98.00	0.0102	98
Cu(I)	1+	96.00	0.0104	96
					Li(I)	1+	78.00	0.0128	78
Ba(II)	2+	71.50	0.0140	143
					Sr(II)	2+	63.50	0.0157	127
Ca(II)	2+	53.00	0.0189	106
					Cd(II)	2+	51.50	0.0194	103
Sn(II)	2+	46.50	0.0215	93
					Mn(II)	2+	45.50	0.0220	91
Ge(II)	2+	45.00	0.0222	90
					Ag(II)	2+	44.50	0.0225	89
Cr(II)	2+	42.00	0.0238	84
					Zn(II)	2+	41.50	0.0241	83

Fe(II)	2+	41.00	0.0244	82
					Co(II)	2+	41.00	0.0244	82
La(III)	3+	40.67	0.0246	122
					Ni(II)	2+	39.00	0.0256	78
Mg(II)	2+	39.00	0.0256	78
					Cu(II)	2+	36.00	0.0278	72
Ce(III)	3+	35.67	0.0280	107
					Au(III)	3+	30.33	0.0330	91
Ce(IV)	4+	23.50	0.0426	94
					Mn(III)	3+	23.33	0.0429	70
Fe(III)	3+	22.33	0.0448	67
					Zr(IV)	4+	21.75	0.0460	87
V(III)	3+	21.67	0.0462	65
					Cr(III)	3+	21.33	0.0469	64
Cr(III)	3+	21.33	0.0469	64
					Co(III)	3+	21.33	0.0469	64
NI(III)	3+	20.67	0.0484	62
					Al(III)	3+	19.00	0.0526	57
Sn(IV)	4+	18.50	0.0541	74
					Se(IV)	4+	17.25	0.0580	69
V(IV)	4+	15.25	0.0656	61
					Cr(IV)	4+	14.00	0.0714	56
Ge(IV)	4+	13.25	0.0755	53
					Mn(IV)	4+	13.00	0.0769	52
V(V)	5+	11.80	0.0847	59

Without being bound by theory, it is believed that adverse redox reactions with other hair treatment chemicals (e.g., permanent oxidative hair coloring, semi-permanent hair coloring, hair bleaching, permanent waving of hair) do not readily occur when the cations are less capable of losing or gaining electrons. If the inorganic cation is selected from metals that can exist in only two oxidation states other than oxidation state "0", more preferably only one oxidation state other than oxidation state "0", then adverse redox reactions are unlikely to occur-for example, copper can exist in only a total of three different oxidation states, i.e., Cu⁰、Cu¹⁺And Cu²⁺. For example, manganese can exist in only four different oxidation states in total, namely Mn⁰、Mn²⁺、Mn³⁺、Mn⁴⁺. For example, aluminum can exist in only two oxidation states, i.e., Al⁰And Al³⁺. In one embodiment, the inorganic cation has a charge of at least 2+, more preferably at least 3 +. In one embodiment, the inorganic cation is not a transition metal. In one embodiment, the inorganic cation is not a metal capable of cleaving hydrogen peroxide. In a preferred embodiment, the inorganic cation is Al³⁺。

The molar ratio of cation to monomer (i.e., cation: monomer) can be from about 1:10 to about 2:1, preferably from about 1:5 to about 3:2, more preferably from about 1:2 to about 1:1, and even more preferably from about 1:3 to about 1: 1. When the ethylenic monomer is added to the monomer composition in the form of a salt, the molar amount of the cation preferably exceeds the molar amount of the counterion of the ethylenic monomer.

The cation may also be present in the monomer composition, the oxidizing formulation, the finishing formulation, and/or combinations thereof. In one embodiment, the monomer composition and/or oxidizing formulation further comprises a cation, wherein the cation is not selected from inorganic cations having a charge density of about 0.04 charge/picometer or less, preferably less than about 0.05 charge/picometer. In one embodiment, the monomer composition and/or oxidizing formulation further comprises a cation and an anion; wherein the cation is selected from inorganic cations having a charge density of 0.05 charge/picometer or greater. In one embodiment, the oxidizing formulation comprises a cation, wherein the cation is selected from inorganic cations having a charge density of about 0.05 charge/picometer or greater, and the amount of the cation is from about 0.001% to about 2%, preferably from about 0.01% to about 1%, more preferably from about 0.04% to about 0.2%, by total weight of the oxidizing formulation.

In one embodiment, the composition or formulation, or a plurality thereof, may comprise an anion. The anion can be selected from the group consisting of sulfate, sulfonate, phosphate, nitrate, chloride, citrate, lactate, formate, and mixtures thereof. Preferred anions are selected from sulfate, sulfonate, and mixtures thereof. In the most preferred embodiment, the anion is sulfate.

In one embodiment, the molar ratio of cation to anion (cation: anion) is from about 1:5 to about 5:1, preferably from about 1:4 to about 3:1, and most preferably from about 2:3 to about 3: 2. Wherein the inorganic metal cation is Al³⁺And the anion is sulfate and the molar ratio of cation to anion is about 2: 3. The anion can be present in the monomer composition, the oxidizing formulation, the finishing formulation, or a combination thereof.

In one embodiment, a composition or formulation as described herein, or a plurality thereof, can be produced by addition via a salt. In one embodiment, a composition or formulation as described herein, or a plurality thereof, comprises a salt. The salt may comprise an anion and a cation having a charge density of about 0.05 charge/picometer or greater. In one embodiment, the salt may comprise an ethylenic monomer.

When applied directly to hair, the pH of the compositions and formulations of the present invention must be suitable for application to human hair, i.e., the compositions and formulations must be cosmetically acceptable. Furthermore, the pH of the present invention must be suitable to ensure that all components of the composition or formulation are dissolved and stable. The monomer composition may have a pH of about 2.0 to about 9.0. In one embodiment, the pH is from about 2.5 to about 7.5, preferably from about 4.0 to about 7.0, more preferably from about 4.0 to about 6.9. In one embodiment, the pH is from about 4.5 to about 6.7, preferably from about 5.0 to about 6.6, more preferably from about 5.2 to about 6.5, even more preferably from about 5.3 to about 6.5, most preferably from about 5.5 to about 6.5, optimally from about 5.5 to about 6.0. In one embodiment, the composition does not have a pH of about 7.0 or above.

As described herein, the composition or formulation, or a plurality thereof, may comprise at least one initiator. Preferred initiators include: peroxydisulfates, peroxides, peracids, perborates, peroxyesters, sodium peroxydisulfate, benzoyl peroxide, peracetic acid, azo initiators, and mixtures thereof. Transition metal catalysts or metal initiators that may exist in a total of three oxidation states other than oxidation state "0" are not suitable for use in the present invention. Preferably, the monomer composition is substantially free of transition metal catalysts or metal initiators that may be present in a total of three oxidation states other than oxidation state "0", more preferably the monomer composition is substantially free of transition metal catalysts or metal initiators that may be present in a total of two oxidation states other than oxidation state "0". In one embodiment, the initiator is provided to the hair via an energy delivery device by applying the device adjacent the scalp. Suitable initiators may include light energy.

After treatment with the monomer composition of the present invention, a finishing composition may be applied to the hair. The finishing composition may comprise a hair conditioning agent. Hair conditioners are generally cationic polymers that provide softness to hair or repair damaged hair. Conditioning polymers generally provide a smooth and non-tacky film on the hair. Typically, the conditioning polymer is cationic, but may also be nonionic, zwitterionic, and amphoteric. The hair conditioning agent may also be an oily and/or silicone compound. Patent application WO2009/107062a2 discloses conditioning agents and cationic polymers, which may be suitable for finishing formulations as described herein. Also potentially suitable for use in the compositions herein are conditioners described by Procter & Gamble Company in U.S. patents 5,674,478 and 5,750,122. Also potentially suitable for use herein are those described in U.S. Pat. Nos. 4,529,586 (Clairol), 4,507,280 (Clairol), 4,663,158 (Clairol), 4,197,865 (L 'Oreal), 4,217,914 (L' Oreal), 4,381,919 (L 'Oreal), and 4,422,853 (L' Oreal).

In one embodiment, the finishing formulation comprises an oxidizing agent. The amount of the oxidizing agent can be from about 0.01% to about 15% by total weight of the finishing formulation.

A composition or formulation as described herein, or a plurality thereof, may comprise a reducing agent, which may be used to reduce disulfide bonds and improve penetration into the hair shaft. Examples of suitable reducing agents include, but are not limited to, sodium thioglycolate, anhydrous sodium thiosulfate, powdered sodium metabisulfite, thiourea, ammonium sulfite, thioglycolic acid, thiolactic acid, ammonium thiolactate, glycerol monothioglycolate, ammonium thioglycolate, thioglycerol, 2, 5-dihydroxybenzoic acid, diammonium dithiodiethanoate, strontium thioglycolate, calcium thioglycolate, zinc formaldehyde sulfoxylate, isooctyl thioglycolate, D/L-cysteine, monoethanolamine thioglycolate, phosphines, and mixtures thereof.

The reducing formulation comprises a reducing agent, and wherein the reducing formulation can be packaged separately from other compositions or formulations. The reducing formulation may comprise from about 1% to about 12%, alternatively from about 4% to about 10%, alternatively from about 8% to about 10%, of the reducing agent by total weight of the reducing formulation.

The compositions or formulations as described herein, or a plurality thereof, may further comprise one or more optional components known or otherwise effective for use in hair care or personal care products, provided that the optional component is physically and chemically compatible with the essential components described herein, or does not otherwise unduly impair product stability, aesthetics or performance. Non-limiting examples of such optional components are disclosed in International Cosmetic Ingredient Dictionary, ninth edition, 2002, and CTFAcosmetic Ingredient Handbook, tenth edition, 2004, both of which are incorporated herein by reference in their entirety. Some non-limiting examples of such optional components are disclosed below and include plasticizers, surfactants (which may be anionic, cationic, amphoteric or nonionic), neutralizing agents, propellants, hair conditioning agents (e.g., silicone fluids, fatty esters, fatty alcohols, long chain hydrocarbons, cationic surfactants, etc.), emollients, lubricants and penetrants, such as various lanolin compounds, vitamins, proteins, preservatives, dyes, hair dyes, bleaches, reducing agents and other colorants, sunscreens, gelling agents, physiologically active compounds for treating hair or skin (e.g., anti-dandruff actives, hair growth actives), non-polymeric thickeners, including clays and perfumes.

Oily compounds may help the ethylenic monomer penetrate into the skin and/or scalp, which is not preferred. In one embodiment, the monomer composition is substantially free of oily compounds. In another embodiment, the monomer composition and oxidizing formulation are substantially free of oily compounds.

The monomer composition of the present invention may have various product forms. It may be in a form selected from a gel, an emulsion, a cream, a spray, a lotion or a mousse. Preferred forms are gels, creams or lotions, more preferably gels, most preferably the monomer composition is in the form of a gel having the appearance of an emulsion. The oxidising formulation may be in the form of a gel, emulsion, cream, spray, lotion, mousse. The most preferred form of oxidizing formulation is a lotion.

According to a first aspect, applying the oxidising formulation to the hair takes place before applying the monomer composition to the hair.

In one embodiment, the method comprises providing a monomer composition to a stylist and/or consumer, wherein the stylist and/or consumer does not need to premix the monomer composition with a second formulation prior to applying the monomer composition to the hair. The second formulation may be selected from: reducing agents, pH adjusting agents, salt agents, initiator agents, oxidizing agents, catalyst agents, and combinations thereof; salt formulations, oxidizing formulations, initiator formulations, and mixtures thereof are preferred.

In one embodiment, during time x, the hair is exposed to heat. In one embodiment, during time x, the hair is exposed to at least about 70% relative humidity within about 1 hour of applying the monomer composition, and the exposure lasts from about 10 to about 90 minutes. Means for applying said relative humidity comprise, for example: hairspa ION from Wella, Darmstadt, Germany; electronic Master Ionic Action from Muster; BlitzSuper Electronic ozano from Ceriotti; beautivap Digital Ozon and OzonoEnergy, available from Areem; mega ozano, from MediaLine; mod.370, from bmp; steam Machine, available from REM; micro Mist (SD 200 NIW) and Belmester (BM-975), available from Takara Belmont. Suitable devices are described in EP 1871194.

The method according to the first aspect may further comprise providing and applying to the hair a hair care and/or hair styling composition. Additionally or alternatively, it may comprise providing and using a tool for applying a styling effect to the hair. The hair care and/or hair styling composition may comprise a hair care and/or hair styling active and a cosmetically acceptable carrier, as described herein. The hair care and/or hair styling actives may be selected from hair styling polymers; conditioning agents, especially cationic polymers; detergents, especially surfactants; a thickener; a glazing agent; a gloss imparting agent; a dye or color-imparting agent; glitter or colored particles; a siloxane; and mixtures thereof. The hair care and/or styling composition may be selected from waxes; gelling; a hair spray; mousse; conditioning compositions, especially leave-on conditioning compositions; finishing the spray; glazing or gloss imparting products; and mixtures thereof. The tool may be selected from a hair dryer; straight hair irons, combs, brushes, curlers, curling tongs, electric hair curling devices, foils, scissors, clips, hair bands, and mixtures thereof.

In another embodiment, the present invention relates to a method for chemically modifying the internal region of a hair shaft, wherein said method comprises:

(i) applying an oxidizing formulation to hair, wherein the oxidizing formulation comprises from about 1% to about 4% hydrogen peroxide by total weight of the oxidizing formulation;

(ii) removing moisture from the hair;

(iii) applying a monomer composition to hair, wherein the monomer composition comprises: an ethylenic monomer having a molecular weight of about 500g/mol or less; a cosmetically acceptable carrier; an anion; and a cation, wherein the cation is selected from inorganic cations having a charge density of about 0.05 charge/picometer or greater.

(i) applying an oxidizing formulation to hair, wherein the oxidizing formulation comprises: from about 1% to about 4% hydrogen peroxide by total weight of the oxidizing formulation; an anion; and a cation, wherein the cation is selected from inorganic cations having a charge density of about 0.05 charge/picometer or greater;

(ii) removing moisture from the hair;

(iii) applying a monomer composition to hair, wherein the monomer composition comprises: from about 5% to about 14%, by total weight of the monomer composition, of an ethylenic monomer having a molecular weight of about 500g/mol or less; and a cosmetically acceptable carrier.

In another embodiment, wherein after chemical modification, the hair exhibits at least one benefit selected from the group consisting of enhanced style retention, enhanced style durability, increased apparent volume, enhanced moisture resistance, and combinations thereof.

In another embodiment, wherein after chemical modification, the hair exhibits increased hair shaft density and/or hair shaft elasticity.

According to a second aspect, the present invention relates to a kit comprising:

(a) instructions for use comprising the method according to the first aspect;

(b) a monomer composition.

In one embodiment, the kit further comprises an oxidising formulation according to the first aspect, which is packaged separately from the monomer composition. Another embodiment relates to a kit comprising:

(a) instructions for use comprising the method according to the first aspect;

(b) a product comprising the monomer composition according to the first aspect;

(c) a product comprising an oxidizing formulation, wherein the oxidizing formulation comprises from about 0.01% to about 15% of an oxidizing agent, by total weight of the oxidizing formulation.

(d) A product comprising a formulation that is different from the monomer composition and the oxidizing formulation, wherein the formulation is a hair treatment selected from the group consisting of oxidizing formulations, finishing formulations, reducing formulations, hairstyling formulations, finishing formulations, conditioning formulations, shampoo formulations, coloring formulations, and combinations thereof.

Another embodiment of the second aspect relates to a kit according to the second aspect, wherein the kit further comprises one or more of the following:

(e) a tool;

(f) provided is a device.

Another aspect relates to the use of a kit according to the second aspect for increasing hair shaft density and/or hair shaft elasticity.

Another aspect relates to the use of a monomer composition for increasing hair shaft density and/or hair shaft elasticity, wherein the monomer composition comprises an ethylenic monomer having a molecular weight of about 500g/mol or less, and a chemically acceptable carrier. The specific embodiments of the monomer composition described above may be applied to this aspect with necessary modifications.

According to another aspect, the present invention also relates to an article of commerce comprising at least one composition or formulation, or a plurality thereof, as described herein, and information relating to the composition and/or formulation. The information may be printed material attached directly or indirectly to a package containing at least one composition and/or formulation according to the present invention. Alternatively, the information may be electronic or broadcast information associated with the hair styling device and/or composition and/or preparation. The information may include a photograph comparing the appearance of a person prior to use of the formulation and/or article with the appearance of the same person after use of the formulation and/or article.

According to another aspect, the present invention comprises a method of marketing a kit comprising an oxidizing formulation and a monomer composition as described herein, wherein the marketing method comprises the steps of obtaining the kit to a consumer, and providing a message to the consumer. The information is: the compositions may provide one or more benefits to the hair, including but not limited to increased hair volume appearance, enhanced hair moisture resistance, increased ease of styling, and/or enhanced style retention. Examples include the day-long hold of a hair style, excellent curl definition, increased body and/or fullness, the ability to curl straight hair, and/or the ability to straighten curls.

¹ H-NMR analysis

Can be used¹H-NMR tracks the kinetics of free radical polymerization of ethylenic monomers in aqueous media. For example, polymerization of potassium 3-sulfopropyl acrylate is shown in reaction X below.

Reaction X

The determination of the conversion can be made by comparing the signal of residual (unpolymerized) ethylenic monomer to the signal of a reference added to the reaction mixture prior to the start of the reaction, and/or by comparing the signals derived from both the polymer and the ethylenic monomer. Triethylene glycol and sodium benzenesulfonate can be used as inert references. The transitions are derived by comparing integrals. When an inert reference is added, the transformation can be calculated according to equation a:

formula A

Wherein i_Sheet: integration of the signal from the ethylenic monomer; n is_{H, sheet}: the number of H atoms in the signal from the ethylenic monomer; x_Sheet: the amount of ethylenic monomer, on a molar basis, prior to the start of the reaction; i.e. i_{Reference to}: integration of the signal from the reference; n is_{H, reference}: the number of H atoms in the signal from the reference; x_{Reference to}: amount of reference, in moles.

For calculating the transition by comparing the signal of the residual ethylenic monomer to the signal of the mixed ethylenic monomer and polymer, equation B can be used:

formula B

Wherein i_Sheet: integration of the signal from the ethylenic monomer; n is_{H, sheet}: the number of H atoms in the signal from the ethylenic monomer; i.e. i_Mixing: integration of the mixed signals from the ethylenic monomer and the polymer; n is_{H, mixing}: the number of H atoms in the mixed signal from the ethylenic monomer and the polymer.

The following experimental procedure can be used: the ethylenic monomer and additives (as appropriate) in a round bottom flask equipped with a silicone stopper were dissolved in 18ml of an appropriate solvent (buffer with or without added salt, or ultra-pure deionized water). Buffers that can be used for the experiments at ph5.8 were prepared as follows: 119.2mg of NaH₂PO₄And 141.9mg of Na₂HPO₄Dissolved in 110ml of ultrapure water and then adjusted to a pH of 5.8 by addition of dilute phosphoric acidAnd (4) final value. The required amount of initiator is some milliliters dissolved in some solvent (the precise amount of solvent is individually adjusted to bring the total weight of the reaction mixture to 25.0 g). The reaction temperature was adjusted by means of an oil bath with a contact thermometer. The reaction was started by transferring the initiator solution to the reaction mixture with a syringe. In the case where no initiator was used, the flask with the raw materials was kept outside the oil bath before the reaction and the moment of contact with the oil bath was taken as the starting point. At defined time points, 3.0ml samples were withdrawn with a syringe. To stop the reaction, the samples were immediately exposed to air and 0.100g of hydroquinone was added. Freeze-drying and using the samples respectively¹H-NMR spectroscopic analysis was used to determine the conversion.

For example, the structure of 3-sulfopropyl acrylate potassium salt is indicated in formula I below, where H₁The positions of the hydrogen atoms that can be analyzed by NMR are indicated.

Formula I

Signals at 6.5 to 6.4ppm (parts per million) correspond to H in residual ethylenic monomer₁An atom. The signals at 3.8 to 3.6ppm correspond to 12H atoms in triethylene glycol. The signals at 4.4 to 4.2ppm correspond to the mixed signal.

Using this technique, fig. 1 shows the conversion of an ethylenic monomer species to a polymer species. The y-axis labeled "C" shows the conversion in mole percent of the ethylenic monomer, and the x-axis labeled "t" shows the time in minutes. In the experiment labeled "Sr", the monomer composition contained 5.0% (by weight) SrCl₂. In the experiment labeled "Al", the monomer composition contained 2.4% (by weight) Al₂(SO₄)₃x18(H₂O) aluminum sulfate octadecahydrate. Both experiments were performed as follows: using 2.00g of 3-sulfoPropyl acrylate as an alkenyl monomer, 1.0% (by weight) Na was used at pH5.8 at 20 ℃ in the presence of oxygen₂S₂O₈As initiator, 127mg of cysteine hydrochloride in a molar ratio of 1:1 to initiator were used, C₆H₅SO₃Na as reference and no hair present.

The conclusions drawn from fig. 1 include that polymerization occurred such that almost all of the ethylenic monomer was converted and that there was only a slight difference in reaction kinetics when comparing compositions comprising aluminum and strontium cations.

GPC analysis

The molar weight of the polymer obtained from the polymerization of the ethylenic monomer can be obtained by conventional GPC in aqueous (anionic) solution. The GPC apparatus includes a single channel degassing System [ WGE-Dr]Isocratic pump [ P1000 from Spectra Physics]GPC-liquid at a flow rate of 1.0 ml/min-0.1 mol/l NaNO₃Autosampler AS1000 from Spectra Physics, sampling 100. mu.l, PSSSUPREMA column (1) Guard (8X 50 mm), (2) Suprema3000A (8X 300 mm; 10. mu.m), (3) Suprema1000A (8X 300 mm; 10. mu.m), (4) Suprema100A (8X 300 mm; 10. mu.m), TECHNLAB GmbH, column oven K-7 from Germany [ at T =30 ℃]UV-Detector UV2000 from Spectra Physics, WGE Dr. Bures, RI-Detector refractometer SEC-2010 from Germany. Calibration was performed with pullulan standards covering the molecular weight range of 0.3 to 710 kDa. Data analysis was performed using software WinGPCUnity provided by PPS.

The GPC data is shown in fig. 2. The x-axis, denoted by the label "a", is the molecular weight in daltons (Da). The y-axis, denoted by the label "b", is intensity. I = according to the invention (dashed line notation); c = control, i.e. not according to the invention (cross-marking). It is known in the art that the molecular weight of the resulting polymer is inversely proportional to the square root of the initial radical concentration, in this case the radical being an ethylenic monomer that has been activated by an initiator. Therefore, it is important to understand the kinetics of consumption of the ethylenic monomer to obtain reliable results from GPC dataAnd (4) concluding. Thus, the applicant utilizes¹H-NMR to follow the kinetics of the conversion of the ethylenic monomer. The conclusions drawn from fig. 2 thus include that monomer compositions comprising aluminum cations result in higher molecular weight polymers relative to monomer compositions comprising strontium cations.

¹⁴ C-experiment: moiety I

The aim of this study was to investigate the polymerization of 3-sulfopropyl acrylate (3-SPA) occurring within the hair. Using 3-SPA¹⁴C-reflective marker version (C-atom of marker:):

the process comprises the following steps: a tress of exactly 20 hair fibers was bleached twice. With common 3-SPA or¹⁴The C-tagged version treats the hair strand. The kind of treatment was according to the following method: (1) with pretreatment formulation (2% H)₂O₂) Treating for 10 minutes; (2) "towel" dry (tissue paper); (3) treatment with 3-SPA in water or in a hair treatment formulation for 30 minutes; (4) optionally rinsed with water. The following exact procedure was performed for each specific strand:

in hair beam by autoradiography¹⁴And (3) detecting C-SPA. The hair tresses were cut to a length of 1.5cm and cross sections of the tresses were exposed to the silver halide photographic emulsion in a dark room for 4 weeks. The film was developed and a photograph thereof was taken using a microscope. The beta particles convert the silver halide to metallic silver, which can be observed as black dots. The results are shown in the following table and in fig. 3.

Explanation and discussion: all hair tresses treated with the labeled 3-SPA clearly show that the radioactive material penetrates not only into the epidermis but also a substantial portion of the cortex of the hair. The most widespread homogeneous distribution (circular) is also seen. Even more convincing than the high concentration of silver particles is that they accumulate in the outer half of the diffusion channel. All the photographs show a preferential accumulation outside the cortex, but for strand D there is a borderline even in the visible area of the inner cortex. This gives a strong suggestion that the silver particles really represent the percolation behavior of the 3-SPA monomer, rather than artefacts, for example due to the cutting process. From the photograph of fig. 3 above, it is less apparent that the result is not affected by the washing. However, the expert opinion of this technique is that the rinsing step has only a low effect on the radioactivity inside the hair. This is another indication that the treatment of the present invention has not only a surface effect.

¹⁴ C-experiment: part II

The process comprises the following steps: optionally water in addition to the pretreatment according to (1); the treatment time with the monomer composition (step [3 ]) was increased to 24 h; and frequently, outside the rinsing (4), according to section I:

the following exact procedure was performed for each specific strand:

in hair beam by autoradiography¹⁴And (3) detecting C-SPA. The results are shown in the following table and in fig. 4.

Explanation and discussion: the experiment shows that₂O₂In all cases of pretreatment, there was radioactivity in the epidermis and cortex, however in the case of pretreatment with water only, the radioactivity would not be present in the epidermis, but still in the cortex. Other in vitro experiments showed that not only the monomer but also poly-3-SPA was water soluble. However, once it is dried, dissolving the polymer (several hours) takes significantly longer than dissolving the dried monomer (a few seconds). These data thus indicate that the difference in wash resistance is due to the polymerization level. By washing without H₂O₂All of the 20 hair fibers of each sample that had been pretreated lost radioactivity in its cuticle area, while all of the other samples retained radioactivity.

Hair density data

The amount of "add-on", i.e. the percentage change in hair weight after treatment, was measured. The switches were weighed on an analytical balance before and after treatment, and the difference was calculated as a percentage. For both weighings, the hair was in dry form. Twenty 2.5cm switches were permed and bleached 2 times before treatment. Then the application contains 2% H₂O₂For 5 minutes. The monomer composition was then applied at 45 ℃ for 30 minutes, wherein the monomer composition contained 12% 3-SPA. The switches were then washed with neutral shampoo and then applied with 2% H₂O₂The finishing formulation of (1). The tress was then air dried and weighed. The results of this addition experiment are shownAn average weight gain of 2.93% was obtained.

And the diameter of each hair fiber was measured with a laser micrometer. 25 individual hair fibers were taken from the same batch of european hair and their diameters were measured before or after the treatment according to the invention. The fibers were bleached twice before treatment. Administration contains 2% H₂O₂Using a monomer composition (containing 12% 3-SPA) and applying a composition containing 2% H₂O₂The finishing formulation of (1). For each fiber, the diameter was measured at multiple points along the length of the fiber, and the measurements of this diameter were averaged for each fiber-an average minimum diameter of about 60 microns and an average maximum diameter of about 86 microns were measured. In addition, the overall average of 25 fibers was also calculated. The result of these experiments was a very slight reduction in average hair diameter relative to untreated hair fibers-the average diameter of the untreated fibers was 73.2 microns (standard deviation 16.7 microns) and the average diameter of the treated fibers was 73.0 microns (standard deviation 16.6 microns).

Explanation and discussion: because there was an increased addition and a slight decrease in hair diameter, it was concluded that the density of the hair fibers was increased.

Consumer and stylist data

The invention was tested on the consumer. The consumer is selected according to his needs. Consumer group 1 includes consumers who desire fuller, larger volume and thicker hair because of their current softness and thin hair. Consumer group 2 includes consumers who desire hair with a smooth and more defined appearance because their hair is now thick and non-compliant.

In the test, each consumer received a treatment according to the invention on one half of his hair and a treatment not according to the invention on the other half. In all cases, the treatment was applied to the wetted hair. After the test is over, the two halves are compared by collecting feedback from the consumer and the stylist. The method of application to the half head of each consumer is shown in the table below with the designation table II.

TABLE II

In this study, a total of 47 consumers received the comparison method, with 26 from consumer group 1 and 21 from consumer group 2. A total of 20 consumers received method 1 of the present invention, with 10 from consumer group 1 and 10 from consumer group 2. A total of 27 consumers received method 2 of the present invention, with 16 from consumer group 1 and 11 from consumer group 2.

Immediately after their visit to the salon where the above method was applied, consumers were asked various questions about their hair, such as "do you feel your hair full? ". For each question, the consumer must select one of five unrelated answers: complete agreement, basic agreement, neither agreement nor objection, basic disagreement, and complete disagreement. For these questions, the percentage of consumers who answered "full consent" or "basic consent" to each half of the head was calculated. Another question is asked whether the beneficial effects of the treatment are they expected. For this question, a five point scale is also used, and the percentage of consumers who answer "over expectations", "fully meet expectations", or "substantially meet expectations" is calculated. The results of asking the above questions immediately after they visit the salon can be seen in table III below.

TABLE III

Consumer group 1	Comparison method	Method 2 of the invention	Consumer group 2	Comparison method	Method 2 of the invention
						Meet/exceed expectations	68%	88%	Meet/exceed expectations	70%	100%
Plump	68%	94%	Is smooth and smooth	87%	100%
						Is smooth and smooth	64%	88%	Gloss of	60%	92%
Health care	59%	75%	Health care	60%	83%
						High toughness	64%	75%	Garment for keeping fit	53%	83%

Four weeks after treatment, the same consumer was asked the same questions. The results of the above problem after four weeks of treatment can be seen in table IV below.

TABLE IV

Consumer group 1	Comparison method	Method 2 of the invention	Consumer group 2	Comparison method	Method 2 of the invention
						Meet/exceed expectations	59%	88%	Meet/exceed expectations	59%	83%
Easy to shape	77%	94%	Easy to shape	67%	83%
						Is smooth and smooth	86%	94%	Is smooth and smooth	67%	75%
Retention property	64%	94%	Health care	60%	67%
						Plump	64%	81%	Moisture retention	60%	58%

Each consumer was asked to maintain a write hair diary during a period of four weeks after treatment. Every day consumers must state whether they notice a difference in their hair versus the state of their hair before treatment. Also, each day they must pay attention to more specifically note how their hair feels, e.g., shine, volume, etc. Using these data, the percentage of consumers who still found a benefit from the treatment after a certain number of washes was calculated. These data are shown in table V below.

TABLE V

In addition, an overall analysis of consumer feedback is performed. Immediately after treatment and four weeks after treatment, the consumer was also asked: how will you rate the overall process? They must respond with one of the following options: excellent, very good, not very good, poor. The number of "excellent" or "very good" consumers answering the question was used to calculate the percentage of "overall rating". In addition to the summary of consumer responses related to whether the treatment met their expectations, these data can also be found in table VI below.

TABLE VI

In addition, the hairdresser's opinion is asked as to the efficacy of the consumer treatment. Each consumer is asked to respond to each criterion using a seven point scale, wherein the stylist may provide a score in one of the following options: +3, +2, +1, 0, -1, -2, -3. The results of this study are shown in table VII below.

TABLE VII

Description of the drawings: the results show that the inventive method is significantly better than the comparative method; the results demonstrate that the inventive method is significantly worse than the comparative method;⁼the result shows that the inventive method is the same as the comparative method.

The conclusions drawn from these consumer and stylist data include that the method according to the invention results in improved performance relative to a comparative method that is not according to the invention.

Examples of the invention

An oxidizing preparation: examples 1 to 3

Phases 1 and 2 were produced separately and then mixed together. The components of phase 1 were mixed together and heated to 80 ℃ until the salicylic acid dissolved. Phase 1 was then stirred and cooled to 40 ℃. Phase 2 was then produced and mixed into phase 1 and stirred for 5 minutes.

The oxidizing formulation is then applied to the hair, which is then dewetted by wiping the hair dry with a towel. Then, the monomer composition is applied to the hair.

Monomer composition: examples 1 to 4

Description of the drawings:¹= from Dow Europe GmbHHEC QP-4400H；²= from CP Kelco AHUBER COMPANYCG-T；³= from Clariant Produkte GmbH (Deutschland)C-100；⁴= from BASF ChemicalsEL；⁵= potassium 3-sulfopropyl acrylate from Raschig.

Phases 1 and 2 were produced separately and then mixed together. Phase 3 without the potassium salt of 3-sulfopropyl acrylate is formed with heating to 40 ℃ and then mixed with the other two phases. Finally the salt was added and the final monomer composition was stirred for 10 minutes.

Monomer composition: examples 5 to 8

Description of the drawings: as above, and⁶= from Herkules250HHR。

Prepare phase 1 and phase 2 separately. Phase 1 was prepared with stirring for 2 minutes, except formic acid, and then heated to 50 ℃ with stirring until the hydroxyethyl cellulose swelled. After cooling the solution to less than 30 ℃, formic acid was added until the pH of phase 1 reached pH 2.5. To prepare phase 2, 2-phenoxyethanol and methylparaben were first mixed until a solution was formed. Coco polyether-10 was then added to the solution at 40 ℃ and stirred. Phase 2 was prepared by subsequent mixing in PEG-35 castor oil and fragrance. Phase 2 was then added to phase 1, and then 3-sulfopropyl acrylate potassium salt was added and the resulting monomer composition was mixed for 5 minutes.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

Claims

1. A method for chemically modifying the internal region of a hair shaft, wherein said method comprises:

(i) applying an oxidizing formulation to the hair;

(ii) removing moisture from the hair;

2. The method of claim 1, further comprising one or more of:

-allowing the monomer composition to remain on the hair for a time x, wherein the time x is from 1min to 120 min;

-rinsing the hair;

-washing the hair.

3. The method according to any preceding claims, comprising providing the monomer composition to a stylist and/or consumer, wherein the stylist and/or consumer does not need to premix the monomer composition with a second formulation prior to applying the monomer composition to hair.

4. The method of any one of the preceding claims, wherein the ethylenic monomer is selected from the group consisting of: mesaconic acid, 2-pentenoic acid, tiglic acid ester, furan-3-acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, maleamic acid, 3-aminocrotonic acid, crotonate, itaconic anhydride, trimethylsilyl acrylate, poly (ethylene glycol) acrylate, N-vinylacetamide, 2-acetamidoacrylic acid, vinylsulfonic acid, tetrahydrofurfuryl acrylate, N-methyl-N-vinylacetamide, vinyl propionate, vinylanisole, vinyl crotonate, methyl 3-hydroxy-2-methylenebutyrate, methacryloyl-L-lysine, N- (2-hydroxypropyl) methacrylamide, 2-acrylamidodiglycolic acid, methacrylic acid, maleic acid ester, 3-aminocrotonic acid ester, itaconic anhydride, trimethylsilyl acrylate, poly (ethylene glycol) acrylate, N-vinylacetamide, 2-acetamidoacrylic acid, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, N-isopropyl methacrylamide, 2-aminoethyl methacrylate, 2-bromoethyl acrylate, propyl 3- (dimethylamino) acrylate, (3-acrylamidopropyl) trimethylammonium salt, [2- (acryloyloxy) ethyl ] -trimethylammonium salt, alkyl acetamidoacrylate, sulfoalkyl (meth) acrylate, 3-sulfopropyl methacrylate, and salts, isomers, derivatives, and mixtures thereof.

5. The method of any preceding claim, wherein the oxidizing agent comprises an oxidizing agent selected from the group consisting of: peroxides, preferably hydrogen peroxide; persulfates, preferably potassium persulfate or sodium persulfate; and mixtures thereof.

6. The method according to any one of claims 2 to 4, wherein the time x is from 5min to 100min, more preferably from 10min to 90min, most preferably from 20 to 60 min.

7. The method according to any of the preceding claims, wherein the oxidizing formulation is allowed to remain on the hair for a period of time y after applying the oxidizing formulation to the hair but before dewetting the hair, wherein time y is from 1min to 120min, preferably from 2min to 45min, more preferably from 3min to 20min, most preferably from 4min to 10 min.

8. The method of any preceding claim, wherein the dewetting of hair comprises applying an absorbent material to hair such that moisture is transferred from hair to the absorbent material, and wherein the moisture comprises a cosmetically acceptable carrier.

9. The method of any preceding claim, wherein the monomer composition and/or the oxidizing formulation further comprises a cation and an anion; wherein the cation is selected from inorganic cations having a charge density of 0.05 charge/picometer or greater.

10. The method of any preceding claim, wherein the monomer composition further comprises a tackifying means.

11. The method of claim 10, wherein the viscosity-increasing means is a viscosity-increasing agent selected from the group consisting of: nonionic thickeners, anionic thickeners, cationic thickeners, amphoteric thickeners, and mixtures thereof.

12. The method according to any one of claims 10 to 11, wherein the viscosifying agent comprises at least one polysaccharide, preferably at least one heteropolysaccharide.

13. The method according to any one of claims 2 to 12, wherein during time x, within 1 hour of applying the monomer composition, hair is exposed to a relative humidity of at least 70% and the exposure lasts from 10 to 90 min.

14. A kit, comprising:

(a) instructions for use comprising the method of any one of the preceding claims;

(b) the monomer composition.

15. The kit of claim 13, further comprising:

(c) an oxidising formulation according to any of the preceding claims, which is packaged separately from the monomer composition.