WO2012100007A2

WO2012100007A2 - Composition for chemically modifying the internal region of a hair shaft

Info

Publication number: WO2012100007A2
Application number: PCT/US2012/021789
Authority: WO
Inventors: Andreas Flohr; Thomas Krause; Marina Loifenfeld
Original assignee: The Procter & Gamble Company
Priority date: 2011-01-19
Filing date: 2012-01-19
Publication date: 2012-07-26
Also published as: EP2561857A2; WO2012100007A3; CA2816735C; EP2561857A3; EP2561857B1; MX2013005288A; JP2013543871A; US20120183486A1; BR112013011428A2; CA2816735A1; CN103501756A

Abstract

A composition for chemically modifying the internal region of a hair shaft, wherein the composition comprises: an ethylenic monomer having a molecular weight of 500 g/mole or less; a cation and an anion; wherein the cation is selected from the group consisting of inorganic cations having a charge density of 0.05 charge/picometre or more; a cosmetically acceptable carrier; wherein the composition has a pH of from 4.0 to 6.9.

Description

COMPOSITION FOR CHEMICALLY MODIFYING THE

INTERNAL REGION OF A HAIR SHAFT FIELD OF THE INVENTION

In a first aspect, the present invention relates to a composition for chemically modifying the internal region of a hair shaft, wherein the composition comprises: an ethylenic monomer having a molecular weight of about 500 g/mole or less; a cation and an anion; wherein the cation is selected from the group consisting of inorganic cations having a charge density of about 0.05 charge/picometre or more; a cosmetically acceptable carrier; wherein the composition has a pH of from about 4.0 to about 6.9.

BACKGROUND OF THE INVENTION

Hair style retention traditionally has been accomplished by the use of styling products comprising polymers and other components that at least partially coat the hair and act on the surface of hair fibres. Several disadvantages are associated with this approach. Loss of hair style due to passage of time, elevated environmental humidity, excessive motion, etc. may cause a consumer to feel the need to refresh a hair style throughout the day. This often requires application of additional styling product(s). The benefits of traditional styling products also may be diminished when applied to hair to which conditioning agents also have been applied. In addition, application of materials to the surface of hair may compromise the natural feel and appearance of the hair and result in a dull appearance and/or a stiff or otherwise unpleasant feel. Furthermore, for certain hair types, it may not be possible to achieve desired hair styles with conventional styling products and treatments at all.

There is a need for consumers with damaged, thin, weak or limp hair to increase the volume and fullness of their hair, particularly consumers that utilise a blow drier. These consumers seek hair styles, treatments and products that allow them to perceive and project to others that they have thicker hair i.e. increased hair volume, bounciness and greater fullness. Improving hair movement and feel are also important desires of these consumers. Therefore, there is also a desire to enable consumers to be able to concurrently achieve increased volume and better hair feel, mobility, texture, healthy appearance and also increased control over their hairstyle. There is a need to allow these consumers to achieve such benefits without the need for back-combing, extensive blow drying, mousse products and/or hairsprays.

There is also a need for consumers with curly and/or unruly and/or frizzy hair to attain greater control of their hair, particularly consumers that utilise hair straighteners. These consumers seek hair styles, treatments and products that allow them to perceive and project to others that they have tamed hair and/or increased curl definition. In other words, all hairs are in place, the hair look is very defined, shiny and healthy-looking. These consumers may seek reduced volume and a straightening of the hair shafts leading to a more perfectly defined look. These consumers may usually resort to the utilisation of conventional means such as the application of styling gels and/or styling mousses. Hence, there is a need to allow these consumers to achieve such benefits without these consumers resorting to these conventional means.

Methods of, and compositions thereof for, chemically modifying the internal region of a hair shaft are known in the art. See for example US2008/0210253A1. Said methods may comprise the steps of applying to the hair a first composition comprising specific monomers and applying to the hair a second composition comprising an initiator. Said methods may result in increased rigidity of the hair shaft after multiple washings and/or wetting of the hair, reduced negative effects of moisture and/or humidity i.e. humidity resistance resulting in less frizziness or limpness, and said methods may require application of less styling products and/or may hold the style for longer periods of time.

Whilst said methods provide satisfactory results to the hair shaft, there is a constant need for providing methods resulting in further improved performance, efficacy and/or efficiency. As far as the improved performance is concerned, there is a specific need for providing improved desired hair shape retention and hairstyle durability. As far as efficiency is concerned, there is a need for improving the penetration of the monomers into the hair shaft and/or improving the polymerization of the monomers, for example increasing the lengths of the polymeric chains within the internal structure of the hair shaft. Furthermore, there is a need for improving the durability of the treatment such that the benefits last for a longer time. There is also a need for potentiating the efficacy of the method, for example such that less active(s) and/or composition(s)/formulation(s)/steps are required to achieve a similar performance. Moreover, there is a need for simplifying the application process, such that it can be carried out by either a trained hairdresser or a consumer at home on their own hair. In addition there is a need for better ensuring that the results are more predictable and reducing the variability of the end result between consumers with different hair types. SUMMARY OF THE INVENTION

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

i. an ethylenic monomer having a molecular weight of about 500 g/mole or less; ii. a cation and an anion; wherein the cation is selected from the group consisting of inorganic cations having a charge density of about 0.05 charge/picometre or more; iii. a cosmetically acceptable carrier;

wherein the composition has a pH of from about 4.0 to about 6.9. In a second aspect, the present invention relates to a kit comprising:

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

(b) a product comprising a formulation, wherein the formulation is a hair treatment agent selected from the group consisting of oxidising formulations, finishing formulations, reducing formulations, hairstyling formulations, conditioning formulations, shampoo formulations, dyeing formulations, and combinations thereof; and wherein the formulation is different to the composition that product (a) comprises.

In a third aspect, the present invention relates to the use of the composition, according to first aspect, for chemically modifying the internal region of a hair shaft.

In a fourth aspect, the present invention relates to a method for chemically modifying the internal region of a hair shaft, wherein the composition according to the first aspect is applied onto hair.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 : Shows the disappearance of monomer over time as measured by proton nuclear magnetic resonance spectroscopy (^H-NMR)

Figure 2: Shows that an increase in molecular weight polymer occurs when the composition of the present invention is utilised compared to a comparative composition, as measured by gel permeation chromatography (GPC).

Figure 3: Shows an improvement in add on and stiffness for a composition according to the present invention versus a comparative composition. DETAILED DESCRIPTION OF THE INVENTION

In all embodiments of the present invention, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise. All ranges are inclusive and combinable. The number of significant digits conveys neither a limitation on the indicated amounts nor on the accuracy of the measurements.

All numerical amounts are understood to be modified by the word "about" unless otherwise specifically indicated. Unless otherwise indicated, all measurements are understood to be made at 25 °C and at ambient conditions, where "ambient conditions" means conditions under 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 byproducts 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. This term encompasses 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 elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.

The term "substantially free from" or "substantially free of as used herein 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%, most preferably about 0%, by total weight of the composition or formulation.

"Hair," as used herein, means mammalian hair including scalp hair, facial hair and body hair, more preferably hair on the human head and scalp. "Hair shaft" means an individual hair strand and may be used interchangeably with the term "hair."

"Internal region of the hair shaft," as used herein, means any non-surface portion of the hair shaft, including the inner portion of the cuticle and underneath the cuticle. "Non-surface portion" may be understood to mean that portion of the hair that is not in direct contact with the outside environment.

"Proximal to the scalp," as used herein, means that portion of an extended, or substantially straightened, hair shaft that is closer in distance to the scalp than to the end of the hair. Thus, about 50% of the hair would be considered proximal to the scalp, and about 50% of the hair would be distal to the scalp, "z cm proximal to the scalp" means a distance "z" along the hair, with one endpoint being on or directly adjacent to the scalp, and the second endpoint being measured "z" centimetres along the length of the extended or substantially straightened hair.

"Cosmetically acceptable," as used herein, means that the compositions, formulations or components described are 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 which have the purpose of being directly applied to keratinous tissue are limited to those being cosmetically acceptable.

"Derivatives," as used herein, includes but is not limited to, amide, ether, ester, amino, carboxyl, acetyl, and/or alcohol derivatives of a given compound.

"Monomer," as used herein, means a discrete, non-polymerised chemical moiety capable of undergoing polymerisation in the presence of an initiator.

"Ethylenic monomer," as used herein, means a chemical species that contains an olefenic carbon-carbon double bond (C=C) and is capable of undergoing polymerization in the presence of an initiator.

"Polymer," as used herein, means a chemical formed from the polymerisation of two or more monomers. The term "polymer" as used herein shall include all materials made by the polymerisation of monomers as well as natural polymers. Polymers made from only one type of monomer are called homopolymers. A polymer comprises at least two monomers. Polymers made from two or more different types of monomers are called copolymers. The distribution of the different monomers can be calculated statistically or block-wise - both possibilities are suitable for the present invention. Except if stated otherwise, the term "polymer" used herein includes any type of polymer including homopolymers and copolymers.

The term "hairstyling polymer" as used herein means hair-fixing polymers which form films on a surface. In the context of hair, this surface is the surface of individual hair fibres or a plurality thereof. The polymer causes them to be glued together to build welds, which are crosslinks that provide the hold benefit. In concert, these welds form a 'hairnet' to provide hair hold and volume benefits to the user. When the net of welds is effectively formed, the hold and volume benefits can last all day and offer good resistance to environmental humidity.

The term "molecular weight" or "M.Wt." as used herein refers to the number average molecular weight unless otherwise stated.

All percentages are calculated by weight unless otherwise stated.

"Chemically modify," or grammatical equivalents thereof, as used herein, means that a chemical moiety such as monomer and/or crosslinker and/or polymer, stably affixes to a second chemical moiety, for example, a keratin protein, another component of hair, and/or another monomer or crosslinker or polymer.

"Separately packaged," as used herein, means any form of packaging that prevents one composition or formulation from coming into physical contact, or admixing, with a second composition or formulation. "Separately packaged" may mean that the individual compositions/formulations are packaged in separate containers, or alternatively in a single container partitioned such that the compositions/formulations are not in physical contact.

"Relative humidity", as used herein, means the amount of water vapour carried in the air.

"High relative humidity" herein refers to a relative humidity higher than that at ambient conditions i.e. at least about 70%. "Environmental humidity" as used herein relates to relative humidity that the consumer may be exposed to once the method of the present invention has been completed. An example of environmental humidity is that due to weather conditions.

"Environmental humidity resistance", as used herein relates to the ability of the hair to better resist negative consequences of environmental humidity.

"Multivalent cation," as used herein, means an element having a net ionic charge of from

2+ to 7+.

"Stably affix" is understood to include both covalent and non-covalent forms of chemical bonds that once formed, remain unchanged through wetting, washing, styling and other types of hair treatment. In general, stably affixed chemical moieties may not be removed from the hair without damaging or substantially destroying the hair.

"Increased style retention and/or durability," as used herein, means that the hair style formed, shaped, and/or obtained after application of the composition of the present invention to the hair is maintained for a longer period of time relative to hair of the same being to which no composition has been applied.

"Increased appearance of volume," as used herein, means that the hair exhibits a visually noticeable greater volume, i.e., distance between the scalp and the outermost layer of hair style and/or distance between individual hairs, after application of a composition of the present invention relative to before a composition was applied.

"Increased resistance to moisture," as used herein, means that after application of a composition of the present invention, the hair fails to exhibit visually noticeable effects, such as loss of volume, loss of style, increase in frizz, etc. upon exposure to water vapour (i.e., relative humidity greater than about 50%) relative to before a composition has been applied. "Kit," as used herein, means a packaging unit comprising a plurality of components. An example of a kit is, for example, a first composition and a separately packaged second composition. Another kit may comprise a first composition and an energy delivery device. A different kit may comprise three different types of separately packaged composition and a hair styling implement. A further kit may comprise application instructions comprising a method and a composition/formulation.

"Separately packaged," as used herein, means any form of packaging that prevents a first composition from coming into physical contact, or admixing, with a second composition. "Separately packaged" may mean that the individual compositions are packaged in separate containers, or alternatively in a single container partitioned such that the compositions are not in physical contact.

"Implement," as used herein, means a device used to facilitate application of a composition to the hair and/or manipulation of the hair. Examples of implements include, but are not limited to, a comb, a means for directed delivery (e.g., an applicator or tube), a covering for the hair (e.g., plastic bag, shower cap, etc.), and combinations thereof.

"Energy delivery device," as used herein, means any device used to deliver energy to keratinous tissue, including the hair and scalp. "Delivery of energy," means that the surface of the keratinous tissue is exposed to the energy emanating from the energy delivery device, where it may penetrate to the desired layers of the 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 radiofrequency waves and microwaves), and combinations thereof.

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

wherein the composition has a pH of from about 4.0 to about 6.9.

The inventors have answered the aforementioned needs by carefully selecting the specific combination of mutually compatible features such that the interaction therewith results in a method for chemically modifying the internal region of a hair shaft with improved performance. Particularly important benefits of the present invention include: improved chemical modification of the internal region of the hair shaft due to higher molecular weight of polymer, and simplification of the process for applying the present invention.

It is described herein that the presence, in the composition of the present invention, of an inorganic cation having a charge density of about 0.05 charge/picometre or more results in superior performance. Without being bound by theory, it is believed that the inorganic cation, due to its positive charge, can bind to a plurality of anionic ethylenic monomers, either when the ethylenic monomer is unpolymerised or after polymerisation when it is a unit of the polymer. For example, the inorganic cation may bind to two or more different polymer chains that carry an anionic charge simultaneously. The benefits of such binding effects include: increased sequestering of ethylenic monomer and polymer into greater proximity to each other resulting in longer polymer chains and/or ionic cross-linking of neighboured polymer chain segments after polymerization. Inorganic cations having a higher charge density are able to bind and out- compete any other cation with a lower charge density for the negatively charged binding site.

It has also been found that a composition comprising the ethylenic monomer can be provided to the consumer and/or stylist in ready-to-use form. In other words, without the need for the composition to be mixed with at least one other formulation/composition, for example a composition comprising an initiator, salt, oxidising agent, acid, base, or catalyst, prior to application onto hair. This represents a significant improvement in the composition and method for applying the present invention onto hair, in terms of reduced application time, transport effort, carbon footprint and cost effectiveness.

The present invention pertains to compositions and methods for chemically modifying the internal region of the hair shaft, more preferably for forming polymer in the internal region of the hair shaft. Without being bound by theory, it is believed that polymer on the external surface of the hair shaft would be more easily washed off whereas polymer inside the hair shaft, for example, underneath the cuticle, would be better protected and hence be substantially more durable. Figure 1 and 2 as detailed herein demonstrate that polymer is formed by the actives utilised in the present invention. Furthermore, Figure 3 demonstrates that an increase in weight occurs following treatment of hair by a composition of the present invention and that the physical properties of the hair, namely its stiffness, are increased, and moreover, these changes being resistant to wash out. The features of the composition according to the first aspect, as well as the other aspects and other relevant components, are described in detail hereinafter.

According to the first aspect, the composition of the present invention comprises an ethylenic monomer having a molecular weight of about 500 g/mole or less. In an embodiment, the ethylenic monomer is selected from the group consisting of: mesaconic acid, 2-pentenoic acid, tiglic acid, tiglic acid esters, furan-3 -acrylic acid, 2-acrylamido-2-methyl-l-propanesulfonic acid, maleamic acid, 3-aminocrotonic acid, crotonic acid esters, itaconic anhydride, trimethylsilylacrylate, poly (ethyleneglycol) aery lates, N-vinylacetamide, 2-acetamidoacrylic acid, vinylsulfonic acid, tetrahydrofurfurylacrylate, N-methyl-N-vinylacetamide, vinylpropionate, vinylanisole, vinylcrotonate, methyl 3-hydroxy-2-methylenebutyrate, methacryloyl-L-lysine, N- (2-hydroxypropyl)methacrylamide, 2-acrylamidodiglycolic acid, 2-ethoxyethyl acrylate, 2- butoxyethyl acrylate, N-isopropylmethacryalmide, 2-aminoethyl methacrylate, 2-bromoethyl acrylate, 3-(dimethylamino)propyl acrylate, (3-acrylamidopropyl)trimethyl ammonium salt, [2- (acryloyloxy)ethyl]-trimethylammonium salt, alkylacetamidoacrylate, sulfoalkyl (meth)acrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and salts, isomers, derivatives and mixtures thereof. In an embodiment, the composition comprises at least one ethylenic monomer, selected from the group cited above, as the sole ethylenic monomer(s). In an embodiment, the ethylenic monomer is selected from the group consisting of 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and salts, derivatives and mixtures thereof. In an embodiment, the only ethylenic monomer(s) present are selected from the group consisting of 3-sulfopropyl acrylate, 3- sulfopropyl methacrylate, and salts, derivatives and mixtures thereof. In an embodiment, the sole ethylenic monomer is 3-sulfopropyl acrylate. In an embodiment, the ethylenic monomer is 3- sulfopropyl acrylate, which is added to the composition as 3-sulfopropyl acrylate potassium salt.

In another embodiment, the ethylenic monomer is selected from the group consisting of: 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-dimethylamino ethyl methacrylate, 2- hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2,4-dihydroxybutyl methacrylate, 2,3-epoxybutyl methacrylate, 2-t-butylaminoethyl methacrylate, 2-(2-diethylamino)ethyl methacrylate, ethylene glycol mono methacrylate, itaconic acid (and salts thereof), vinyl pyridine, resorcinol, and mixtures thereof. The molecular weight of the ethylenic monomer is important because of the need for the monomer to penetrate into the hair shaft prior to polymerisation. Large and/or bulky monomers would penetrate less easily into the hair shaft. In an embodiment, the ethylenic monomer has a molecular weight of from about 50 g/mole to about 500 g/mole, preferably from about 75 g/mole to about 400 g/mole, more preferably from about 100 g/mole to about 400 g/mole, even more preferably from about 150 g/mole to about 300 g/mole. In an embodiment, the ethylenic monomer does not have a molecular weight of below about 50 g/mole, preferably below about 75 g/mole, more preferably below about 100 g/mole, even more preferably below about 150 g/mole, nor above about 500 g/mole, preferably nor above about 400 g/mole, even more preferably nor above about 300 g/mole.

The ethylenic monomer may be present in an amount of 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%, most preferably from about 11% to about 12.5%, by total weight of the composition.

In an embodiment, two or more different ethylenic monomers are present in the composition pursuant to the first aspect. The resultant polymers may be copolymers.

The composition may comprise a crosslinker having a molecular weight suitable to penetrate the hair shaft. The purpose of the crosslinker is to covalently bond the monomer to the hair, monomer to other monomer, and polymer to other polymer.

The molecular weight of the crosslinker may be about 500 g/mole or less, preferably from about 100 g/mole to about 500 g/mole, more preferably from about 100 g/mole to about 400 g/mole, even more preferably from about 200 g/mol to about 400 g/mole.

The crosslinkers may be selected from the group consisting of: 1 ,4-bisacryloylpiperazine, methylenebisacrylamide, ethylenebisacrylamide, divinylbenzene, poly-ethyleneglycol 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] phosphate, N,N'-bis(acryloyl)cystamine, Ν,Ν-diallylacryalmide, triallyl cyanurate, 3- (acryloyloxy)-2-hydroxypropyl methacrylate, and mixtures thereof.

In an embodiment, the ratio of the weight percentage of the ethylenic monomer to the weight percentage of the crosslinker (i.e. ethylenic monomencrosslinker) is from about 50: 1 to about 10:1, alternatively from about 40: 1 to about 10: 1, and alternatively from about 20:1 to about 10:1. The present invention relates to a composition for chemically modifying the internal region of the hair shaft. In an embodiment, the chemically modifying is selected from the group consisting of: the formation of a polymer in the internal region of the hair shaft; the modification of the internal region of the hair shaft with a polymer; and combinations thereof. In an embodiment, the polymerisation that occurs is free radical polymerisation.

In an embodiment, the composition is substantially free of oxidising agents and/or initiators. In another embodiment, the composition is substantially free of oxidising agents selected from the group consisting of: peroxides, preferably hydrogen peroxide; persulfates, preferably potassium persulfate or sodium persulfate; and mixtures thereof. In another embodiment, the composition is substantially free of an alpha-methylene lactone compound. In another embodiment, the composition is in ready-to-use form, wherein ready-to-use form means that no pre-mixing is required prior to application onto hair. In another embodiment, the composition is substantially free of at least one of the following: a reducing agent, a transition metal.

A composition or formulation as mentioned herein, or a plurality thereof, may further comprise a monomer that does not penetrate into the internal region of the hair shaft, which will be referred to as a non-penetrating monomer hereinafter. Reasons for non-penetration include hydrophobicity, insolubility, too large a molecular weight i.e. greater than about 500 g/mol, and also highly reactive monomers that may polymerise before reaching the hair shaft. It is hence implicit that such non-penetrating monomers are not capable of chemically modifying the internal region of a hair shaft. However, non-penetrating monomers may be capable of chemically modifying the external surface of the hair shaft and that this modification may be capable of enduring a plurality of washings/shampooings. This external modification may enhance the benefits of the present invention. Non-penetrating monomers include those of cyano- acrylate chemistry and reactive silicones. Such non-penetrating monomers include those disclosed in US7357921B2, US 7780742, US 7740664.

A composition or formulation as described herein, or a plurality thereof, may further comprise a viscosity-increasing means selected from the group consisting of viscosity-increasing agents and viscosity-increasing systems. Viscosity is important when the composition is in the form of gel, cream, lotion, emulsion etc because it prevents the composition from sliding off the hair. However, lower viscosities allow actives to penetrate/diffuse more easily into the internal region of the hair shaft. The viscosity of the composition when it is in the form of a gel is: preferably from about 500 mPa-s to about 7000 mPa-s, more preferably from about 1000 mPa-s to about 5000 mPa-s, even more preferably from about 1500 mPa-s to about 4500 mPa-s, most preferably from about 1900 mPa-s to about 4000 mPa-s, measured with a Brookfield Viscosimeter RVDV III Ultra CP 52 at 25 °C and 1 rpm.

The viscosity-increasing agent may be selected from the group consisting of non-ionic thickeners, cationic thickeners, anionic thickeners, amphoteric thickeners, and mixtures thereof; preferably non-ionic thickeners, anionic thickeners, and mixtures thereof. The viscosity- increasing agent may be present in the composition in an amount of from about 0.1% to about 10%, preferably about 0.2% to about 5.0%, by total weight of the composition.

Non-ionic or anionic thickeners (or mixtures thereof) are preferred for the composition due to the typically anionic chemistry of polymerised ethylenic monomer. Non-ionic or anionic thickeners are less likely to interact directly with the formed polymer and hence the formation of insoluble complexes or precipitates is also less likely. The viscosity-increasing means is also preferably stable at the required pH and does not substantially affect the active levels of ethylenic monomer. The viscosity-increasing agent may be a cross-linked or a non-crosslinked polymer.

In an embodiment, the viscosity-increasing agent is a hydrophobically-modified polyacrylate polymer. Such hydrophobically-modified polyacrylate polymers are particularly suitable when the composition/formulation is created by the addition of at least one salt. The composition may comprise from about 0.5% to about 1.5% of the hydrophobically-modified polyacrylate polymer, by total weight of the composition. Suitable hydrophobically-modified polyacrylate polymers include: acrylates/C10-C30 alkylacrylates copolymers such as Ultrez^® 20/21 from Lubrizol, and Permulen^® TR1 from Lubrizol; acrylates/beheneth-25 methacrylate copolymers such as Aculyn^® 28 from Rohm & Haas; acrylates/ceteth-20 itaconate copolymers such as Structure^® 3001 or 2001 from Akzo Nobel.

In an embodiment, the viscosity-increasing agent is a non-crosslinked associative thickening polymer. The composition may comprise from about 0.5% to about 3% of the non- crosslinked associative thickening polymer, by total weight of the composition. Suitable associative thickeners include polyurethane-based polymers such as polyurethane-30 e.g. LuvigelSTAR^® from BASF. Also EO-PO-block copolymers may be useful, for example Pluronics^® from BASF.

In an embodiment, the viscosity-increasing agent comprises at least one polysaccharide, preferably at least one heteropolysaccharide. The total polysaccharide present in the composition may be from about 0.2% to about 5%, more preferably from about 0.5% to about 4%, by total weight of the composition. Suitable polysaccharides and heterosaccharides include starches and derivatives thereof, e.g. mono- or di-esters with phosphoric acid, cellulose types and their derivatives, xanthan gums, carrageenans. Preferred heteropolysaccharides include xanthan gum such as Keltrol^® T from Kelco, and Natrosol^® 250 HHR from Herkules. In an embodiment, the polysaccharide is selected from the group consisting of hydroxyethylcellulose, hydroxypropylcellulose, xanthan gum, carrageenans, and mixtures thereof. Xanthan gums and derivatives thereof are present in an amount of from about 0.2% to about 1.5%, more preferably about 0.5% to about 0.9%, by total weight of the composition. Starches and derivatives thereof are present in an amount of from about 3% to about 4% by total weight of the composition. A preferred starch is hydroxypropyl starch phosphate such as Structure^® XL from National Starch. In an embodiment, the composition comprises two different polysaccharide viscosity-increasing agents.

In an embodiment, a viscosity-increasing system is employed. The viscosity-increasing system may employ a viscosity-increasing agent as defined above. Alternatively or additionally, the viscosity-increasing system comprising a non-polymer system which provides internal structure to the product. The non-polymer system is selected from the group consisting of: a surfactant system preferably comprising lauryl ether sulphate plus sodium chloride; a liquid crystal system for example a cationic conditioner made of fatty alcohol plus cationic surfactant; an emulsion of the water in oil (w/o) type; an emulsion of the oil in water (o/w) type; an inorganic thickening system, for example bentonites, montmorillonites. In another embodiment, the viscosity-increasing system is free of a polymeric viscosity-increasing agent or polymeric thickener.

The composition comprises a cosmetically acceptable carrier. Another composition or formulation as described herein, or a plurality thereof, may also comprise a cosmetically acceptable carrier. The composition/formulation may comprise from about 60% to about 99.9%, alternatively from about 70% to about 95%, and alternatively from about 80% to about 90%, of a cosmetically acceptable carrier, by total weight of the composition or formulation. Cosmetically acceptable carriers suitable for use include, for example, those used in the formulation of tonics and gels. Cosmetically acceptable carrier may comprise water; silicones such as volatile silicones, amino or non-amino silicone gums; organic compounds such as C2-C1₀ alkanes, acetone, methyl ethyl ketone, volatile organic C1-C12 alcohols, esters of C1-C2₀ acids and of Ci-C₈ alcohols such as methyl acetate, butyl acetate, ethyl acetate, and isopropyl myristate, dimethoxyethane, diethoxyethane, C1₀-C₃₀ fatty alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol; C1₀-C₃₀ fatty acids such as lauric acid and stearic acid; C1₀- C₃₀ fatty amides such as lauric diethanolamide; C1₀-C₃₀ fatty alkyl esters such as C1₀-C₃₀ fatty alkyl benzoates; hydroxypropylcellulose, and mixtures thereof. In an embodiment, the carrier comprises water, fatty alcohols, volatile organic alcohols, and mixtures thereof. In a most preferred embodiment the carrier is water.

In an embodiment, the composition comprises a cation, wherein the cation is selected from the group consisting of inorganic cations having a charge density of about 0.05 charge/picometre or more, preferably about 0.052 charge/picometre or more. In an embodiment the inorganic cation is a metal. In an embodiment, the cation may not be selected from inorganic cations having a charge density of about 0.04 charge/picometre or less, preferably less than about 0.05 charge/picometre. In an embodiment, the cation is selected from the group consisting of inorganic cations having a charge density of about 0.050 charge/picometre to about 0.090 charge/picometre, preferably from about 0.052 charge/picometre to about 0.080 charge/picometre, more preferably to about 0.070 charge/picometre, even more preferably to about 0.060 charge/picometre, most preferably to about 0.053 charge/picometre.

The charge density of an ion is calculated by dividing the charge by the ionic radius which results in charge per picometre, the charge density. For example, Sr²⁺ has an ionic radius of 127 pm and a charge of 2. Consequently, the charge per picometre is 0.0157 charge/pm. Tables of ionic radii tables can be found in common inorganic chemistry textbooks, for example Atkins P.W., Physical Chemistry, 6^th Edition, 2001. Ion radii of common metals can be found in Table I.

Picometre (pm) per Charge density Ion radius

Metal Charge charge (charge/pm) (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

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

Ta ble l

Without being bound by theory, it is believed that unfavourable redox reactions with the chemistry of other hair treatments (such as permanent oxidative hair colouring, semi-permanent hair colouring, hair dyeing, hair bleaching, or permanent waving of the hair) are less likely to occur when the cation is less able to lose or gain electrons. Unfavourable redox reactions are less likely to occur if the inorganic cation is selected from metals that can only exist in two oxidation states other than oxidation state "0", more preferably in only one oxidation state other than oxidation state "0". Copper, for example, can only exist in a total of three different oxidation states, namely Cu°, Cu¹⁺ and Cu²⁺. Manganese, for example, can only exist in a total of four different oxidation states, namely Mn°, Mn^¾ Mn^¾ Mn⁴⁺. Aluminium, for example, can only exist in a total of two oxidation states, namely Al° and Al³⁺. In an embodiment, the inorganic cation has a charge of at least 2+, more preferably at least 3+. In an embodiment, the inorganic cation is not a transition metal. In an 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 the cation to the monomer (i.e. cation:monomer) may 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, even more preferably from about 1:3 to about 1:1. The molar amount of cation is preferred to be in excess of the molar amount of counterion of the ethylenic monomer when the ethylenic monomer is added into the composition in the form of a salt.

The inorganic cation may also be present in the oxidising formulation, the finishing formulation, and/or a combination thereof. In an embodiment, the oxidising formulation further comprises a cation, wherein the cation is not selected from inorganic cations having a charge density of about 0.04 charge/picometre or less, preferably less than about 0.05 charge/picometre. In an embodiment, the oxidising formulation comprises a cation, wherein the cation is selected from the group consisting of inorganic cations having a charge density of about 0.05 charge/picometre or more, and the cation is present in an amount of from about 0.001% to about 2%, preferably about 0.01% to about 1%, more preferably about 0.04% to about 0.2%, by total weight of the oxidising formulation.

In an embodiment, the present invention comprises an anion. The anion may be selected from the group consisting of sulfate, sulfonate, phosphate, nitrate, chloride, citrate, lactate, formate, and mixtures thereof. Preferred anions are selected from the group consisting of sulfate, sulfonate, and mixtures thereof. In a most preferred embodiment, the anion is sulfate.

In an embodiment, the molar ratio of the cation to the anion (cation:anion) is from about 1:5 to about 5:1, preferably from about 1:4 to about 3:1, most preferably from about 2:3 to about 3:2. Where the inorganic metal cation is Al³⁺ and the anion is sulfate, the molar ratio of the cation to the anion is about 2:3. The anion may also be present in the oxidising formulation, the finishing formulation, and a combination thereof. In an embodiment, a composition or formulation as described herein, or a plurality thereof, comprises a salt. In an embodiment, a composition or formulation as described herein, or a plurality thereof, may be created via the addition of a salt. The salt may comprise a cation having a charge density of about 0.05 charge/picometre or more and an anion. In an embodiment, the salt may comprise the ethylenic monomer.

The pH of the compositions and formulations of present invention, when applied to hair directly, must be suitable for application onto 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 composition has a pH of from about 4.0 to about 6.9. In an 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. In an embodiment, the composition does not have a pH of about 7.0 or more.

A composition or formulation as described herein, or a plurality thereof, may comprise at least one oxidising agent. The oxidizing formulation comprises an oxidising agent. The oxidising agent may be selected from the group consisting of: peroxides, preferably hydrogen peroxide; persulfates, preferably potassium persulfate or sodium persulfate; and mixtures thereof. In an embodiment, the composition comprising the ethylenic monomer does not comprise an oxidising agent. In an embodiment, the oxidizing formulation is substantially free of hair colouring agents, or substantially free of oxidative dyes and/or direct dyes.

The oxidising agent may be present in an amount of from about 0.01% to about 15%, by total weight of the composition/formulation. When a persulfate oxidising agent is used, it may be in powder form and mixed as a liquid immediately prior to application onto hair. The final amount 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 oxidising agent is a peroxide, the peroxide may be present in an amount of 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.

When the oxidising formulation comprises peroxide, the oxidising formulation may comprise a buffer system to stabilise the pH. Suitable buffers may also act as chelating agents. Chelation of transition metals, for example copper or iron from pipes which might be present in trace amounts in tap water, is important because peroxides are sensitive to cleavage by transition metals. In the absence of a buffer system the transition metal may 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. An example of a suitable buffer system is phosphoric acid and disodium phosphate. Another example of a suitable buffer system is citric acid and sodium hydroxide. In an embodiment, the composition comprises a buffer system.

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

Following treatment with the composition of the present invention, a finishing composition may be applied to the hair. The finishing composition may comprise a hair conditioning agent. The hair conditioning agent is typically a cationic polymer that provides softness to the hair or that repair damaged hair. Conditioning polymers generally provide a film on the hair that is smooth and not tacky. Typically, the conditioning polymers are cationic but may also be nonionic, zwitterionic, and amphoteric. The hair conditioning agent may also be an oily and/or a silicone compound. Patent application WO 2009/107062 A2 discloses conditioning agents and cationic polymers, which may be suitable for the finishing formulation as described herein. Also potentially suitable for use in the compositions herein are the conditioning agents described by the Procter & Gamble Company in U.S. Pat. Nos. 5,674,478, and 5,750,122. Also potentially suitable for use herein are those conditioning agents 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 an embodiment, the finishing formulation comprises an oxidising agent. The oxidising agent may be present in an amount of 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 useful for allowing reducing disulfide bonds and improved 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, glyceryl monothioglycolate, ammonium thioglycolate, thioglycerol, 2,5-dihydroxybenzoic acid, diammonium dithioglycolate, strontium thioglycolate, calcium thioglycolate, zinc formosulfoxylate, isooctyl thioglycolate, D/L-cysteine, monoethanolamine thioglycolate, phosphines, and mixtures thereof.

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

A composition or formulation 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 components are physically and chemically compatible with the essential components described herein, or do 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 CTFA Cosmetic Ingredient Handbook, Tenth Edition, 2004, both of which are incorporated by reference herein 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, tints, bleaches, reducing agents and other colorants, sunscreens, gelling agents, physiologically active compounds for treating the hair or skin (e.g., anti-dandruff actives, hair growth actives), non-polymeric thickeners including clays, and perfume.

Oily compounds may aid the penetration of the ethylenic monomer into the skin and/or scalp, which is not preferred. In an embodiment, the composition is substantially free from oily compounds. In another embodiment, the composition and the oxidising formulation are substantially free from oily compounds. In an embodiment, at least one performance benefit as described herein, which the present invention provides, is still noticeable to at least about 40% of consumers after about 15 washes, preferably to at least about 45% of consumers, more preferably to at least about 50% of consumers, even more preferably to at least about 55% of consumers, most preferably to at least about 60% of consumers, optimally to at least about 65% of consumers, more optimally to at least about 70% of consumers. In an embodiment, the consumers are selected from the group consisting of: consumers that regularly style their hair and have thin and/or limp hair, and consumers that regularly style their hair and have thick and/or unruly hair.

The composition of present invention may be in different product forms. It may be in a form selected from the group consisting of a gel, an emulsion, a cream, a spray, a lotion, or a mousse. Preferred forms are a gel, a cream or a lotion, more preferably a gel, most preferably the composition is in the form of a gel that has the appearance of an emulsion. The oxidising formulation may be in the form of gel, an emulsion, a cream, spray, lotion, mousse. The most preferred form for the oxidising formulation is a lotion.

In an embodiment according to the first aspect, the present invention relates to a composition for chemically modifying the internal region of a hair shaft, wherein the composition comprises:

i. an ethylenic monomer having a molecular weight of about 500 g/mole or less; ii. a cation and an anion; wherein the cation is Al³⁺;

iii. a cosmetically acceptable carrier;

wherein the composition has a pH of from 4.0 to 6.9; and wherein the composition further comprises a viscosity-increasing agent being a polysaccharide; and wherein the ethylenic monomer is present in an amount of from 7% to 13%, by total weight of the composition.

In another embodiment according to the first aspect, the present invention relates to a composition for chemically modifying the internal region of a hair shaft with a polymer, wherein the composition comprises:

i. an ethylenic monomer having a molecular weight of from about 150 g/mole to about 300 g/mole;

ii. a cation and an anion; wherein the cation is Al³⁺; and wherein the anion selected from the group consisting of sulfate, sulfonate, and mixtures thereof; iii. a cosmetically acceptable carrier; wherein the composition has a pH of from 4.0 to 6.9; and wherein the composition further comprises a viscosity-increasing agent being a polysaccharide; and wherein the ethylenic monomer is present in an amount of from 7% to 13%, by total weight of the composition. In a second aspect, the present invention relates to a kit comprising:

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

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

(c) an applicator;

(d) an instruction guide;

(e) a device.

A different embodiment of the second aspect, relates to a kit comprising:

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

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

In a third aspect, the present invention relates to use of the composition, according to the first aspect, for chemically modifying the internal region of a hair shaft. Another embodiment of the third aspect relates to use of the composition, according to the first aspect, for chemically modifying the internal region of a hair shaft with a polymer. Another embodiment relates to use of the composition, according to the first aspect, for styling the hair. Another embodiment relates to use of the composition, according to the first aspect, for creating a defined and/or tamed look to the hair. Another embodiment relates to use of the composition, according to the first aspect, for creating a fuller and/or thicker appearance to the hair. Another embodiment relates to use of the composition, according to the first aspect, for increasing the density of the hair shaft and/or elasticity of the hair shaft. In a fourth aspect, the present invention relates to method for chemically modifying the internal region of a hair shaft, wherein the composition according to the first aspect is applied onto hair. Another embodiment of the fourth aspect, relates to a method for chemically modifying the internal region of a hair shaft, wherein an oxidising formulation is applied onto hair, wherein the oxidising formulation comprises an oxidising agent and the composition according to the first aspect. The oxidising agent may be selected from the group consisting of: peroxides, preferably hydrogen peroxide; persulfates, preferably potassium persulfate or sodium persulfate; and mixtures thereof. In an embodiment, the composition is mixed with an oxidising formulation prior to application onto hair. Another embodiment relates to a method for increasing the density of the hair shaft and/or elasticity of the hair shaft, comprising applying the composition according to the first aspect is applied onto hair.

A different embodiment of the fourth aspect relates to a method for chemically modifying the internal region of a hair shaft, wherein the method comprises:

(i) applying an oxidising formulation to the hair, wherein the oxidising formulation comprises from about 0.01% to about 15% oxidising agent, by total weight of the oxidising formulation;

(ii) de-wetting the hair;

(iii) applying a composition according to the first aspect to the hair, wherein the composition comprises: an ethylenic monomer having a molecular weight of about 500 g/mole or less; a cosmetically acceptable carrier; an anion; and a cation, wherein the cation is selected from the group consisting of inorganic cations having a charge density of about 0.05 charge/picometre or more.

In this embodiment, the applying an oxidising formulation to the hair occurs prior to the applying the composition to the hair. Particular benefits of the method according to this embodiment include: reduced variability in the efficacy of the present invention between consumers with different hair types, and simplification of the process for applying the present invention. Without being bound by theory it is believed that a wide range of hair types exist in consumers, for example consumers may have highly damaged hair or undamaged hair. Further, it is believed that different hair types also contain different levels of redox active species that catalyze the decay of the initiator required to start the radical polymerization of an ethylenenically unsaturated monomer. Such redox active species could for example be residual amounts of metal (e.g. Fe, Co) present in the hair (e.g. from tap water), or cysteine, an amino acid found in keratin, a protein from which the hair shaft is made. The level at which those redox actives are present in human hair varies between different consumers depending upon how damaged their hair is. It is well established in polymer science that the molecular weight of a polymer made by radical polymerization is inversely proportional to the square root of the initial radical concentration. Therefore, it is believed that variability in the concentration of redox active species in consumer' s hair leads to a variability of the molecular weight of the polymer created inside hair, which correlates with its wash fastness. A higher concentration of the redox active species will lead to lower molecular polymer created inside the hair, hence inferior wash fastness, and vice versa. Whilst the professional hair stylist may be able to judge the level of macroscopic damage of the hair which may have some degree of correlation to this amount of damage, it is neither efficient nor cost-effective to provide methods and compositions that are tailor-made to each consumer hair type. Consequently, as embodied in an embodiment of the fourth aspect of the present invention, the inventors have surprisingly found that the application of an oxidising formulation to the hair prior to the application of the composition according to the first aspect results in improved performance. It is believed that this oxidising step results in the normalisation of concentration of the redox active species between hair types. A reduction step may also reduce the variability of the different hair types as well, but would at the same time also demand a significant reduction in initiator concentration to keep the initial radical concentration low. However, the initiator concentration would need to be lowered to a level at which it cannot be handled under realistic application conditions.

As described above, in an embodiment of the fourth aspect, the method of the present invention comprises de-wetting the hair. In an embodiment the de-wetting the hair comprises the application of an absorbent material to the hair such that wetness is transferred from the hair to the absorbent material and wherein the wetness comprises the cosmetically acceptable carrier. The absorbent material may be selected from the group consisting of: towel, absorbent paper, and combinations thereof. In an embodiment, the de-wetting the hair comprises allowing moisture to evaporate from the hair wherein the moisture comprises the cosmetically acceptable carrier. In an embodiment, the de-wetting the hair comprises towel drying the hair such that the oxidising formulation no longer drips from the hair. In an embodiment, the de-wetting the hair comprises removing superficial oxidising formulation from the hair. In an embodiment, the de-wetting the hair does not comprise rinsing the oxidising formulation from the hair. The de-wetting the hair may last for time z, wherein time z is from about 1 min to about 120 mins, preferably from about 2 mins to about 45 mins, more preferably from about 3 mins to about 20 mins, most preferably from about 4 mins to about 10 mins. In an embodiment, after applying the oxidising formulation to the hair but prior to de- wetting the hair, the oxidising formulation is allowed to remain on the hair for a period of time y, wherein time y is from about 1 min to about 120 mins, preferably from about 2 mins to about 45 mins, more preferably from about 3 mins to about 20 mins, most preferably from about 4 mins to about 10 mins.

In an embodiment of the fourth aspect, the method comprises providing the composition to a hair stylist and/or consumer, wherein the hair stylist and/or consumer does not need to pre- mix the composition with a second formulation prior to applying the composition to the hair. The second formulation may be selected from the group consisting of: reducing formulations, pH adjusting formulations, salt formulations, initiator formulations, oxidising formulations, catalyst formulations, and combinations thereof; preferably salt formulations, oxidising formulations, initiator formulations, and mixtures thereof.

According to the fourth aspect, the method may further comprise one or more of the following: allowing the composition according to the first aspect to remain on the hair for a period of time x, wherein time x is from about 1 min to about 120 mins; rinsing the hair; washing the hair. The time x may be from about 5 mins to about 100 mins, more preferably from about 10 mins to about 90 mins, most preferably from about 20 to about 60 mins. In an embodiment, during time x, the hair is exposed to heat. In an embodiment, during time x, the hair is exposed to a relative humidity of at least 70%, within about 1 hour of applying the composition according to the first aspect, and said exposure lasting for about 10 to about 90 min. Devices for applying said relative humidity include, for example: Hairspa ION, by Wella, Darmstadt, Germany; Electronic Master Ionic Action, by Muster; Blitz Super Electronic Ozono, by Ceriotti; Beautivap Digital Ozon and Ozono Energy, by Artem; Mega Ozono, by MediaLine; Mod. 370, by bmp; Steam Machine, by REM; Micro Mist (SD200NIW) and Belmaster (BM-975), by Takara Belmont. A suitable device is described in EP1871194.

The method according to the fourth aspect may further comprise providing and applying to hair a hair care and/or hair styling composition. Additionally or alternatively it may comprise providing and utilising an implement for applying styling effects 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. Said hair care and/or hair styling active may be selected from the group consisting of hair fixing polymers; conditioning agents, particularly cationic polymers; cleansing agents, particularly surfactants; thickeners; glossing agents; shine-imparting agents; dyes or colour- imparting agents; glitter or coloured particles; silicones; and mixtures thereof. The hair care and/or styling composition may be selected from the group consisting of waxes; gels; hair sprays; mousses; conditioning compositions, particularly leave-in conditioning compositions; finishing sprays; glossing or shine-imparting products; and mixtures thereof. The implement may be selected from the group consisting of blow dryers; flat irons, combs, brushes, curlers, curling tongs, electrical curling devices, foils, scissors, clips, hair bands, and mixtures thereof.

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

According to another aspect, the present invention may further relate to an article of commerce comprising at least one composition and/or formulation, as described herein, and a communication pertaining to the composition and/or formulation. The communication may be printed material attached directly or indirectly to packaging containing at least one composition and/or formulation pursuant to the present invention. Alternatively, the communication may be an electronic or a broadcast message that is associated with a hairstyling device and/or the composition and/or formulation. The communication may comprise images comparing the appearance of a person prior to use of the composition and/or formulation to the appearance of the same person after using the composition and/or formulation.

According to a further aspect, the present invention comprises a method of marketing a kit comprising the oxidizing formulation and the composition according to the first aspect, as described herein, wherein the method of marketing comprises the step of making available to a consumer the kit, and providing a communication to the consumer that the compositions may provide one or more benefits to the hair, including but not limited to increased appearance of hair volume, increased resistance of the hair to moisture, increased ease of styling, and/or increased retention of a hair style. Examples include all-day hold of style, excellent curl definition, increased body and/or fullness, the ability to curl straight hair, and/or the ability to straighten curly hair.

^-NMR Analysis

The kinetics of the free radical polymerisation of ethylenic monomer in aqueous media can be followed using ^-NMR. For example, the polymerisation of potassium 3- sulphopropylacrylate is shown in Reaction X below.

Reaction X

Determination of the conversion may be performed by comparison of the signals of the residual (unpolymerised) ethylenic monomer to a signal of a reference substance added to the reaction mixture before start of the reaction and/or by comparison to signals stemming from both polymer and ethylenic monomer. Triethylene glycol and sodium benzenesulfonate can be used as inert reference substances. The conversion is deduced by comparison of the integrals. When an inert reference substance is added, the conversion can be calculated according to Equation A:

conversion [%] 1 00

Equation A

wherein i_mono: integral of the signal from ethylenic monomer; nn, _mon₀: number of H atoms in signal from ethylenic monomer; X_mono: amount of ethylenic monomer before start of the reaction in moles; i_ref: integral of the signal from reference; nn, _ref: number of H atoms in signal from reference; X_ref: amount of reference in moles.

For calculation of the conversion by comparison of residual ethylenic monomer signals and combined ethylenic monomer and polymer signals, Equation B can be utilised:

conversion [%] = ^• 1 00

Equation B

wherein i_mono: integral of the signal from the ethylenic monomer; nn, _mon₀: number of H atoms in signal from ethylenic monomer; i_COmb: integral of the combined signal from ethylenic monomer and polymer; nn, con*: number of H atoms in combined signal from ethylenic monomer and polymer.

The following experimental procedure may be employed: ethylenic monomer and additives (when appropriate) in a round flask fitted with a silicone stopper are dissolved in 18 ml of the appropriate solvent (buffer with or without addition of salt, or ultra-pure demineralised water). The buffer that can be utilised for experiments at pH 5.8 is prepared as follows: 119.2 mg of NaH₂P0₄ and 141.9 mg of Na₂HP0₄ is dissolved in 110 ml of ultra pure water, then the pH is adjusted to the final value of 5.8 by addition of diluted phosphoric acid. The desired amount of initiator is dissolved in some ml of the same solvent (exact amount of solvent is adjusted individually to bring the total weight of the reaction mixture to 25.0 g). The reaction temperature is adjusted by an oil bath with contact thermometer. The reaction is started by transfer of the initiator solution to the reaction mixture with a syringe. In case no initiator is used, the flask with the starting materials is kept outside the oil bath before the reaction and the moment of contact with the oil bath is regarded as the starting point. At defined points in time, samples of 3.0 ml are drawn with a syringe. To stop the reaction, these samples are immediately exposed to air and 0.100 g of hydroquinone is added. The samples are freeze-dried separately and analysed by NMR spectroscopy for the determination of the conversion.

As an example, the structure of 3-sulfopropyl acrylate potassium salt is indicated below in Formula I, wherein the Hi indicates the position of the hydrogen atom that can be analysed by NMR.

Formula I

Signals at 6.5 to 6.4 ppm (parts per million) corresponds to Hi atom in the residual ethylenic monomer. Signals at 3.8 to 3.6 ppm corresponds to 12 H atoms in triethylene glycol. A signal at 4.4 to 4.2 ppm corresponds to the combined signal.

Utilising this technique, Figure 1 demonstrates the conversion of ethylenic monomer species into polymer species. The y axis labelled "C" shows conversion in percentage by mole of ethylenic monomer and the x-axis, which is labelled 't', shows time in mins. In the experiment labelled "Sr", the composition comprised 5.0% (by weight) SrCl₂. In the experiment labelled "Al", the composition comprised 2.4% (by weight) Al₂(S0₄)₃ x 18(¾0) i.e. aluminium sulfate octadecahydrate. Both experiments were carried out using 2.00 g 3-sulfopropyl acrylate as ethylenic monomer, in the presence of oxygen, at pH 5.8, at 20°C, utilising 1.0% (by weight) Na₂S₂C>8 as initiator, 127 mg cysteine hydrochloride at a 1:1 molar ratio with the initiator, wherein C₆H₅S0₃Na was utilized as a reference substance, and in the absence of hair. Conclusions drawn from Figure 1 include that polymerisation occurs such that almost all ethylenic monomer is converted and that there is only a subtle difference in reaction kinetics when compositions comprising aluminium and strontium cations are compared.

GPC Analysis

The molecular weights of polymer resultant from the polymerisation of ethylenic monomers may be obtained by routine GPC in water-based (anionic) solution. The GPC equipment comprises a single-channel degassing system [WGE-Dr.Bures], an isocratic pump [P 1000 of Spectra Physics], GPC-liquid 0.1 mol/1 NaN0₃ at a flux rate of 1.0 ml/min, auto-sampler AS 1000 of Spectra Physics, sampling ΙΟΟμΙ, PSS SUPREMA column (1) Guard (8 x 50 mm), (2) Suprema 3000 A (8 x 300 mm; ΙΟμηι), (3) Suprema 1000 A (8 x 300 mm; ΙΟμηι), (4) Suprema 100 A (8 x 300 mm; ΙΟμηι), column-oven K-7 of TECHLAB GmbH, Germany [at T=30°C], a UV -Detector UV 2000 of Spectra Physics, an RI-Detector Refractometer SEC-2010 of WGE Dr. Bures, Germany. Calibration was performed with Pullulan-Standards over a molecular weight range of 0.3 to 710 kDa. Data analysis was done using software WinGPC Unity by PSS.

The GPC data is presented in Figure 2. The x-axis represented by the letter 'a' is the molecular weight in Daltons (Da). The y-axis represented by the letter 'b' is the intensity. I = as per the invention (dash marker); C = comparative i.e. not per the invention (cross marker).

It is known in the art that the resulting polymer molecular weight is inversely proportional to the square root of the initial radical concentration - a radical in this sense being a ethylenic monomer having been activated by an initiator. Thus, it is important to understand the kinetics of ethylenic monomer consumption in order to make reliable conclusions from the GPC data. Hence, the applicant has utilised ^-NMR to follow the kinetics of ethylenic monomer conversion. Conclusions drawn from Figure 2 thus include that a higher molecular weight polymer results for a composition comprising aluminium cations versus for a composition comprising strontium cations.

Add-On Analysis

The amount of "add-on" i.e. the percentage change in weight of the hair following treatment is measured. Before and after treatment, the switches are weighed on an analytical balance and the difference calculated as a percent. For both weighings, the hair is in dry form. The switches are first treated with a reducing agent and then treatment with a composition pursuant to the present invention or a comparative composition follows. The switches are then weighed. The switches are then shampooed ten times with Pantene® clarifying shampoo and re- weighed. Subsequent treatments did not involve a reduction step, only the 2-step polymer treatment was applied. A total of 5 treatments are performed. For each experiment there are three repeats.

The add-on data is presented in Figure 3. The percentage add-on is shown on the y-axis represented by the letter z. When the data points taken are shown on the x-axis, labelled "x". Data point A (see x-axis) shows the measurement after treatment, A+10 (see x-axis) is after ten washes. B (see x-axis) is after then second treatment, B+10 (see x-axis) is after ten washes. C (see x-axis) is after the third treatment and C+10 (see x-axis) after ten washes. D (see x-axis) is after the fourth treatment. Data points and line "I" = treatment as per the invention (cross markers, narrow line); data points and line "C" = comparative treatment i.e. not per the invention (closed circles, dashed line). Formula I comprises: 8.0% 3-sulfopropylacrylate potassium salt, 2.45% aluminium sulfate hexadecahydrate, 1.0% sodium persulfate. Formula C comprises: 8.0% 3-sulfopropylacrylate potassium salt, 2.45% strontium chloride hexahydrate, 1.0% sodium persulfate.

Omega Loop Analysis

The same switches used for the "add on" experiment are utilised for omega loop measurement. This procedure involves forming the hair switch lengthwise into the shape of the Greek letter omega (Ω) known as an "omega loop". The hair is clamped at the roots and tips, but the O-shaped part of the hair is not fixed. Compression is then applied on top of the O-part of the omega loop. The amount of force necessary to compress the hair a defined distance is measured. There is a positive correlation between the amount of force and the stiffness of the hair. A TAJCTPlus Texture Analyzer by Texture Technologies is utilized to measure the force and the software is called Texture Exponent.

The omega loop data is also presented in Figure 3. The force in grams (g) is shown on the y-axis represented by the letter y. The omega loop measurement also occurs when the switches are weighed. Data points and line "I" = as per the invention (closed square markers, thick line); data points and line "C" = comparative i.e. not per the invention (open diamonds, dotted line). The formulas are the same as for add-on.

Conclusions drawn from Figure 3 thus include that an improvement in add-on and stiffness result for a composition according to the present invention versus a comparative composition. EXAMPLES

Composition Examples 1 - 4

Key: ¹ = Cellosize^® HEC QP-4400H from Dow Europe GmbH; ² = Keltrol CG-T from CP Kelco A HUBER COMPANY; ³ = Genapol C-100 from Clariant Produkte GmbH (Deutschland); ⁴ = Cremophor EL from BASF The Chemical Company; ⁵ = 3-sulfopropyl acrylate potassium salt from Raschig. Phase 1 and phase 2 are created separately and then mixed together. Phase 3 without the 3- sulfopropyl acrylate potassium salt is formed with heating to 40 °C, and then mixed with the other two phases. Finally the salt is added and the final composition stirred for 10 mins.

Oxidising Formulation: Examples 1 - 3

Phase 1 and phase 2 are created separately and then mixed together. The phase 1 components are mixed together and heated to 80°C until the salicylic acid is dissolved. Phase 1 is then stirred and cooled to 40°C. Then phase 2 is created and mixed in with phase 1 with stirring for 5 min.

Oxidising Formulation: Examples 4 - 6

Ex. 4 Ex. 5 Ex. 6

Phase 1

Purified water 48.00 48.00 48.00

Disodium phosphate 0.08 0.08 0.08

Salicylic acid 0.10 0.10 0.10

Phase 2

Purified water 49.96 47.35 49.56 Hydrogen peroxide 1.80 2.00 2.20

Aluminium sulfate octadecahydrate - 2.40 -

Phosphoric acid 0.06 0.07 0.06

Total 100.00 100.00 100.00

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, 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

CLAIMS What is claimed is:

1. Composition for chemically modifying the internal region of a hair shaft, wherein the composition comprises:

i. an ethylenic monomer having a molecular weight of 500 g/mole or less;

ii. a cation and an anion; wherein the cation is selected from the group consisting of inorganic cations having a charge density of 0.05 charge/picometre or more;

iii. a cosmetically acceptable carrier;

wherein the composition has a pH of from 4.0 to 6.9.

2. The composition according to claim 1, further comprising a viscosity-increasing means selected from the group consisting of viscosity-increasing agents and viscosity-increasing systems.

3. The composition according to any of the preceding claims, wherein the pH is from 4.5 to 6.7, preferably from 5.0 to 6.6, more preferably from 5.2 to 6.5, even more preferably from 5.3 to 6.5, most preferably from 5.5 to 6.5.

4. The composition according to any of the preceding claims, wherein the ethylenic monomer is present in an amount of from 0.1% to 20%, preferably from 1% to 15%, more preferably from 5% to 14%, most preferably from 7% to 13%, by total weight of the composition.

5. The composition according to any of the preceding claims, wherein the ethylenic monomer is selected from the group consisting of: mesaconic acid, 2-pentenoic acid, tiglic acid, tiglic acid esters, furan-3-acrylic acid, 2-acrylamido-2-methyl-l- propanesulfonic acid, maleamic acid, 3-aminocrotonic acid, crotonic acid esters, itaconic anhydride, trimethylsilylacrylate, poly(ethyleneglycol)acrylates, N-vinylacetamide, 2- acetamidoacrylic acid, vinylsulfonic acid, tetrahydrofurfurylacrylate, N-methyl-N- vinylacetamide, vinylpropionate, vinylanisole, vinylcrotonate, methyl 3-hydroxy-2- methylenebutyrate, methacryloyl-L-lysine, N-(2-hydroxypropyl)methacrylamide, 2- acrylamidodiglycolic acid, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, N- isopropylmethacryalmide, 2-aminoethyl methacrylate, 2-bromoethyl acrylate, 3- (dimethylamino)propyl acrylate, (3-acrylamidopropyl)trimethyl ammonium salt, [2- (acryloyloxy)ethyl]-trimethylammonium salt, alkylacetamidoacrylate, sulfoalkyl(meth)acrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and salts, isomers, derivatives, and mixtures thereof.

6. The composition according to any of the preceding claims, wherein the ethylenic monomer has a molecular weight of from 50 g/mole to 500 g/mole, preferably from 75 g/mole to 400 g/mole, more preferably from 100 g/mole to 400 g/mole.

7. The composition according to any of the preceding claims, wherein the inorganic cation is Al³⁺.

8. The composition according to any of the preceding claims, wherein molar ratio of the cation to the monomer is from 1:10 to 2:1, preferably from 1:5 to 3:2, more preferably from 1:2 to 1:1, even more preferably from 1:3 to 1:1.

9. The composition according to any of claims 2 to 8, wherein the viscosity-increasing agent comprises at least one polysaccharide, preferably at least one heteropolysaccharide.

10. A kit comprising:

(a) a product comprising the composition according to any of claims 1 to 9;

11. The kit comprising according to claim 10, wherein the kit further comprises one or more of the following:

(c) an applicator;

(d) an instruction guide;

(e) a device.

12. Use of the composition, according to any of claims 1 to 9, for chemically modifying the internal region of a hair shaft.

13. Method for chemically modifying the internal region of a hair shaft, wherein the composition according to any of claims 1 to 9 is applied onto hair.

14. Method for chemically modifying the internal region of a hair shaft, wherein an oxidising formulation is applied onto hair, wherein the oxidising formulation comprises an oxidising agent and the composition according to any of claims 1 to 9.

15. Method according to claim 14, wherein the oxidising agent is selected from the group consisting of: peroxides, preferably hydrogen peroxide; persulfates, preferably potassium persulfate or sodium persulfate; and mixtures thereof.