RS56378B1 - Method for conditioning hair and skin - Google Patents

Description

Description

Field of invention

[0001] The present invention generally relates to compositions and methods for treating hair, especially for restoring disulfide bonds in hair. Compositions and procedures for skin treatment are also described.

Prior art of the invention

[0002] Hair consists of many long chains of proteins that make up the amino acids that represent their building blocks. These chains, or polymers, are linked to each other by 1) hydrogen bonding, 2) salt bridges that form between acid and base groups, and 3) disulfide bonds. Water reversibly cuts hydrogen bonds. In this way, wet hair can be easily styled and maintained. When the water evaporates, hydrogen bonds form in new places, keeping the hair in place. In highly acidic solutions, such as those with a pH of 1.0 to 2.0, both hydrogen bonds and salt bridges are broken. Disulfide bonds, however, under such conditions, can still hold the protein chains in the hair shaft.

[0003] At a slightly basic pH of 8.5, some disulfide bonds are broken (Dombrink et al, Chem Matters, 1983, page 8). Washing again with a weak base shampoo damages the hair in such a way that disulfide bonds are increasingly broken. This causes the cuticle or the outer layer of the hair shaft to become wavy and generally leaves the hair in a wet, tangled, and generally unmanageable condition. This is one of the causes of "blooming ends." Once hair is dry, it is often left in a dry, coarse, or frizzy state. Additionally, coarse hair catches light unevenly, making hair look dull and dry. Hair can also have an increased level of static after drying, which can affect combing and lead to a condition commonly referred to as "flyaway hair."

[0004] Disulfide bonds are also broken due to heating or the use of various treatments with a reducing effect. Current compositions and procedures for creating waves and straightening mammalian hair use reducing agents such as thioglycolic acid, particularly in the form of the ammonia salt, to cleave the cystine disulfide bonds in the hair. Once the disulfide bonds are broken, the hair is stressed until the final style (eg, straight, wavy, or curly) is established by reestablishing the disulfide bonds. To restore the reduced bonds, oxidation can be achieved by simply exposing the hair to atmospheric oxygen, but this oxidation step is very slow and often of very little practical use. Generally, hydrogen peroxide or sodium bromate are used as oxidizing agents. However, the newly formed disulfide bonds are under stress to hold the new shape of the hair, therefore, they can easily break, resulting in a reversal of the hair's condition over time. In addition, the use of peroxide in the hair styling process can lead to damage to the hair, removal of color that is not natural from the hair, and/or the hair can be left frizzy. In addition, some latent free thiols may remain in the hair even after oxidative treatment.

[0005] Treatment with peroxides used in the hair styling process leads to the following reaction:

2 K-S-H H2O2→ K-S-S-K 2 H2O (Rxn I)

where K represents the keratin in the hair. However, if two K-S-H groups are not present for the reaction (Rxn I) to occur, it is considered that in that case the following reaction occurs, which results in damage to the hair.

K-S-H 3 H2O2→ K-SO2-OH 3 H2O (Rxn II)

Keratin is also a major component in the skin. Damage to the disulfide bonds in keratin can cause the skin to look unhealthy and flaky. Maintaining the disulfide bonds in keratin keeps the skin healthy and prevents cracking and splitting.

[0006] Various approaches have been developed to alleviate these problems, including the application of hair conditioners after shampooing, such as leave-in products that require rinsing. In general, rinsing the conditioner causes greasiness, especially on the damaged part of the hair where the cuticle has become wavy, considering that conditioners fit best in these parts. However, too much or too strong a conditioner can make the hair stickier, therefore more attractive to impurities and can often make multiple shampooing sessions necessary. Usually conditioners do not bind free thiols in the hair.

[0007] The use of cationic polymers to form coacervates wherein the hair benefits from the conditioner is known, as described in International Published Applications WO 93/08787 by King et al. and WO 95/01152 by Napolione et al. The most commonly used cationic polymer deposits include natural polymers, such as guar gum polymers, which have been modified with cationic substituents. Selecting a cationic guar polymer with sufficient charge density and molecular weight results in sufficient deposition of conditioning agents when incorporated into a shampoo or body wash. However, a relatively high level of such cationic guar polymer must generally be deposited on the skin or hair. In addition, the price of such guar polymer is relatively high. Incorporation of cationic guar polymer may, as a result, increase the production costs of shampoos having such compositions. Additionally, these shampoo compositions are typically useful for regenerating wet hair, but are unable to provide the satisfactory feel of smooth dry hair. Furthermore, these conditioners do not bind free thiols in the hair.

[0008] U.S. Patent No. 5,656,265 to Bailey et al., discloses a process for regenerating and styling hair for use after treating hair with a reducing agent. The method involves contacting the hair with a compound having an electrophilic group and at least one hydrophobic group. According to Bailey, electrophilic groups react with thiol groups to produce a multitude of hydrophobic groups on the hair. However, these conditioners together do not bind the free thiols in the hair.

[0009] There is a need for hair formulations and treatments that can provide better regeneration conditions for hair. In particular, there is a need to provide a long-lasting feeling of hydration, a smooth touch, and the ability to control the hair when it dries. There is also a need for hair formulations and treatments that restore latent free thiols in the hair.

[0010] There is a need for hair formulations and treatments that repair and/or strengthen damaged hair and re-establish stronger bonds in hair treated with reducing agents.

[0011] There is also a need for skin formulations and treatments that provide better conditions for skin regeneration and/or hydration. In particular, there is a need to ensure a long-lasting feeling of hydration and a smooth feeling on the skin. There is also a need for skin formulations and treatments that replenish free thiols in the skin.

[0012] Therefore, the aim of the present invention is to provide improved compositions and methods for repairing and/or strengthening damaged hair.

[0013] Also, the aim of the present invention is to provide compositions and methods for using these compositions that repair and/or strengthen the hair after washing or reducing treatment.

[0014] It is also an aim of the present invention to provide compositions and methods for regenerating, hydrating, and/or otherwise treating the skin.

OVERVIEW OF THE INVENTION

[0015] Compositions, putties, and procedures for repairing (restoring) bonds that have been previously damaged, for example, disulfide bonds, in hair or on the skin are presented. The compositions provide improved conditions for the regeneration of dry hair and skin hydration. Specifically, the compositions provide a long-lasting feeling of hydration and a smooth feel without leaving hair greasy, improved appearance (eg, shine), increased dry strength (tensile strength), easy brushing when wet or dry, less hair breakage, and reduced frizz. The compositions also provide long-lasting hydration and a smooth feel on the skin.

[0016] The compositions contain one or more compounds that interact with keratin through one or more binding events (eg, absorption, binding, etc.) which may include reaction with one or more thiols in the hair or skin. Here bonding is defined as the formation of covalent, ionic or hydrogen bonds, etc. Under normal hair washing conditions, including shampooing and conditioner application, the covalent bonds that are formed are not subject to reduction or hydrolysis. Use of the bonding compositions prevents reversion of the repaired bonds in the hair to their free thiol state for at least one week, two weeks, three weeks, four weeks, one month, or two months, or longer, after application of the composition.

[0017] Advanced hair styling procedures are provided, for example permanent hair waves, hair curling, and hair straightening. The binding compositions can be applied each time the hair is washed or daily, once a week, twice a week, fortnightly, once a month, every other month, or at less frequent intervals. Preferably, the bonding compositions are applied weekly or once a month to achieve the desired results.

[0018] Traditional procedures for obtaining permanent hair waves, hair curls or straightening use hydrogen peroxide to re-establish the disulfide bonds after a reducing treatment. It generally takes three days to complete the process. The procedures shown here use bonding agents to restore hair; these bonders are washed out the same day they are applied to the individual's hair. In some embodiments, the coupling agents and the free thiol groups form a carbon-sulfur covalent bond. Under the same conditions, such as temperature and humidity, hair treated with bonding agents takes longer to recover than the same hair that has not been treated. The binding agent may contain one or more reactive groups, wherein the reactive functional groups are attached to the surface.

[0019] In one embodiment, the binding agent contains a binding group or "spacer" and two or more reactive functional groups, wherein the reactive functional groups are bound by ionic bonds to the binding group or "spacer". In other embodiments, the binding agent contains one or more reactive groups wherein the reactive functional groups interact with the hair surface or functional groups on the hair.

DETAILED DESCRIPTION OF THE INVENTION

I. Definitions

[0020] The term "hair" refers to one or more strands of hair, as well as natural hair components, such as body oils. Hair also refers to natural hair or processed hair, for example hair that has been exposed to wave or straightening formulations.

[0021] "Effective amount", eg, of the binding agents or compositions described herein, refers to the amount of binding agents in the composition or formulation that, when administered as part of the desired dosage regimen, binds free thiols in the hair.

[0022] "Pharmaceutically acceptable" and "cosmetically acceptable" are used interchangeably and refer to those compounds, materials, compositions, and/or dosage forms which, within sound medical judgment, are suitable for use in contact with human and animal tissues without excessive toxicity, irritation, allergic response, or other problems or complications commensurate with a reasonable benefit/risk ratio. More specifically, pharmaceutically acceptable refers to a material, compound, or composition that is suitable for use in contact with the skin, scalp, or hair. Pharmaceutically acceptable materials are known to those of ordinary skill in the art.

[0023] "Shampoo", as used herein, generally refers to a liquid or semi-solid formulation applied to the hair containing a detergent or hair washing soap.

[0024] "Conditioner", as used herein, generally refers to a formulation (eg, liquid, cream, lotion, gel, semi-solid) that is applied to the hair to soften, smooth, and/or change the shine of the hair.

[0025] "Analog" and "Derivative" are used interchangeably herein, and refer to a compound that has the same base as the parent compound, but differs from the parent compound in the order of bonds, the absence or presence of one or more atoms and/or groups of atoms, and combinations thereof. A derivative may differ from the parent compound, for example, in one or more substituents found on the base, which may include one or more atoms, functional groups, or substructures. In general, it is considered that the derivative from the parent compound is formed, at least theoretically, by chemical and/or physical processes.

[0026] "Electrophilic group" or "electrophilic residue" are used interchangeably and refer to one or more functional groups or residues that have an affinity for or attract electrons.

[0027] A "Michael acceptor", as used herein, is a type of electrophilic group or residue that participates in nucleophilic addition reactions. A "Michael acceptor" may be or may contain an α,β-unsubstituted group or a carbonyl-containing residue, such as a ketone. Other Michael acceptors include pi-bonds, such as double and triple bonds conjugated to another pi-bond containing other electron-withdrawing groups, such as nitro groups, nitrile groups, and carboxylic acid groups.

[0028] "Alkyl," as used herein, refers to a radical or substituted or unsubstituted aliphatic groups, including straight chain alkyl, alkenyl, or alkynyl groups, branched chain alkyl, alkenyl, or alkynyl groups, cycloalkyl, cycloalkenyl, or cycloalkynyl (alicyclic) groups, alkyl substituted with cycloalkyl, cycloalkenyl, or cycloalkynyl groups, and cycloalkyl. substituted alkyl, alkenyl, or alkynyl groups. Unless otherwise indicated, a straight or branched alkyl chain has essentially 30 or fewer carbon atoms (eg, C1-C30 for a straight chain, C3-C30 for a branched chain), more preferably 20 or fewer carbon atoms, more preferably 12 or fewer carbon atoms, and most preferably 8 or fewer carbon atoms. In some embodiments, the chain has 1-6 carbons. Similarly, preferred cycloalkyls have from 3-10 carbon atoms in their ring structure, and more preferably have 5, 6 or 7 carbon atoms in their ring structure. The ranges listed above include all values between the minimum value and the maximum value.

[0029] The term "alkyl" includes both "unsubstituted alkyls" and "substituted alkyls", the latter referring to alkyl groups with one or more substituents replacing a hydrogen atom on one or more carbon atoms in a hydrocarbon side chain. Such substituents include, but are not limited to, halogen, hydroxyl, carbonyl (such as carboxyl, alkoxycarbonyl, formyl, or acyl), thiocarbonyl (such as thioester, thioacetate, or thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino, amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamide, sulfonyl, heterocyclyl, aralkyl, or an aromatic or heteroaromatic residue.

[0030] Unless the number of carbon atoms is otherwise indicated, "lower alkyl" as used herein means an alkyl group, as defined above, but containing from one to ten carbon atoms, preferably from one to six carbon atoms in the main chain structure. Similarly, "lower alkenyl" and "lower alkynyl" have similar chain lengths. Preferred alkyl groups are lower alkyl.

[0031] Alkyl groups may also contain one or more heteroatoms at the base of the carbon chain. Examples include oxygen, nitrogen, sulfur, and combinations thereof. In certain embodiments, the alkyl group contains between one and four heteroatoms.

[0032] "Alkenyl" and "Alkynyl" as used herein refer to unsubstituted aliphatic groups containing one or more double or triple bonds of similar length (eg, C2-C30) and optional substitution of alkyl groups as described above.

[0033] "Aryl," as used herein, refers to 5-, 6-, and 7-membered aromatic rings. The ring may be a carbocyclic, heterocyclic, fused carbocycle, fused heterocycle, bicarbocyclic, or biheterocyclic ring system, which is optionally substituted as described above for alkyl. Broadly defined, "Ar" as used herein includes 5-, 6-, and 7-membered single-ring aromatic groups that may include from zero to four heteroatoms. Examples include, but are not limited to, benzene, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine. Those aryl groups having heteroatoms in the ring structure may also be called "heteroaryl", "aryl heterocycles", or "heteroaromatic compounds". The aromatic ring may be substituted at one or more ring positions with substituents as defined above, for example, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic residues, perfluoroalkyl, and cyano. The term "Ar" also includes a polycyclic ring system wherein two or more cyclic rings are shared by two adjacent rings (the rings are "fused rings") wherein at least one of the rings is aromatic, e.g., the other cyclic rings may be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, and/or heterocycles, or both rings are aromatic.

[0034] "Alkylaryl", as used herein, refers to an alkyl group substituted with an aryl group (eg, an aromatic or heteroaromatic group).

[0035] "Heterocycle" or "heterocyclic", as used herein, refers to a cyclic radical that is attached through a carbon or nitrogen ring of a monocyclic or bicyclic ring containing 3-10 ring atoms, and preferably of 5-6 ring atoms, containing carbon and one to four heteroatoms each selected from non-peroxide oxygen, sulfur, and N(Y) where Y is absent or H, O, (C1-4) alkyl, phenyl or benzyl, and optionally contains one or more double or triple bonds, and is optionally substituted with one or more substituents. The term "heterocycle" also includes substituted and unsubstituted aryl rings. Examples of heterocyclic rings include, but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl, chromenyl, quinriolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, dihydrofuro[2,3-b]tetrahydrofuranyl, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phthalazinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole, pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl, pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolisinyl, quinoxalinyl, quinoclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 6H-1,2,5-thiadiazinyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienoxazolyl, thienoimidazolyl, thiophenyl, and thienoxazolyl. xanthenyl.

[0036] "Heteroaryl", as used herein, refers to a monocyclic aromatic ring with five or six ring atoms containing carbon and 1, 2, 3, or 4 heteroatoms each selected from non-peroxide oxygen, sulfur, and N(Y) wherein Y is absent or is H, O, (C1-C8) alkyl, phenyl, or benzyl. Non-limiting examples of heteroaryl groups include furyl, imidazolyl, triazolyl, triazinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, pyrrolyl, pyrazinyl, tetrazolyl, pyridyl, (or its N-oxide), thienyl, pyrimidinyl (or its N-oxide), indolyl, isoquinolyl (or its N-oxide), quinolyl (or its N-oxide), and the like. The term "heteroaryl" may include ortho-fused bicyclic heterocycle radicals of about eight to ten ring atoms derived therefrom, particularly the benz-derivative or derivatives formed by fusion of propylene, trimethylene, or tetramethylene radicals therewith. Examples of heteroaryls include, but are not limited to, furyl, imidazolyl, triazolyl, triazinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, pyrrolyl, pyrazinyl, tetrazolyl, pyridyl (or its N-oxide), thienyl, pyrimidinyl (or its N-oxide), indolyl, isoquinolyl (or its N-oxide), quinolyl (its N-oxide), and the like.

[0037] "Halogen," as used herein, refers to fluorine, chlorine, bromine, or iodine.

[0038] The term "substituted" as used herein refers to all permitted substituents of the compounds described herein. In the broadest sense, allowed substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, but are not limited to halides, hydroxyl groups, or any other organic group containing any number of carbon atoms, preferably 1-14 carbon atoms, and optionally include one or more heteroatoms such as oxygen, sulfur, or nitrogen that are grouped into linear, branched, or cyclic structural formats. Representative substituents include alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, phenyl, substituted phenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, halo, hydroxyl, alkoxy, substituted alkoxy, phenoxy, substituted phenoxy, aroxy, substituted aroxy, alkylthio, substituted alkylthio, phenylthio, substituted phenylthio, arylthio, substituted arylthio, cyano, isocyano, substituted isocyano, carbonyl, substituted carbonyl, carboxyl, substituted carboxyl, amino, substituted amino, amido, substituted amido, sulfonyl, substituted sulfonyl, sulfonic acid, phosphoryl, substituted phosphoryl, phosphonyl, substituted phosphonyl, polyaryl, substituted polyaryl, C3-C20cyclic, substituted C3-C20 cyclic, heterocyclic, substituted heterocyclic, amino acid, peptide, and polypeptide groups.

[0039] Heteroatoms, such as nitrogen, may have hydrogen substituents and/or any of the allowed substituents of the organic compounds described herein satisfying the valence of the heteroatom. It is understood that "substitution" or "substituted" includes the implicit condition that the substitution is in accordance with the allowed valence of the substituted atom and the substituent, and that the substitution results in a stable compound, ie. a compound that does not undergo spontaneous transformation such as translocation, cyclization, elimination, etc.

[0040] "Polymer", as used herein, refers to a molecule containing more than 10 monomer units.

[0041] "Water soluble", as used herein, generally means that at least 10, 50, 100, 125, 150, 200, 225, or 250 g is soluble in 1 L of water at 25°C.

[0042] "Binding agent", as used herein, means as used herein, refers to a molecule that forms covalent, ionic or hydrogen bonds, e.g. with hair and generally involves the formation of at least one covalent bond with a free thiol.

II. Binding formulations

[0043] The formulations presented herein relate to the treatment of hair or skin. In particular, the formulations can restore hidden disulfide bonds in hair or skin. Additionally, the formulations can also react with free amines in the hair to provide a regenerating effect.

[0044] The formulations contain one or more binding agents (also referred to herein as "compounds" or "active agents").

[0045] Binding agents can be combined with one or more acceptable pharmaceutical carriers and/or excipients that are considered safe and effective for human hair, skin, and/or human scalp, but that can be applied to the individual's hair without causing undesirable adverse side effects, such as burning, itching, and/or redness, or similar adverse reactions. The formulations may further contain an excipient that causes the formulations to have a neutral pH, or a pH in the range of about pH 3 to about pH 12, preferably about pH 5 to pH 8.

[0046] The binder is typically present in an amount ranging from about 0.01 wt% to about 50 wt% of the formulation, preferably from about 1 wt% to about 25 wt% of the formulation, more preferably from about 1 wt% to about 15 wt%, most preferably from about 1 wt% to about 10 wt%. Generally, the binding agent is about 2.5-3 wt% of the formulation.

[0047] The binding agent is stable in aqueous solution for a period of at least 2, 3, 4, 5, 6, 8, 9, 10, 11, or 12 months or longer at a pH of 6 to 8 and at a temperature of about 25-30°C, preferably about 25°C. "Stable" as used herein with respect to shelf life means that at least 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% of the reactive moieties are intact or to the extent that the reactive groups react with water, the resulting product is also electrophilic.

a. Binding agent

[0048] The coupling agent contains at least two reactive moieties capable of reacting with a thiol. The coupling agent optionally contains a linking group between two or more reactive moieties. A vesujuda group forms two or more ionic bonds with reactive residues. Reactive residues after the reaction with the thiol are grouped on the hair follicle, forming bonds that are stable, for example, hydrolytically stable. "Stable" as used in reference to bonds formed between thiol groups on hair follicles means that the bonds remain intact for at least one week, two weeks, three weeks, four weeks, one month, or two months or longer when exposed to water at pH 6-8 at a temperature of from about 5°C to about 100°C, preferably from about 20°C to about 75°C, more preferably from about 20°C to about 50°C, more preferably from about 25°C to about 40°C, most preferably from about 25°C to about 30°C. In some embodiments, the temperature is about 25 °C. It is also preferred that the coupling reaction occurs at a temperature close to room temperature, for example, from about 15°C to about 35°C, preferably from about 20°C to about 30°C, more preferably from about 22°C to about 27°C.

[0049] Binding agents are usually low molecular weight and compatible with aqueous or solvent delivery systems. In some embodiments, the compound is water soluble. A low molecular weight is preferred, as it allows the molecule to diffuse into and out of the hair at a reasonable rate. Molecular weights of less than 10,000 Da, 8,000 Da, 6,000 Da, 5,000 Da, 4,000 Da, 3,000 Da, 2,000 Da, or 1,000 Da are preferred. In some embodiments, the molecular weight is less than 1500 Da, preferably less than 800 Da, most preferably less than 500 Daltons to achieve adequate diffusion rates in conventional aqueous hair care systems.

and. Binding agents defined by formula I

[0050] Binding agents have a structure according to formula I:

whereby they

A, B, C, and D reactive moieties that can react with free thiol groups each containing one or more batches, wherein each of the A, B, C, and D reactive groups independently contains a residue selected from the group consisting of vinyl sulfone, 30 acrylate groups, methacrylate groups, styrene groups, acryl amide groups, methacryl amide groups, maleate groups, fumarate groups, and itaconate groups; (R) is a binding group containing two or more charges, wherein the charges are opposite to the reactive residues, wherein R is a monomer, n=1-10, and wherein (R) is a polymer, and the sum of the charges is zero, and wherein the reactive residues are ionically bonded to the bonding group; and each occurrence of p, q, r, and s is independently a number from 0 to 25, preferably from 0 to 10, more preferably from 0 to 2. The sum of p q r s is equal to or greater than 2; provided that the binding agent of the formula i is not a trimealate salt of

H2N-(CH2)3-N<1>(G)-(CH2)4-NH2

wherein G is a substituent that is attached to the secondary amine group of spermidine, which is selected from chained or unchained, linear or branched alkyl groups formed from 1 to 6 carbon atoms, whereby one or more carbon atoms are optionally replaced with fluorine, that is methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene; an aryl or aryl-alkyl group, such as phenyl, naphthyl, benzyl, tolyl, wherein one or more carbon atoms are optionally replaced by fluorine, and wherein said aryl-alkyl groups include saturated or unsaturated, linear or branched alkyl groups formed from 1 to 6 carbon atoms, wherein one or more carbon atoms are optionally replaced by fluorine, i.e. methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene; chained or unchained cycloalkyl groups formed by 3 to 8 carbon atoms that are optionally replaced with chained or unchained, linear or branched alkyl groups formed by 1 to 6 carbon atoms, wherein one or more carbon atoms are optionally replaced by fluorine, that is methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene.

[0051] Reactive residues can be located on any atom of the bonding group. In some embodiments, the reactive moieties are the same. In some embodiments, one or more active residues are different.

[0052] In some embodiments, the reactive moieties have a negative charge and the linking group or "spacer" has positively charged moieties. In other embodiments, the reactive moieties have a positive charge and the linking group or "spacer" has negatively charged moieties.

ii. Linking group

[0053] Reactive residues on the binding agents are linked by means of the linking group (R)n. The term "linking group", as used herein, refers to one or more polyfunctional, e.g. bifunctional residues, trifunctional molecules, tetrafunctional molecules, etc., which can be used to ionic bond two or more reactive residues and which do not interfere with the reactive properties of the binding agents. Reactive moieties can be attached to any part of the linking group.

[0054] Linking groups can be a single atom, such as a heteroatom (ie, O or S), a group of atoms, such as a functional group (ie, amine, -C(=O)-, -CH 2 -), or multiple groups of atoms, such as an alkylene chain. Suitable linking groups include, but are not limited to, oxygen, sulfur, carbon, boron, nitrogen, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, ether, and amine.

[0055] The linking group is optionally independently substituted with one or more substituents including hydrogen, halogen, cyano, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine, hydroxy, formyl, acyl, carboxylic acid (-COOH), -C(O)R<1>, -C(O)OR<1>, carboxylate (-COO-), primary amide (ie, -CONH2), secondary amide (ie, -CONHR<1>), -C(O)NR<1>R<2>, -NR<1>R<2>, -NR<1>S(O)2R<2>, -NR<1>C(O)R<2>, -S(O)2R<2>, -SR<1>, and -S(O)2NR<1>R<2>, sulfinyl group (ie, -SOR<1>), and a sulfonyl group (ie, -SOOR<1>); wherein R<1> and R<2> can each independently be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl and heteroaryl; wherein each of R<1> and R<2> is optionally substituted independently with one or more substituents independently selected from the group consisting of halogen, hydroxy, cyano, nitro, amino, alkylamino, dialkylamino, alkyl optionally substituted with one or more halogen or alkoxy or aryloxy, aryl optionally substituted with one or more halogen or alkoxy or alkyl or trihaloalkyl, heterocycloalkyl which is optionally substituted with aryl or heteroaryl or =O or alkyl optionally substituted with hydroxy cycloalkyl optionally substituted with hydroxy, heteroaryl optionally substituted with one or more halogen or alkoxy or alkyl or trihaloalkyl, haloalkyl, hydroxyalkyl, carboxy, alkoxy, aryloxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl and dialkylaminocarbonyl.

[0056] In some embodiments, the linking group can be alkoxy, ether, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, or amine. The vesujuda group is not a polymer.

iv. Reactive residues that react with thiols

[0057] The coupling agent contains at least two reactive moieties that react with thiols to form covalent bonds. Reactive residues can react with a thiol group in hair or skin, forming a stable covalent bond. The reactive residue is usually an electrophilic residue that can form a salt with any bonding group. Alternatively, the reactive moiety can be a free radical forming moiety.

[0058] The binding agent contains at least two reactive moieties. However, the linker may contain three, four, five, six, or more than six reactive moieties.

[0059] The reaction between the reactive residue thiol groups can be initiated at room temperature and pressure when the reactive residue makes contact with a thiol group in hair or skin. In some embodiments, the reaction may require the presence of an initiator, such as heat, a catalyst, basic conditions, or a free radical initiator. The rate of reaction between the reactive moiety and the thiol can be increased by changes in temperature, pH, and/or by the addition of one or more excipients, such as a catalyst; however, this is generally not necessary.

[0060] Two or more reactive moieties on the binding agent may be the same. In some embodiments, the two or more reactive moieties are different.

[0061] In some embodiments, the reactive moieties can undergo a conjugate addition reaction. Reactive moieties may independently be or contain a vinyl sulfone, an acrylate group, a methacrylate or methacrylate group, a styrene group, an acrylamide group, a methacrylamide group, a maleate group, a fumarate group, or an itaconate group.

Vinyl sulfone

[0062] The chemistry of vinyl sulfones with respect to attack by nucleophiles is analogous to α,β-unsubstituted ketones where they can undergo a type of 1,4 Michael addition without releasing any undesirable side products.

Groups that form free radicals

[0063] The binding agent can contain at least two groups that form free radicals that can react with thiols. The free radical forming groups on the binding agent can be the same. Alternatively, the free radical forming groups may be different. Suitable free radical forming groups include acrylate groups, methacrylate groups, styrene groups, acryl amide groups, methacryl amide groups, maleate groups, fumarate groups and itaconate groups. For example, suitable coupling agents include ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, and di- and triacrylates, mixed acrylates which, like the acrylate groups, further contain ethylenic substituents. Other examples of coupling agents include N,N'-methylenebisacrylamide and N,N'-methylenebismethacrylamide, esters of unsaturated mono- or polycarboxylic acids of polyols, such as diacrylate or triacrylate, for example butanediol diacrylate, butanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate and also trimethylolpropane triacrylate and allyl compounds, such as allyl (meth)acrylate, and diallyl maleate. Other examples of coupling agents include di- and triacrylates of 3- to 15-fold ethoxylated glycerol, of 3- to 15-fold ethoxylated trimethylolpropane, of 3- to 15-fold ethoxylated trimethylolethane, especially di- and triacrylates of 2- to 6-fold ethoxylated glycerol or of 2- to 6-fold ethoxylated trimethylolpropane, from 3-fold propoxylated glycerol, from 3-fold propoxylated trimethylolpropane, and also from 3-fold mixed ethoxylated or propoxylated glycerol, from 3-fold mixed ethoxylated or propoxylated trimethylolpropane, from 15-fold ethoxylated glycerol, from 15-fold ethoxylated with trimethylolpropane, from 40-fold ethoxylated glycerol, from 40-fold ethoxylated trimethylolethane and also from 40-fold ethoxylated trimethylolpropane, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, N,N<1>-methylenebisacrylamide, N,N'-methylenebismethacrylamide, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, triallyl cyanurate, diallyl maleate, di- and tri-acrylates of 3- to 15-fold ethoxylated glycerol, di- and tri-acrylates of 3- to 15-fold ethoxylated trimethylolpropane, and di- and tri-acrylates of 3- to 15-fold ethoxylated trimethylolethane. As used herein, the term "fold" refers to the number of monomer units in the ethoxylated chain.

[0064] Reactive free radical residues may require the presence of one or more initiators. Suitable initiators include, but are not limited to, peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds, and redox initiators. Suitable organic peroxides include acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl perisobutyrate, tert-butyl per-2-ethylhexanoate, tert-butyl perisononanoate, tert-butyl permaleate, tert-butyl perbenzoate, di(2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, diacetyl peroxydicarbonate, allyl peresters, cumyl peroxynodecanoate, tertbutyl per-3,5,5-trimethylhexanoate, acetylcyclohexylsulfonyl peroxide, dilauryl peroxide, dibenzoyl peroxide, and tert-aryl perneodecanoate. Suitable azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), preferably water-soluble azo initiators such as, but not limited to, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, 2,2'-azobis-(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride and 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride. For redox initiators, the oxidizing component is at least one of the peroxo compounds as listed above and the reducing component is, for example, ascorbic acid, glucose, sorbose, ammonium bisulfite, ammonium sulfite, ammonium thiosulfate, ammonium hyposulfite, ammonium pyrosulfite, ammonium sulfide, alkali metal bisulfite, alkali metal sulfite, alkali metal thiosulfate, alkali metal hyposulfite, alkali metal pyrosulfite, alkali metal sulfide, or sodium hydroxymethylsulfoxylate.

[0065] In some embodiments, the molecule is:

or

[0066] In some embodiments, the binding agent has the structure:

[0067] The reaction with thiol groups on hair follicles is as follows:

[0068] Other agents include, but are not limited to, acids containing electrophiles, such as acrylic acid and bromoacetic acid and similar compounds.

b. Excipients

[0069] Formulations usually contain one or more cosmetically acceptable excipients. Cosmetically acceptable excipients include, but are not limited to, water, preservatives, antioxidants, chelating agents, sunscreens, vitamins, dyes, hair dyes, proteins, amino acids, natural extracts such as plant extracts, humectants, fragrances, perfumes, oils, emollients, lubricants, butters, penetrants, hardening agents, viscosity modifiers, polymers, resins, hair fixatives, film formers, surfactants, detergents, emulsifiers, delay agents, volatiles, propellants, liquid carriers, carriers, salts, pH adjusting agents (eg, citric acid), neutralizing agents, buffers, hair conditioners, anti-static agents, anti-frizz agents, anti-dandruff agents, absorbents, and combinations thereof.

[0070] The formulations may contain at least two or more cosmetically acceptable excipients. In some embodiments, the formulations contain a binding agent, water, and optionally a preservative and/or fragrance.

[0071] The hair treatment formulations may be in a suitable physical form. Suitable forms include, but are not limited to, low to moderately viscous liquids, lotions, milks, foams, sprays, gels, creams, shampoos, conditioners, and the like. Suitable excipients, such as those listed above, are included or excluded from hair care formulations depending on the form of the formulation to be used (eg, hair spray, cream, conditioner, or shampoo).

[0072] Formulations for treating the skin may be in a suitable physical form. Suitable forms include, but are not limited to low to moderate viscosity liquids, lotions, milks, mousses, foams, sprays, gels, creams, ointments, and the like. Suitable excipients, such as those listed above, are included or excluded from skin formulations depending on the form of use of the formulation (eg, lotion, gel, ointment, or cream).

[0073] The pharmaceutical excipient is typically present in an amount ranging from about 10 wt% to about 99.99 wt% of the formulation, preferably from about 40 wt% to about 99 wt%, more preferably from about 80 wt% to about 99 wt%.

i. Surfactants

[0074] Surfactants are surface active agents that can reduce the surface tension of water and cause the formulation to slide over the skin or on the skin or hair. Surfactants also include detergents and soap. Surfactants can be amphoteric, anionic, or cationic. Suitable surfactants that may be used in the formulation include, but are not limited to, 3-aminopropane sulfonic acid, almond amide, amidopropyl betaine almond, amidopropylamine oxide almond, aluminum hydrogenated fatty glutamate, aluminum lanolate, aminoethyl sulfate, aminopropyl lauryl glutamine, ammonium C12-15alkyl sulfate, ammonium C12-15parate sulfate, ammonium C12-16alkyl sulfate, ammonium C9-10perfluoroalkylsulfonate, ammonium caprylate sulfate, ammonium caprylet-3 sulfate, ammonium monoglyceride sulfate, ammonium sulfate, ammonium isothionate, ammonium cocoyl sarcosinate, ammonium cumene sulfonate, ammonium dimethicone copolyol sulfate, ammonium dodecylbenzenesulfonate, ammonium isostearate, ammonium laureth sulfate, ammonium laureth-12 sulfate, ammonium laureth-5 sulfate, ammonium laureth-6 carboxylate, ammonium laureth-7 sulfate, ammonium laureth-8 carboxylate, ammonium laureth-9 sulfate, ammonium lauroyl sarcosinate, ammonium lauryl sulfate, ammonium lauryl sulfosuccinate, ammonium myrrhet sulfate, ammonium myristyl sulfate, ammonium nonoxynol-30 sulfate, ammonium nonoxynol-4 sulfate, ammonium oleate, palm ammonium kernel sulfate, ammonium polyacrylate, ammonium stearate, ammonium thalate, ammonium xylene sulfonate, ammonium xylene sulfonate, Amp-Isostearoyl Gelatin/ Keratin Amino Acids/Lysine Hydroxypropyltrimonium Chloride, Amp-Isostearoyl Hydrolyzed Collagen, Apricot Kernel Oil, PEG-6 Esters, Apricot Amide, Apricot Amidopropyl Betaine, Arachide-20, Avocadamide, Avocadamidopropyl Betaine, Babasuamide, Babasuamidopropyl Betaine, Babasuamidopropylamine Oxide, Behenalkonium Chloride, Behenamide, Behenamide, Behenamidopropyl Betaine, behenamine oxide, sodium laureth sodium lauryl sulfate, lauryl alcohol polyoxyether or ceteareth-20, or combinations thereof.

[0075] Suitable anionic surfactants include, but are not limited to, those containing carboxylate, sulfonate, and sulfate ions. Examples of anionic surfactants include sodium, potassium, ammonia long chain alkyl sulfonates and alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate; dialkyl sodium sulfosuccinates, such as sodium dodecylbenzene sulfonate; dialkyl sodium sulfosuccinates and, such as sodium bis-(2-ethylthioxyl)-sulfosuccinate; and alkyl sulfates such as sodium lauryl sulfate. Cationic surfactants include, but are not limited to, quaternary ammonia compounds such as benzalkonium chloride, benzethonium chloride, cetrimonium bromide, stearyl dimethylbenzyl ammonium chloride, polyoxyethylene, and coco amine. Examples of nonionic surfactants include ethylene glycol monostearate, propylene glycol myristate, glyceryl monostearate, glyceryl stearate, polyglyceryl-4-oleate, sorbitan acylate, sucrose acylate, PEG-150 laurate, PEG-400 monolaurate, polyoxyethylene monolaurate, polysorbates, polyoxyethylene octylphenyl ether, PEG-1000 cetyl ether, polyoxyethylene tridecyl ether, polypropylene glycol. butyl ether, Poloxamer 401, stearoyl monoisopropanolamide, and polyoxyethylene hydrogenated tallow amide. Examples of amphoteric surfactants include sodium N-dodecyl-beta-alanine, sodium N-lauryl-β-iminodipropionate, myristoamphoacetate, lauryl betaine, and lauryl sulfobetaine.

[0076] More than one surfactant may be included in the formulation.

[0077] Surfactants are optionally included in an amount ranging from about 0.1% to about 15% by weight of the formulation, preferably about 1% to about 10% by weight of the formulation.

ii. Emollients

[0078] Emollient refers to a material that protects against moisture or irritation, softens, soothes, coats, lubricates, moisturizes, protects, and/or cleans the skin. Suitable emollients for use in the formulations include, but are not limited to, silicone compounds (eg, dimethicone, cyclomethicone, dimethicone copolyol or a mixture of cyclopentasiloxane and dimethicone/vinyldimethicone via polymer, cyclopentasiloxane polysilicone), polyols such as sorbitol, glycerin, propylene glycol, ethylene glycol, polyethylene glycol, caprylyl glycol, polypropylene glycol, 1,3-butane diol, hexylene glycol, isoprene glycol, xylitol; ethylhexyl palmitate; and a triglyceride such as caprylic/caprid triglyceride and a fatty acid ester such as cetearyl isononanoate or cetyl palmitate. In a specific embodiment, the emollient is dimethicone, amidodimethicone, dimethiconol, cyclopentasiloxane, potassium dimethicone PEG-7 pantenyl phosphate, or a combination thereof. More than one emollient may be included in the formulation.

[0079] The emollient is optionally included in an amount ranging from about 0.5% to about 15% by weight of the formulation, preferably from about 1% to about 10% by weight of the formulation.

iii. Emulsifiers

[0080] Formulations may also contain one or more emulsifiers. Suitable emulsifiers include, but are not limited to, copolymers of unsaturated esters and styrene sulfonate monomer, cetaryl alcohol, glyceryl ester, polyoxyethylene glycol ether cetaryl alcohol, stearic acid, polysorbate-20, cetaret-20, lecithin, glycol stearate, polysorbate-60, or polysorbate-80, or combinations thereof. More than one emulsifier may be included in the formulation.

[0081] The emulsifier is optionally included in an amount ranging from about 0.05% to about 15% by weight of the formulation, preferably from about 0.1% to about 10% by weight of the formulation.

iv. Preservatives

[0082] One or more preservatives may be included in the formulations to prevent the growth of microorganisms in the formulations. Suitable preservatives include, but are not limited to, compounds containing glycerin (eg, glycerin or ethylhexylglycerin or phenoxyethanol), benzyl alcohol, parabens (methylparaben, ethylparaben, propylparaben, butylparaben, isobutylparaben, eg), sodium benzoate, ethylenediaminetetraacetic acid (EDTA), potassium sorbate, and/or grapefruit seed extract, or combinations thereof. More than one preservative may be included in the formulation. Other preservatives are known in the cosmetics industry and include salicylic acid, DMDM hydantoin, formaldehyde, chlorphenism, triclosan, imidazolidinyl urea, diazolidinyl urea, sorbic acid, methylisothiazolinone, sodium dehydroacetate, dehydroacetic acid, quaternium-15, stearalkonium chloride, zinc pyrithione, sodium metabisulfite, 2-bromo-2-nitropropane, chlorhexidine digluconate, polyaminopropyl biguanide, benzalkonium chloride, sodium sulfite, sodium salicylate, citric acid, "Neem" oil, essential oils (various), lactic acid, and vitamin E (tocopherol).

[0083] The preservative is optionally included in an amount ranging from about 0.1% to about 5% by weight of the formulation, preferably from about 0.3% to about 3% by weight of the formulation. Preferably, the formulations are paraben free.

v. Regeneration agents

[0084] One or more regenerating agents may be included in the formulations. Suitable conditioning agents include, but are not limited to, silicone-based agents (e.g., quaternary-8 silicone), panthenol, hydrolyzed wheat and/or soy protein, amino acids (e.g., wheat amino acids), rice wax, wheatgrass seed oil, mango seed oil, grape seed oil, jojoba seed oil, sweet almond oil, hydroxyethyl behenamidopropyl dimonium chloride, aloe leaf extracts, aloe vera leaf juice, phytantriol, panthenol, retinyl palmitate, behentrimonium methosulfate, cyclopentasiloxane, quaternium-91, stearamidopropyl dimethylamine, and their combinations.

[0085] The regeneration agent(s) is/are included as needed in an amount ranging from about 0.1% to about 5% by weight of the formulation, preferably from about 0.3% to about 3% by weight of the formulation.

vi. Solvents

[0086] Solvent, as used herein, refers to a substance(s) that dissolves a binding agent. The preferred solvent is water. The formulations generally contain greater than one percent (wt) water, preferably greater than five percent (wt) water, more preferably greater than 50% (wt) water, and most preferably greater than 80% (wt) water. Alcohols, such as ethyl alcohol and isopropyl alcohol, may be used at low concentrations (about 0.5% by weight of the formulation) to improve penetration into hair or skin and/or reduce odor.

vii. Viscosity modifiers

[0087] Formulations may contain one or more viscosity modifying agents, such as viscosity increasing agents. Classes of such agents include, but are not limited to, viscous liquids, such as polyethylene glycol, semi-synthetic polymers, such as semi-synthetic cellulose derivatives, synthetic polymers, such as carbomers, poloxamers, and polyethyleneimines (e.g., PEI-10), naturally occurring polymers, such as acacia, tragacanth, alginates (e.g., sodium alginate), carrageenan, vegetable gums, such as xanthan gum, petroleum jelly, waxes, particle-binding colloids, such as bentonite, colloidal silicon dioxide, and microcrystalline cellulose, surfactants, such as PPG-2 hydroxyethyl coco/isostearamide, emulsifiers, such as distearate-75 IPDI, and salts, such as sodium chloride, and combinations thereof.

viii. Antioxidants

[0088] Formulations may contain one or more antioxidants. Examples include, but are not limited to, tocopheryls, BHT, ascorbic acid, camellia sinensis leaf extract, ascorbyl palmitate, magnesium ascorbyl phosphate, carotenoids, resveratrol, triethyl citrate, arbutin, kojinic acid, tetrahexydecyl ascorbate, superoxide dismutase, zinc, sodium metabisulfite, lycopene, ubiquinone, and combinations thereof.

ix. Means for delay

[0089] Formulations may contain one or more delaying agents. Delaying agents are added to formulations to make them opaque. Suitable delaying agents include, but are not limited to, glycol distearate and ethoxylated fatty acid alcohols.

c. Forms of formulation

i. Sprays

[0090] Formulations can be in the form of a spray. The spray usually includes a binding agent and a cosmetically acceptable carrier. In some embodiments, the carrier is water or a mixture of alcohol and water. The spray formulation optionally includes an antioxidant, sunscreen, vitamin, protein, peptide, plant extract, humectant, oil, emollient, lubricant, hardening agent, hair conditioner, polymer, and/or surfactant. Preferably, the spray formulation includes a preservative. In some embodiments, the formulation includes a fragrance. In some embodiments, the formulation includes a surfactant. In some embodiments, the formulation contains water, a fragrance, a preservative, and a binding agent. In some embodiments, the formulation contains water, a fragrance, a preservative, and a binding agent. In some embodiments, the formulation contains water, a fragrance, a preservative, and a binding agent. In some embodiments, the formulation contains water, a fragrance, a preservative, a binding agent and an anti-static agent. In some embodiments, the formulation contains water, a fragrance, a preservative, a binding agent, and a hair conditioning agent. In some embodiments, the formulation comprises water, a fragrance, a preservative, a binding agent, and a surfactant.

[0091] Hair spray formulations can be sprayed from containers that include aerosol dispensers or pump spray dispensers. Such sprayers are known in the art and are commercially available from various manufacturers.

Propellants

[0092] When the hair formulation is sprayed from a pressurized aerosol container, a propellant can be used to expel the composition from the container. Suitable propellants include, but are not limited to, liquid gas or halogenated propellant. Examples of suitable propellants include dimethyl ether and hydrocarbon propellants such as propane, n-butane, iso-butane, CFCs, and CFC-substitute propellants. Propellants can be used in single or mixed form.

[0093] The amount of propellant can range from about 10% to about 60% by weight of the formulation. The propellant can be separated from the hair conditioning formulation using a container containing two compartments. Other suitable spray aerosols are those characterized in that the propellant is contained in compressed air, which can be filled into the spray using a pump or similar device prior to use. Conventional non-aerosol pump sprayers, i.e., atomizers, can be used to apply hair strengthening formulations to the hair.

ii. Regenerators

[0094] Formulations can be in the form of a conditioner. The regenerator usually includes a binding agent in a suitable carrier. Additionally, the conditioner may include cationic polymers derived from polysaccharides, for example cationic cellulose derivatives, cationic starch derivatives, cationic guar derivatives and cationic locust bean derivatives, synthetic cationic polymers, mixtures or combinations of these agents. The formulations may contain other synthetic or natural polymers or polymers resulting from biological production processes, which are functionalized with, where possible, for example cationic or neutral groups. These polymers can have a stabilizing or strengthening effect on the compositions, and/or an effect on regeneration (deposition on the skin or hair).

[0095] The binding agent may be included in any suitable concentration. Common concentrations of binders in the conditioner range from low amounts such as approximately 0.01% (w/w), preferably at least 0.1% (w/w), to higher amounts such as up to 50% (w/w). Preferably the conditioner contains a binding agent in a concentration ranging from 0.1% (w/w) to 5% (w/w), more preferably from 0.1% w/w to 3% (w/w). While higher concentrations of binders should be present in the conditioner, they are generally not needed to achieve the desired results.

iii. Shampoos

[0096] Formulations for hair regeneration can be in the form of shampoos. Shampoo usually includes a binding agent in a suitable carrier. The binding agent may be included in any suitable concentration. Common concentrations of binding agent in shampoo range from low amounts such as approximately 0.01% (w/w), preferably at least 0.1% (w/w), to higher amounts such as up to 50% (w/w). Preferably the shampoo contains a binding agent in a concentration ranging from 0.1% (w/w) to 5% (w/w), more preferably from 0.1% (w/w) to 3% (w/w). While higher concentrations of binding agents should be found in the shampoo, they are generally not needed to achieve the desired results.

[0097] Additionally, the shampoo may include from about 0.5% to about 20% surfactant material. Surfactants used in shampoo compositions are well known in the art and are disclosed, for example, in U.S. Pat. Patent No. 6,706,258 to Gallagher et al. and U.S. Patent No. 7,598,213 to Geary et al.

iv. Creams

[0098] Formulations can be in the form of a cream. The cream usually includes a binding agent in a suitable carrier. The binding agent may be included in any suitable concentration. Common concentrations of the binding agent in the cream range from low amounts such as approximately 0.01% (w/w), preferably at least 0.1% (w/w), to higher amounts such as up to 50% (w/w). Preferably the cream contains a binding agent in a concentration ranging from 0.1% (w/w) to 5% (w/w), more preferably from 0.1% (w/w) to 3% (w/w). While higher concentrations of binding agents should be present in the cream, they are generally not needed to achieve the desired results.

[0099] Additionally, the cream may include an oil, a hair conditioner, and/or a hardening agent. The cream may also include a fragrance, plant extract, and/or a surfactant. The cream can be packed in a tube, box, bottle, or other suitable container.

c. Liquid formulations for bonding

[0100] In some embodiments, a liquid binder formulation is provided, which is mixed prior to use with another formulation, such as coloring or lightening formulations. In these embodiments, the liquid binding formulation may contain any suitable concentration of the binding agent in a suitable carrier, usually a solvent, as described above. The concentration of the binding agent is suitable to provide a mixture with the appropriate final volume and final concentration of the binding agent.

[0101] For example, a liquid binder formulation may contain a binder concentration that ranges from about 5% (w/w) to about 50% (w/w) or more. In a preferred embodiment, the liquid binder formulation contains about 20% (w/w) binder.

[0102] The terms "lightening" and "whitening" are used interchangeably herein. For brightening applications, prior to use, a sufficient volume of the liquid binder formulation is mixed with a sufficient volume of the brightener formulation to form a brightener mixture having the desired binder concentration. Typical concentrations of binders in the brightening composition range from low amounts, such as approximately at least 0.01% (wt), preferably at least 0.1% (wt), to large amounts, such as up to 50% (wt). Preferably the brightening composition contains a binder in a concentration ranging from 0.1% (w/w) to 5% (w/w), more preferably from 0.1% (w/w) to 3% (w/w). While higher concentrations of binders should be present in the brightening mixture, they are generally not necessary to achieve the desired results.

[0103] Alternatively, two separate formulations are applied, such that the first formulation contains a bleaching agent (ie, the brightening formulation), and the second formulation contains a binding agent (ie, the binding formulation) in an effective amount to covalently bind the free thiol groups. A lightening formulation can be applied first, creating free thiol groups in the hair. Then, another binding formulation can be applied to bind the free thiol groups.

III. Whale

[0104] Hair treatment kits typically contain a binding formulation containing an effective amount of binding agent to covalently bind the latent free thiol group in the hair.

[0105] Instructions for use of the putty are also provided.

[0106] The subject invention provides a kit containing:

(a) a first formulation containing a reducing agent capable of reducing disulfide bonds in the hair to produce free thiol groups in the hair and

(b) a second formulation containing a binding agent in an effective amount to covalently bind free thiol groups in the hair, wherein the binding agent is represented by formula I:

whereby they

A, B, C, and D reactive residues capable of reacting with free thiol groups each containing one or more moieties, wherein each of the A, B, C, and D reactive residues independently contains a residue selected from the group consisting of vinyl sulfone, acrylate group, methacrylate group, styrene group, acryl amide group, methacryl amide group, maleate group, fumarate group, and itaconate group; (R) of binding groups containing two or more batches, wherein the batches are opposite to the batches of <reactive residues, wherein R is a monomer, n = 1-10, and wherein (R)>n<is not a polymer, and the sum of these batches is >zero, and wherein the reactive residues are ionically bound to the binding group;

wherein p, q, r, and s are each independently a number from 0 to 25, and wherein the sum of p q r s is equal to or greater than 2.

[0107] The kit can further contain a formulation, also referred to herein as a reducing formulation, which can reduce the disulfide bonds in the hair thereby yielding free thiol groups.

a. Reducing formulations

[0108] The first formulation may be a rare formulation. The Redukujuda formulation contains a reducing agent that can reduce the disulfide bonds in the hair, resulting in free thiol groups. Redukujuda formulation may vary depending on desired hair styling treatment (such as creating waves or straightening), hair texture, user's skin sensitivity, etc.

[0109] Formulations containing reducing agents and their selection are well known to those skilled in the cosmetic industry. Suitable reducing agents include, but are not limited to, thioglycolic acid and thioglycolic acid salts and esters, thiolactic acid and thiolactic acid salts and esters, cysteine thioglycerol, thioglycoline hydrazide, thioglycolamide, glycerol monothioglycolate, sodium metabisulfite, betamercaptopropionic acid, N-hydroxyethyl mercapto-acetamide, N-methyl mercapto-acetamide, betamercapto-ethylamine, beta-mercaptopropionamide, 2-mercapto-ethanesulfonic acid, dimercaptoadipic acid, dithiothreitol, homocysteinethiolactone, cysteine derivatives, polythiol derivatives, derivatives formed by the addition of cysteamine to maleic anhydride-alkylvinyl ether copolymer, inorganic sulfites, inorganic bisulfites, cystamine and its derivatives, dithioerythritol, organic phosphines, and Japanese correctors.

[0110] In some embodiments, the putty contains a reducing formulation, which contains a reducing agent for permanent hair waves and curling hair such as acid perms, base perms, perms with a neutral pH, or perms that use buffered base lotions to create waves. Such reducing agents include, but are not limited to, thioglycolic acid and its derivatives and esters, thiolactic acid derivatives, its salts and esters, cysteine and its derivatives, cystamine and its derivatives, inorganic sulfites, and inorganic bisulfites such as sodium metabisulfite, dithiothreitol, dithioerythritol, organic phosphines, and Japanese correctors.

[0111] In other embodiments, the putty comprises a reducing formulation, which contains a reducing hair straightening agent. Such reducing agents include, but are not limited to, inorganic bisulfites such as sodium metabisulfite, inorganic sulfites, and ammonium thioglycolate, dithiothreitol, dithioerythritol, organic phosphines, and Japanese correctors.

[0112] The amount of reducing agent in the reducing formulation is sufficient to disrupt a sufficient number of disulfide bonds to effectively create hair waves, curl hair, or straighten hair as understood by one of ordinary skill in the art.

b. Coloring formulations

[0113] The first formulation may be a coloring treatment. The first formulation may be formulated wherein the two or more components may be mixed together prior to application to the hair. For example, the first formulation may be in the form of two components such as a dye precursor and an oxidant. Typically, a hair dye formulation contains a reducing agent that can reduce the disulfide bonds in the hair, resulting in free thiol groups. Suitable reducing agents include, but are not limited to, thioglycolic acid, thiolactic acid, dihydrolipoate, thioglycerol, mercaptopropionic acid, sodium bisulfite, ammonium bisulfide, zinc formaldehyde sulfoxylate, sodium formaldehyde sulfoxylate, sodium metabisulfite, potassium borohydride, pegylated thiols, and hydroquinone. The amount of reducing agent in the first formulation is sufficient to disrupt a sufficient number of disulfide bonds for efficient diffusion of the hair coloring ingredients as understood by one of ordinary skill in the art.

[0114] The components of the first formulation may vary depending on the desired hair coloring treatment (such as for semi-permanent, medium-permanent, or permanent hair coloring), hair texture, skin sensitivity of the user, and the like. Hair coloring formulations for various hair coloring treatments, hair textures, hair sensitivities are well known to those skilled in the art.

c. Binding formulation

[0115] The binding formulation contains an effective amount of binding agent to bind free thiols in the hair. Suitable formulations containing binding agents are discussed above. The binding formulation may be in a suitable form. Suitable forms include, but are not limited to, low to moderately viscous liquids, lotions, milks, foams, sprays, gels, creams, shampoos, conditioners, and the like. The binding formulation is contained in a suitable container, which depends on the form of the formulation.

[0116] In one embodiment, the binding formulation is provided as two or more separate active ingredients. For example, the binding agent may be provided as a dry powder in a sealed package and the excipient may be provided in a vial or other container. A suitable mixing container for the binder and excipient may be provided.

[0117] Optionally, the binding agent is pre-mixed with the shampoo or conditioner. In some embodiments, the setting formulation (or other formulation) is mixed with the first formulation (reduced formulation or hair color treatment), and the mixture is applied to the hair.

c. Other materials in the kit

[0118] The kit optionally contains shampoos and conditioners. Suitable shampoos and conditioners include, but are not limited to, LiQWd® Hydrating Shampoo and LiQWd® Hydrating Conditioner.

[0119] The putty may further contain an odor remover. A deodorizing agent may be included in the reducing formulation. Alternatively, the deodorizer is contained in a convenient container for use before or after rinsing the setting formulation from the hair. Some suitable deodorizers are known to one of ordinary skill in the art.

IV. Usage procedures

[0120] The subject invention provides a method for treating hair, wherein the hair contains two or more free thiol groups, which consists of:

(a) applying to the hair a formulation comprising a binding agent of formula I

whereby they

A, B, C, and D reactive residues capable of reacting with free thiol groups each containing one or more batches, wherein each of the A, B, C, and D reactive residues independently contains a residue selected from the group consisting of vinyl sulfone, acrylate group, methacrylate group, styrene group, acryl amide group, methacryl amide group, maleate group, fumarate group, and itaconate group; (R) is a group that contains two or more batches, where the batches are opposite to the batches of the reactive residues, where R is a monomer, n = 1-10, and where (R) is a polymer, and the sum of the batches is zero, and where the reactive residues are bound by ionic bonds to the binding group;

wherein p, q, r, and s are each independently a number from 0 to 25, and wherein the sum of p q r s is equal to or greater than 2, in an amount effective to covalently bind free thiol groups; provided that the binding agent of formula I is not a trimaleate salt of

H2N-(CH2)3-N1(G)-(CH2)4-NH2

wherein G is a substituent that is attached to the secondary amine group of spermidine, selected from chained or unchained, linear or branched alkyl groups formed from 1 to 6 carbon atoms, whereby one or more carbon atoms can be replaced by fluorine if necessary, i.e. methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene; aryl or aryl-alkyl groups, such as phenyl, naphthyl, benzyl, tolyl, wherein one or more carbon atoms are optionally replaced by fluorine, and wherein said aryl-alkyl groups include substituted or unsubstituted, linear or branched alkyl groups forming 1 to 6 carbon atoms, wherein one or more carbon atoms are optionally substituted with fluorine, i.e. methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene-om; chained or unchained cycloalkyl groups forming 3 to 8 carbon atoms which are optionally substituted with chained or unchained, linear or branched alkyl groups forming 1 to 6 carbon atoms, whereby one or more carbon atoms are optionally replaced by fluorine, for example methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene.

[0121] The procedures presented herein deal with the treatment of hair with free thiol groups.

A. Treatment of damaged hair with free thiol groups

[0122] In one embodiment, prior to treatment with the binding agent, the hair is damaged and the thiol groups in the hair are free thiols. A binding agent can be applied to the hair to bind the free thiol groups. Preferably, the bonding agent is applied at least within one week from when the hair is damaged, preferably three days, more preferably during two days, most preferably, during the same day.

a. Rinsing or washing hair

[0123] Optionally, the hair may be shampooed and/or conditioned prior to application of the setting formulation. Alternatively, the hair can be rinsed with water only before applying the setting formulation.

b. Applying the binding formulation to the hair

[0124] After shampooing, conditioning and/or rinsing the hair, the setting formulation is applied to the hair. Alternatively, the hair does not need to be washed or rinsed before applying the setting formulation. In this embodiment, the setting formulation is applied to dry hair.

[0125] Bonding formulations can be used as a daily regenerating hair treatment.

[0126] Typically, the amount of binding formulation applied is sufficient to cause graying of the hair.

[0127] The setting formulation can be applied to the hair as a single application, or the application of the setting agent can be repeated one or more times. Normally, the amount of setting formulation applied in each application is sufficient to saturate the hair. The volume of the bonding formulation applied to the hair in each application can be about 1 to about 100 mL per person depending on the length and volume (density of the hair). In some embodiments, the application of the binding agent can be repeated rapidly (eg, in about 10 to 15 seconds) or between one and five minutes, more than five minutes, between five and ten minutes, more than ten minutes, between ten and dvdest minutes (20) minutes after the first application.

c. Removing the setting formulation from the hair

[0128] Preferably, the hair is washed or rinsed after application of the setting formulation. The hair can be rinsed and then washed quickly (eg, within 10, 15, 25, 30, 45, 60 seconds (one minute), two minutes, three minutes, four, or five minutes after application) after the final application of the setting agent. Alternatively, the hair can be rinsed and washed within about 30 minutes after application, preferably between about 5 minutes and about 20 minutes, more preferably about 10 minutes after the final application of the bonding agent to the hair, depending on the hair type.

[0129] Alternatively, the hair does not need to be washed or rinsed after application of the setting formulation.

[0130] The binding agent covalently binds the hidden thiols in the hair. The thiols remain attached for at least one week, preferably at least one month, after application of the coupling agent. The thiols can remain attached for a long period of time, such as about two months or more after application of the binding agent. The binding reaction is a stable reaction, so the thiols can remain bound even if they are subjected to a hair coloring treatment (at the same time or after the binding reaction).

B. Chemical treatment of hair with a reducing agent

[0131] In one embodiment, prior to treatment with the binding agent, the hair is subjected to a reducing agent used to create waves (also referred to herein as hair perms or permanent waves), curling, and/or hair straightening.

a. Applying a reducing agent to the hair

[0132] The first step in getting waves, curls, or straightening hair is to break the cysteine disulfide bonds to form free thiol residues. The process of breaking cysteine disulfide bonds is carried out using a reducing agent. The procedure for applying the reducing agent includes the following normal procedures for perming or straightening hair, which are known to those skilled in the art. For example, in order to get a perm on your hair, the hair is first washed and placed on perm sticks of different sizes. Second, a reducing agent, such as a reducing thioglycollate solution or lotion, is applied to the hair. The hair is left for a certain period of time, after which the thioglycolate solution is washed off the hair.

[0133] In this procedure, the application of hydrogen peroxide is optional. In some procedures, such as previously chemically treated hair, hydrogen peroxide is generally not used. In other procedures, such as applying perms to natural hair, hydrogen peroxide may be added. In these embodiments, hydrogen peroxide is usually added after washing out the reducing agent. The hydrogen peroxide is then rinsed from the hair before the setting agent is added.

b. Application of a binding agent

[0134] After the reduction treatment, one or more binding agents, or formulations thereof, are applied to the hair. Although the binder is usually applied on the same day as the reducing agent treatment, it can be applied later, such as within 1 to 2 weeks after the reducing agent test.

[0135] Usually, the amount of the binding formulation applied is sufficient to effect the graying of the hair. The setting agent is usually rinsed and shampooed from the hair after the desired level of wave, curl, or straightening has been achieved. In some embodiments, the setting agent is quickly rinsed from the hair (eg, within 10, 15, 25, 30, 45, or 60 seconds after application) followed by final application of the setting agent. Alternatively, the hair can be rinsed and washed within about 30 minutes after application, preferably between about 5 minutes and about 20 minutes, more preferably about 10 minutes after the final application of the binding agent to the hair, depending on the hair type. The setting agent can be washed out of the hair within 10, 15, 25, 30, 45, 60 seconds from the hair after application, and still achieve the desired level of hair wave, curl, or straightening.

[0136] The binding agent can be applied to the hair as a single application, or the application of the binding agent can be repeated one or more times. Normally, the amount of setting formulation applied in each application is sufficient to set the hair. In some embodiments, the volume of setting formulation applied to the hair in each application is about 1 to about 10 mL per curling wand. In some embodiments, application of the binding agent may be repeated rapidly (eg, within 10 to 15 seconds) or approximately 1, 5, 7.5, 10, 12.5, 15, 17.5, or 20 minutes after the initial application. In some embodiments, the second administration is about 7 minutes to about 10 minutes after the first administration.

[0137] The binding agent is rinsed from the hair after its application. The hair can be rinsed and washed quickly (eg within 10 to 15 seconds after application) after the final application of the setting agent. Alternatively, the hair can be rinsed and washed about 10 minutes or later after the final application of the binding agent, such as about 15 minutes to about 30 minutes, preferably about 20 minutes after repeated application of the binding agent to the hair.

[0138] The binding agent covalently binds free thiols in the hair. Thiols remain attached for at least one week, two weeks, three weeks, four weeks, one month, two months or more.

[0139] Bonding agents are generally washed out of an individual's hair on the same day they are applied. In contrast, traditional perms that use only hydrogen peroxide (and do not include the addition of a cross-linking agent) are generally not rinsed out for at least 48 hours after application (washing hair before 48 hours after a traditional perm treatment can result in a significant loss of curl and/or damage to the hair).

[0140] The compositions described herein improve hair quality, such as appearance (eg, shine) and feel, increase dry hair strength (eg, tensile strength), and reduce hair breakage when the hair is subjected to subsequent treatments, such as coloring.

[0141] In some embodiments, hair breakage is reduced by 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75% or more after treatment with the binding agent compared to untreated hair in the same individual. Hair breakage is a significant problem encountered during the dyeing process and other treatments.

C. Applying the coloring formulation to the hair

[0142] The coloring formulation is generally applied to the individual's hair following normal hair coloring procedures known to those skilled in the art. Typically, hair coloring treatments involve two complementary processes: bleaching the natural hair pigment and/or other artificial pigments found in the hair, and diffusion of the dye precursor into the hair, followed by a coupling reaction that leads to the formation of chromophores in the hair shaft, which are too large to diffuse out of the hair shaft. The hair coloring formulation may be a lightening formulation, which is formed by mixing bleach powder and developer. More complex dyes may contain several precursors and many coupling agents, and may involve multiple reactions.

[0143] Color precursors can contain several ingredients, each with different functions. The first ingredient is usually an alkalizing agent (usually ammonia and/or an ammonia substitute, such as monoethanolamine [MEA]). The alkalizing agent has various roles in the hair coloring process including swelling of the hair fiber in order to diffuse the dye precursor. Dye precursors generally include p-diamines and p-aminophenols. Precursors are oxidized to active intermediates once they penetrate the hair membrane. Intermediates can react with dye coupling agents to form wash-fast dyes. More specifically, the intermediates, in the presence of an oxidant, couple with another oxidized dye intermediate to form a large fused ring of dye compounds within the membrane hair. The precursor intermediate needs to penetrate the hair membrane prior to the coupling reaction since the fused product is too large to penetrate the hair membrane. Coupling agents modify the color obtained by the process of oxidation of the precursor compound. The main difference between medium-permanent and permanent products is the alkalizing agent and peroxide concentration. The cuticle does not swell to a great degree with medium-permanent colors, which makes color penetration less efficient than with permanent coloring products.

[0144] Several color formulations use a reducing agent, such as sodium bisulfate, to break the disulfide bonds in the hair, thereby allowing deeper penetration of the hair color dyes into the hair. Specifically, the process involves reducing some of the cysteine disulfide bonds in the hair membranes to thiol groups while breaking the hydrogen bonds. The reducing process changes the chemical and cosmetic characteristics of the hair, which are not desirable.

[0145] The hair coloring procedure can be followed by a shampoo and conditioner treatment, a neutral rinse or an acidic balanced shampoo that contains, together with cationic or amphoteric surfactants, cationic active emollients and quaternary polymers. Alternatively, the hair coloring procedure may be followed by the application of the setting formulations described herein, prior to shampoo and/or conditioner treatment.

a. Application of the binding formulation

[0146] The setting formulation can be applied simultaneously with the hair coloring formulation or after the application of the hair coloring formulation. For example, the setting formulation can be mixed with a hair coloring treatment and the mixture, which together contains the setting formulation of the hair coloring treatment, can be applied to the hair.

[0147] Alternatively, after coloring the hair, a setting formulation, or a formulation thereof, is applied to the hair. Although the bonding agent is usually applied on the same day as the coloring treatment, it can be applied later such as within 1 to 2 weeks after the reducing agent treatment. Typically, an amount of setting formulation (or a mixture of setting formulation and hair coloring formulation) is applied sufficient to effect hair dyeing. The setting formulation can be applied to the hair as a single application, or the application of the setting agent can be repeated one or more times. Usually, the amount of setting formulation applied in each application is sufficient to effect the hair graying. The volume of the bonding formulation applied to the hair in each application can be about 1 to about 100 mL per person depending on the length and density of the hair. In some embodiments, application of the binding agent may be repeated rapidly (eg, within 10 to 15 seconds) or approximately 1, 5, 7.5, 10, 12.5, 15, 17.5, or 20 minutes after the initial application.

[0148] The binding agent can be rinsed and shampooed from the hair quickly after application, for example within 10, 15, 25, 30, 45, or 60 seconds, or two, three, four, or five minutes after application. Alternatively, the bonding agent can be washed off the hair within 30 minutes after application, preferably between about 5 minutes and about 20 minutes, more preferably about 10 minutes after application of the bonding agent to the hair, depending on the hair type.

[0149] If the setting formulation is combined with a hair coloring treatment and applied as a mixture to the hair, then the mixture remains on the hair as long as necessary for the hair coloring treatment. Usually the mixture is applied for approximately 10 minutes. The mixture is removed from the hair according to standard procedures for hair coloring treatments, eg, rinsing and shampooing, approximately 10 minutes after application of the mixture.

[0150] The binding formulation is rinsed from the hair after application. The hair can be rinsed and then washed quickly (eg within 10 to 15 seconds after application) after the final application of the setting agent. Preferably, the hair is rinsed and/or washed about 10 minutes or later after the final application of the binding agent, such as about 15 minutes to about 30 minutes, optionally about 20 minutes after repeated application of the binding agent to the hair.

[0151] The binding agent covalently binds free thiols in the hair. The thiols remain attached for at least one week, two weeks, three weeks, four weeks, one month, or two months, or more.

[0152] Bonding agents are generally rinsed from an individual's hair on the same day as application. In contrast, traditional perms that use only hydrogen peroxide (and do not include the addition of a cross-linking agent) are generally not rinsed out for at least 48 hours after application (washing the hair before 48 hours after a traditional perm treatment can result in a significant loss of curl and/or damage to the hair).

[0153] The compositions described herein improve hair quality, such as appearance (eg, shine) and feel, increase in dry hair strength (eg, tensile strength), and decrease in hair breakage when the hair is subjected to subsequent treatments, such as coloring.

[0154] In some embodiments, hair breakage is reduced by 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% or more after treatment with the binding agent compared to untreated hair in the same individual. Hair breakage is a significant problem encountered during the dyeing process and other treatments.

Examples

Example 1: Comparison of a traditional perm versus a perm that uses bismaleate as a bonding agent

General

[0155] Hair samples are obtained from a human subject by cutting them into 1⁄2 inch wide sections.

[0156] Reducing Agents: Ammonium Thioglycolate (ATG) is obtained from the permanent wave putty made by Zotos. 300 mg of Dithiothreitol in 10 g of solution which is also used as a reducing agent.

[0157] Binding formulation: The bismaleate binding agent 2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-1-amine) di-maleate is used at a concentration of 300 mg in 10 g of the total solution (water).

Procedures

A procedure for putting a perm on the hair using a binding agent

[0158] The hair is washed with a cleansing shampoo, towel dried, and then twisted around the wave rod. Ammonium thioglycollate or dithiothreitol is then applied to the hair and left on the hair for 10 minutes to 1 hour. The hair is then rinsed for 30 seconds to 1 minute and dried with a towel.

[0159] The binding formulation is applied to the hair, through an applicator with a needle holder, with which the hair is soaked. The binding agent remains on the hair for a period of about 7.5 minutes. The hair is soaked a second time with the setting formulation and left for another 7.5 minutes, for a total of 15 minutes. After that, the hair is rinsed with water for about 1-2 minutes while untwisting the curling iron. After the hair is separated from the curling wand, the hair is shampooed and conditioned with various salon brands of shampoo and conditioner including LiQWd® Hydrating Shampoo and Hydrating Conditioner. The washing and rinsing steps are repeated 40 times.

[0160] The other section of hair is exposed to the perm as described above, except that hydrogen peroxide is used instead of the setting formulation.

Results

[0161] Both perms (using a setting formulation or hydrogen peroxide) show only a partial reduction in overall frizz after 40 wash and dry cycles with the same shampoo and conditioner. However, the look and texture of a perm using a setting formulation shows more shine and less frizz compared to a perm using hydrogen peroxide.

Example 2: Comparison of hair breakage due to repeated application of traditional perming and setting formulations.

Procedures

[0162] Two hair samples were obtained. Both samples are treated with dithiothreitol or ammonium thioglycolate as described in Example 1. One of the hair samples is then treated with a setting formulation, while the other is neutralized with hydrogen peroxide. The procedure is completed on the same day when the hair is treated with the binding formulation. The procedure is completed in three days with hydrogen peroxide (traditional permanent).

[0163] The procedure is repeated three times for each hair sample during a 48-hour time period.

Results

[0164] Upon visual inspection, another hair sample treated with the setting formulation shows little or no signs of breakage. However, the first hair sample treated with hydrogen peroxide shows significant breakage.

Example 3: Comparison of the degree of damage in previously relaxed hair with a Japanese straightener

Procedures

[0165] Two hair samples were obtained, the first pre-straightened with a Japanese straightener (Yuko), and the second pre-straightened with a lye-free straightener (African Pride Miracle Deep Conditioning). The samples were treated as described in Examples 1 and 2 using the binding formulations.

[0166] A second hair sample was obtained, previously straightened with a lye-free straightener (African Pride Miracle Deep Conditioning). The sample is treated with a traditional permanent hair straightener (Zotos).

Results

[0167] Hair samples that were treated with the binding formulation did not show any noticeable damage. However, a sample treated with a traditional perm shows significant breakage, even during application.

Example 4: Hair shine and texture after treatment with a bonding formulation.

Generally

[0168] A sample of untreated natural gray hair is obtained from a human subject.

[0169] Binding formulation: The bismaleate binding agent in Example 1 (300 mg) is dissolved in water (10 g). The resulting solution is mixed with LiQWD volume regenerator® in a 1:1 ratio.

Procedures

[0170] A section of natural gray hair is washed with LiQWD® Hydrating Shampoo and towel dried. The hair is then combed with a wide-toothed comb followed by a 2-minute brushing with a fine-toothed comb.

[0171] After combing, the binding formulation (about 4 mL) is manually applied to the hair sample and then combed through the hair sample for 1 minute. The hair sample is left undisturbed for 10 minutes, after which it is rinsed with water, and then washed with LiQWD® volumizing shampoo and conditioner before testing.

[0172] The hair sample is washed and conditioned an additional (5) times with LiQWD® Shampoo and Volume Conditioner.

[0173] Another section of natural gray hair, the control, is treated identically to above, except that the binding formulation is applied to the control hair sample. Therefore, after the hair is combed, LiQWD volume regenerator® is applied manually to the hair (no binding agent).

Results:

[0174] The hair sample treated with the binding formulation was shinier and softer to the touch compared to the original untreated sample. The treated hair sample resulted in a healthier appearance compared to the control sample.

[0175] Shine, texture, and overall appearance remained intact after five treatments with shampoo and conditioner.

Example 5: Hair shine and texture after treatment with a bonding formulation.

Generally

[0176] A sample of untreated natural blonde hair described as highly porous and difficult to comb was obtained from a human subject.

[0177] Binding formulation: The bismaleate binding agent in Example 1 (300 mg) is dissolved in water (10 g). The resulting solution is mixed with LiQWD reinforcing regenerator® in a ratio of 1:1.

Procedures

[0178] Part of natural blonde hair is washed with LiQWD® Hydrating Shampoo. The hair is then combed with a wide-toothed comb followed by a 5-minute combing with a fine-toothed comb.

[0179] The binding formulation (about 7 mL) is manually applied to the hair sample and combed through for 2 minutes. The hair sample is not touched for a period of about 5 minutes, after which the hair is treated again with the bonding formulation (about 4 mL). The brush is passed through the hair sample for approximately 10 seconds and is not touched for about 5 minutes.

[0180] The hair sample is then rinsed with water and subsequently washed with LiQWD® Strengthening Shampoo and Sulfate Free Conditioner prior to testing.

[0181] After the initial test, the sample is washed and conditioned an additional two (2) times with LiQWD® LiQWD® Strengthening Shampoo and Conditioner.

[0182] Another section of natural blonde hair, the control, is treated identically to above, except that the setting formulation is not applied to the control hair sample. Therefore, after combing the hair, LiQWD Volumizing Conditioner® is applied manually to the hair (no binding agent).

Results:

[0183] The hair sample treated with the bonding formulation has more shine and is softer to the touch compared to the original untreated sample. The treated hair sample has a healthier appearance compared to the control sample.

[0184] Shine, texture, and overall appearance remains unchanged after two treatments with shampoo and conditioner.

Example 6: Retention of color and texture of dyed hair that has been treated with a setting agent.

Generally

[0185] Three hair samples were obtained from a human subject and cut into 1⁄2 inch wide sections.

[0186] Coloring Formulation: The permanent coloring formulation was obtained from a L'Oreal® Permanent Coloring Service (L'Oreal® Majirel Permanent Color #10 with 20 volume peroxide).

[0187] Binding formulation: The bismaleate binding agent, 2,2-(ethane-1,2-diylbis(oxy))bis(ethane-1-amine) di-maleate, is used at a concentration of 300 mg in 10 g of total solution (water).

Procedures

[0188] Samples that are washed with a cleansing shampoo and then dried with a towel. The samples are then dyed with the L'Oreal® Permanent Hair Color Service, which remains on the hair samples for approximately 35-40 minutes.

[0189] The first tertian hair sample ("control") was then rinsed and washed with Liqwd® Hydrating Shampoo and Conditioner five times before photography.

[0190] The binding formulation is applied to hair samples treated with the second and third colors using a spray bottle and massaging with fingers. The setting formulation remains on the second hair sample for a period of about 1 minute and on the third sample for a period of about 10 minutes. Hair samples are then rinsed, and then washed with Liqwd® Hydrating Shampoo and Conditioner five times before testing.

Results:

[0191] Hair samples treated with the setting formulations show better color retention, more shine, and less frizz compared to the control. Hair samples treated with the bonding formulation feel softer to the touch and combined with less frizz and added shine give an overall healthier look compared to the control.

Example 7: Comparison of color retention in traditionally permed hair and permed hair using bonding formulations.

Procedure

[0192] A 1⁄2 inch wide section of hair sample is obtained from a human subject, and rinsed with a cleansing shampoo and then towel dried. Ammonium thioglycolate or dithiothreitol is mechanically brushed through the hair with a wide and fine comb several times, after which it is left on the hair for 10 minutes to 1 hour. The hair is then rinsed with water for 30 seconds to 1 minute, after which it is dried with a towel.

[0193] The binding formulation, described in Example 1, is then applied by soaking to the hair using an applicator with a needle holder and left on for 7.5 minutes. This step is repeated for 15 minutes. Hair is then rinsed for 1-2 minutes, shampooed, and conditioned with various salon brands of shampoo and conditioner, including LiQWd® Hydrating Shampoo and Hydrating Conditioner.

[0194] Another hair sample is straightened, as described above, using hydrogen peroxide instead of a setting formulation. Hair samples are washed and treated with conditioner with repetition.

Hair color comparison:

[0195] After both samples were washed five times with LiQWd® Hydrating Shampoo and LiQWd® Hydrating Conditioner, the samples were tested for their color retention.

Results

[0196] The hair sample that was treated with the setting formulation had a color of similar intensity to the hair sample before the first wash, compared to the hair that was treated with hydrogen peroxide.

Example 8: Comparison of hair treated with a lightening formulation co-administered with a setting formulation and hair treated with a lightening formulation alone

[0197] The binding formulation in Example 1 contains a bismaleate binding agent at concentrations of 2400 mg in 10 g of total solution (water).

[0198] Two samples of human hair were tested. A sample taken from the same head, 1 inch wide, and split in half. The color was medium brown and was previously treated with an unknown professional hair color.

[0199] Sample 1, 1/2 inch wide and 8 inches long, was lightened with traditional lightening ingredients mixed with a setting formulation. 1oz of Joico Verocolor Veroxide -20 volume developer is mixed with 1oz of Joico Verolight bleach powder to form a lightening formulation. After that, 9mL of the binding formulation is added to the brightening formulation to obtain a mixture.

[0200] The mixture is applied using an applicator brush to the hair sample 1 as the hair is on the aluminum foil. The foil is then wrapped around the sample and the process is allowed to continue for 35 minutes. After that, the sample is rinsed once and washed with shampoo.

[0201] Sample 2, a control, 1/2 inch wide and 8 inches long, is lightened with traditional lightening ingredients in the absence of a binder formulation. 1oz of Joico Verocolor Veroxide -20 volume developer is mixed with 1oz of Joico Verolight Bleaching Powder to create a creamy lightening formulation.

[0202] The lightening formulation is applied to hair sample 2 using a brush applicator as the hair rests on the aluminum foil. The foil is then wrapped around the sample and the process is allowed to continue for 35 minutes. After that, the sample is rinsed once and washed with shampoo.

Results

[0203] A noticeable difference in hair quality was observed between sample 1 and sample 2. Hair sample 1 was softer, less frizzy, felt hydrated, with more shine compared to the control, sample 2.

[0204] Both samples were washed and treated with conditioner 5 five times more with the same noticeable benefits of sample 1 (treated with a mixture of lightening formulation and setting formulation) compared to the control, sample 2 (treated only with lightening formulation).

[0205] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as understood by one of ordinary skill in the art to which the disclosed invention pertains. The publications cited and referenced herein are specifically incorporated by reference.

[0206] Those skilled in the art will recognize, or will be able to determine using more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be covered by the following claims.

Claims (70)

PATENT CLAIMS 1. A process for treating hair, where the hair contains two or more free thiol groups, which includes: (a) applying to the hair a formulation comprising a binding agent of formula I where, A, B, C, and D are reactive moieties capable of reacting with free thiol groups each containing one or more charges, wherein each of the reactive moieties A, B, C, and D independently contains a group selected from the group consisting of vinyl sulfone, acrylate group, methacrylate group, styrene group, acrylamide group, methacrylamide group, maleate group, fumarate group, and itaconate group; (R)ne bond is a group containing two or more charges, in which the charges are opposite to the charges of the reactive parts, where R is a monomer, n = 1-10, and where (R)n is a polymer, and the sum of charges is zero, and where the reactive parts are ionically bound to the bonding group; wherein each p, q, r, and s is independently an integer from 0 to 25, and wherein the sum of p q r s is one or greater than 2, in an amount effective to covalently bind free thiol groups; with the proviso that the binding agent of formula I is not a trimethylate salt H2N-(CH2)3-N<1>(G)-(CH2)4-NH2 where G is a substituent that is attached to the secondary amino group of spermidine, selected from fused or unfused, linear or branched alkyl groups formed from 1 to 6 carbon atoms, where one or more carbon atoms are optionally replaced with fluorine, namely methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene; aryl or aryl-alkyl groups, such as phenyl, naphthyl, benzyl, tolyl, where one or more carbon atoms are optionally replaced by fluorine, and wherein said aryl-alkyl groups include substituted or unsubstituted, linear or branched alkyl groups formed with 1 to 6 carbon atoms, where one or more carbon atoms are optionally substituted with fluorine, namely methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene; substituted or unsubstituted cycloalkyl groups of 3 to 8 carbon atoms which are optionally substituted with substituted or unsubstituted, linear or branched alkyl groups of 1 to 6 carbon atoms, where one or more carbon atoms are optionally substituted with fluorine, namely methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene. 2. The process of claim 1, wherein the reactive moieties and thiol groups react to form carbon-sulfur (C-S) covalent bonds. 3. The method of any one of claims 1-2, wherein A, B, C and D are the same. 4. The process according to any one of claims 1-2, wherein at least one of A, B, C and D is different from other reactive moieties. 5. The process according to any one of claims 1-4, wherein the linking group is a polyfunctional molecule and where the linking group is optionally independently substituted with one or more substituents including hydrogen, halogen, cyano, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine, hydroxy, formyl, acyl, carboxylic acid (-COOH), -C(O)R<1>, -C(O)OR<1>, carboxylate (-COO-), primary amide (eg, -CONH2), secondary amide (eg, -CONHR<1>), -C(O)NR<1>R<2>, -NR<1>R<2>, -NR<1>S(O)2R<2>, -NR<1>C(O)2’-, -S(O)2R<2>, -SR<1>, and -NR<1>S(O)2R<2>. S(O)2NR<1>R<2>, a sulfinyl group (eg, -SOR<1>), and a sulfonyl group (eg, -SOOR<1>); where R<1> and R<2> can each independently be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl and heteroaryl; where each of R<1> and R<2> is optionally independently substituted with one or more substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, amino, alkylamino, dialkylamino, alkyl optionally substituted with one or more halogen or alkoxy or aryloxy, aryl optionally substituted with one or more halogen or alkoxy or alkyl or trihaloalkyl, heterocycloalkyl optionally substituted with aryl or heteroaryl or =O or alkyl optionally substituted with hydroxyl, cycloalkyl optionally substituted with hydroxyl, heteroaryl optionally substituted with one or more halogen or alkoxy or alkyl or trihaloalkyl, haloalkyl, hydroxyalkyl, carboxy, alkoxy, aryloxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, and dialkylaminocarbonyl. 6. The method according to any one of claims 1-5, wherein the binding agent is: or 7. The method according to any one of claims 1-6, where the reactive moieties A; B, C and D independently contain a group selected from the group consisting of a vinyl sulfone, a styrene group, an acrylamide group, a methacriamide group, a maleate group and a fumarate group. 8. The method of any one of claims 1-7, wherein the molecular weight of the binding agent is less than about 5000 daltons. 9. The method according to any one of claims 1-8, wherein the formulation further comprises one or more cosmetically acceptable excipients, wherein one or more excipients are selected from the group consisting of water, surfactants, vitamins, natural extracts, preservatives, chelating agents, perfumes, maintenance agents, antioxidants, chelating agents, hair dyes, proteins, amino acids, wetting agents, fragrances, emollients, penetrating agents, thickening agents, viscosity modifiers, hair strengtheners, film agents, emulsifiers, delaying agents, propellants, liquid agents, carriers, salts, pH adjusting agents, neutralizing agents, buffers, hair conditioners, antistatic agents, anti-frizz agents, anti-dandruff agents and combinations thereof. 10. The method according to claim 9, where the binding agent is present in an amount of 0.01 wt.% to 50 wt.% of the formulation. 11. The method of any one of claims 9-10, wherein the binding agent is about 3 wt.% of the formulation. 12. The method according to any one of claims 9-11, wherein the excipient is present in an amount ranging from 10 wt.% to 90 wt.% of the formulation. 13. The method according to any one of claims 1-12, wherein the formulation is in the form of a gel, cream, lotion, shampoo or conditioner. 14. The method according to any one of claims 1-13, wherein step (a) is repeated one or more times. 15. The method according to any one of claims 1-14, wherein step (a) is repeated 1 minute to 20 minutes after the first application of the formulation. 16. The method according to any one of claims 1-15, further comprising (b) rinsing, shampooing and/or conditioning the hair, wherein step (b) takes place after step (a). 17. The method of claim 16, wherein step (b) is performed within 10 seconds to 30 minutes after step (a). 18. The method of any one of claims 1-17, further comprising steps applying a first formulation containing a reducing agent capable of reducing disulfine bonds in the hair to obtain free thiol groups, where the step is performed prior to application of the formulation containing the binding agent. 19. The method according to claim 18, which is a reducing agent selected from the group consisting of thioglycolic acid and its derived salts and esters, thiolactic acid and its derived salts or esters, cysteine and its derivatives, cysteamine and its derivatives, neobranch sulfites, sodium metabisulfite, other inorganic bisulfites, dithiothreitol, dithioerythritol, organic phosphines, and Japanese rectifier. 20. A process according to any one of claims 1-19, wherein the thiols remain attached for at least one week. 21. The method of any one of claims 1-20, wherein the molecular weight of the binding agent is less than 500 daltons. 22. A formulation containing a binding agent, an aqueous solvent, and one or more preservatives, stabilizers or combinations thereof, wherein the binding agent is represented by formula I where A, B, C, and D are reactive moieties capable of reacting with free thiol groups each containing one or more charges, wherein each of reactive moieties A, B, C, and D independently contains a group selected from the group consisting of vinyl sulfone, acrylate group, methacrylate group, styrene group, acrylamide group, methacrylamide group, maleate group, fumarate group, and itaconate group; (R)bonds are groups containing two or more charges, where the charges are opposite to the charges of the reactive parts, where R is a monomer, n = 1-10, and where (R)n is a polymer, and the sum of the charges is zero, and where the reactive parts are ionically bound to a bonding group; where p, q, r, and s are each independently an integer from 0 to 25, and where the sum of p q r s is equal to or greater than 2. 23. The formulation according to claim 22, wherein the binding agent is: or 24. Procedure for coloring hair which includes: (a) applying a first formulation comprising a hair coloring agent and a reducing agent capable of reducing disulfide bonds in the hair to produce free thiol groups, (b) applying to the hair a second formulation comprising a binding agent of formula I where, A, B, C, and D are reactive moieties capable of reacting with free thiol groups each containing one or more charges, wherein each of the reactive moieties A, B, C, and D independently contains a group selected from the group consisting of vinyl sulfone, acrylate group, methacrylate group, styrene group, acrylamide group, methacrylamide group, maleate group, fumarate group, and itaconate group; A (R)bond is a group containing two or more charges, where the charges are opposite to the charges of the reactive parts, where R is a monomer, n = 1-10, and where it is not a (R)npolymer, and the sum of the charges is zero, and where the reactive parts are ionically bound to the bonding group; where each p, q, r, and s is independently an integer from 0 to 25, and where the sum of p q r s is equal to or greater than 2, in an effective amount to bind covalently to free thiol groups. 25. Procedure for extracting light strands, which includes: (a) applying a first formulation containing a bleach to lighten the hair and obtain free thiol groups, (b) applying to the hair a second formulation comprising a binding agent of formula I where, A, B, C, and D are reactive moieties capable of reacting with free thiol groups each containing one or more charges, wherein each of the reactive moieties A, B, C, and D independently contains a group selected from the group consisting of vinyl sulfone, acrylate group, methacrylate group, styrene group, acrylamide group, methacrylamide group, maleate group, fumarate group, and itaconate group; (R)bonds are groups containing two or more charges, where the charges are opposite to the charges of the reactive parts, where R is a monomer, n = 1-10, and where (R)n is a polymer, and the sum of the charges is zero, and where the reactive parts are ionically bound to the bonding group; where p, q, r, and s are each independently an integer from 0 to 25, and where the sum of p q r s is equal to or greater than 2, in an effective amount to bind covalently to free thiol groups. 26. The method according to claim 24 or 25, wherein steps (a) and (b) are performed simultaneously. 27. The method of claim 24 or 25, wherein steps (a) and (b) are performed sequentially, with step (a) performed prior to step (b). 28. The method of claim 26, wherein prior to step (a), the first formulation and the second formulation are mixed together. 29. The process of any one of claims 24-28, wherein the reactive moieties and thiol groups react to form carbon-sulfur (C-S) covalent bonds. 30. The method of any one of claims 24-29, wherein A, B, C and D are the same. 31. The process according to any one of claims 24-29, wherein at least one of A, B, C and D is different from the other reactive moieties. 32. The method according to any one of claims 24-31, wherein the linking group is a polyfunctional molecule, wherein the linking group is optionally independently substituted with one or more substituents including hydrogen, halogen, cyano, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine, hydroxy, formyl, acyl, carboxylic acid (-COOH), -C(O)R<1>, -C(O)OR<1>, carboxylate (-COO-), primary amide (eg, -CONH2), secondary amide (eg, -CONHR<1>), -C(O)NR<1>R<2>, -NR<1>R<2>, -NR<1>S(O)2R<2>, -NR<1>C(O)R<2>, - S(O)2R<2>, -SR<1>, and -S(O)2NR1R2, a sulfinyl group (eg, -SOR<1>), and a sulfonyl group (eg, -SOORI<1>); where R<1> and R<2> can each independently be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl and heteroaryl; where each R<1> and R<2> is optionally independently substituted with one or more substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, amino, alkylamino, dialkylamino, alkyl optionally substituted with one or more halogen or alkoxy or aryloxy, aryl optionally substituted with one or more halogen or alkoxy or alkyl or trihaloalkyl, heterocycloalkyl optionally substituted with aryl or heteroaryl or =O or alkyl optionally substituted with hydroxyl, cycloalkyl optionally substituted with hydroxyl, heteroaryl optionally substituted with one or more halogen or alkoxy or alkyl or trihaloalkyl, haloalkyl, hydroxyalkyl, carboxy, alkoxy, aryloxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, and dialkylaminocarbonyl. 33. The method according to any one of claims 24-32, wherein the binding agent is: or 34. The method according to any one of claims 24-33, wherein the second formulation further comprises one or more cosmetically acceptable excipients, and wherein one or more excipients are selected from the group consisting of water, surfactant, vitamins, natural extracts, conditioners, chelating agents, perfumes, conditioners, antioxidants, proteins, amino acids, wetting agents, fragrances, emollients, penetration enhancers, thickening agents, viscosity modifiers, hair strengtheners, film formers, emulsifiers, delay agents, propellants, liquid agents, carriers, salts, agents for pH adjustment, neutralizing agents, buffers, hair conditioners, antistatic agents, anti-frizz agents, anti-dandruff agents and combinations thereof. 35. The method according to claim 34, wherein the binding agent is present in an amount ranging from 0.01 wt.% to 50 wt.% of the second formulation, preferably from 0.01 wt.% to 10 wt.% of the second formulation. 36. The method of any one of claims 33-35, wherein the binding agent is present in an amount ranging from 2.5 to 3% by weight of the second formulation. 37. The method according to any one of claims 33-35, where the excipient is present in an amount of 10 wt.% to 99.99 wt.%. % of the second formulation, preferably from 50 wt.% to 90 wt.% of the second formulation. 38. The method according to any one of claims 24-37, wherein the second formulation is in the form of a gel, cream, lotion, shampoo or conditioner. 39. The method according to any one of claims 24-38, wherein step (b) is repeated one or more times. 40. The method according to any one of claims 24-39, further comprising (c) rinsing, shampooing and/or conditioning the hair, wherein step (c) occurs sequentially after step (b). 41. The method according to claim 40, wherein step (c) is performed within 10 seconds to 30 minutes, preferably between 1 minute and 20 minutes, more preferably about 10 minutes after step (b). 42. The method according to any one of claims 24-41, wherein the coloring agent is selected from the group consisting of lightening agents, permanent coloring agents, medium permanent coloring agents and semi-permanent coloring agents. 43. Kit containing (a) a first formulation comprising a reducing agent capable of reducing disulfide bonds in the hair to produce free thiol groups, and (b) a second formulation containing a binding agent in an amount effective to covalently bind to free thiol groups in the hair, wherein the binding agent is represented by formula I where A, B, C, and D are reactive moieties capable of reacting with free thiol groups each containing one or more charges, wherein each of the reactive moieties A, B, C, and D independently contains a group selected from the group consisting of vinyl sulfone, acrylate group, methacrylate group, styrene group, acrylamide group, methacrylateamide group, maleate group, fumarate group, and itaconate group; (R)bonds are groups containing two or more charges, where the charges are opposite to the charges of the reactive parts, where R is a monomer, n = 1-10, and where (R)n is a polymer, and the sum of the charges is zero, and where the reactive parts are ionically bound to the bonding group; where p, q, r, and s are each independently an integer from 0 to 25, and where the sum of p q r s is equal to or greater than 2. 44. The kit of claim 43, further comprising shampoo, conditioner, instructions for use, developer, mixing bowl, odor eliminator, gloves, or combinations thereof. 45. A putty according to any one of claims 43-44, wherein the first formulation is a bleaching, straightening, waving, curling or coloring formulation. 46. The kit according to any one of claims 43-45, wherein A, B, C and D are the same. 47. The kit according to any one of claims 43-46, wherein at least one of A, B, C and D is different from the other reactive moieties. 48. The kit according to any one of claims 43-47, wherein the binding agent is a polyfunctional molecule wherein the binding agent is optionally independently substituted with one or more substituents selected from the group consisting of hydrogen, halogen, cyano, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine, hydroxy, formyl, acyl, carboxylic acid (-COOH), -C(O)R<1>, -C(O)OR<1>, carboxylate (-COO-), primary amide (eg, -CONH2), secondary amide (eg, -CONHR<1>), -C(O)NR<1>R<2>, -NR<1>R<2>, -NR<1>S(O)2R<2>, -NR<1>C(O)R<2>, -S(O)2R<2>, -SR<1>, and -S(O)2NR<1>R<2>, a sulfinyl group (eg, -SOR<1>), and a sulfonyl group (eg, -SOOR<1>); where R<1> and R<2> can each independently be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl and heteroaryl; where each of R<1> and R<2> is optionally independently substituted with one or more substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, amino, alkylamino, dialkylamino, alkyl optionally substituted with one or more halogen or alkoxy or aryloxy, aryl optionally substituted with one or more halogen or alkoxy or alkyl or trihaloalkyl, heterocycloalkyl optionally substituted with aryl or heteroaryl or =O or alkyl optionally substituted with hydroxyl, cycloalkyl optionally substituted with hydroxyl, heteroaryl optionally substituted with one or more halogen or alkoxy or alkyl or trihaloalkyl, haloalkyl, hydroxyalkyl, carboxy, alkoxy, aryloxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, and dialkylaminocarbonyl. 49. The kit of any one of claims 43-48, wherein the reactive moieties and thiol groups react to form carbon-sulfur (C-S) bonds. 50. The putty according to any one of claims 43-49, wherein the bonding agent is or 51. Putty according to any one of claims 43-50, wherein the second formulation further contains one or more cosmetically acceptable excipients selected from the group consisting of water, surface active agents, vitamins, natural extracts, preservatives, hetalizing agents, perfumes, maintenance agents, antioxidants, chelating agents, hair coloring agents, proteins, amino acids, moisturizing agents, fragrances, emollients, penetrating agents, thickening agents, viscosity modifiers, hair strengtheners, film formers, emulsifiers, delaying agents, propellants, liquid agents, carriers, salts, pH adjusting agents, neutralizing agents, buffers, conditioners, antistatic agents, anti-frizz agents, anti-dandruff agents and combinations thereof. 52. Putty according to any one of claims 43-51, wherein the binding agent is present in an amount ranging from 0.01 wt.% to 50 wt.%. % of other formulations. 53. The kit according to any one of claims 43-50, wherein the excipient is present in an amount ranging from 10 wt.% to 90 wt.% of the second formulation. 54. The kit according to any one of claims 43-53, wherein the first and second formulations are previously mentioned. 55. The kit according to any one of claims 43-54. where the second formulation is pre-mixed with shampoo or conditioner. 56. The kit according to any one of claims 43-55, wherein the second formulation is in the form of a liquid, lotion, milk, mousse, spray, gel, cream, shampoo or conditioner. 57. The kit according to any one of claims 43-56, wherein the second formulation is obtained as two or more separate ingredients. 58. A kit according to any one of claims 43-57, wherein the binding agent is provided as a dry powder in a heated package and the pharmaceutically acceptable excipient is provided in a vial or other container. 59. The kit according to any one of claims 43-58, wherein: (1) the first formulation is a whitening formulation; and (2) the binding agent in the second formulation is 60. The kit of claim 59, wherein the bleaching formulation further comprises a developer. 61. The kit according to any one of claims 59-60, further comprising a shampoo, a conditioner, an instruction for use, a developer, a mixing vessel, a deodorizer, or a combination thereof. 62. A shampoo or conditioner containing an effective amount of a binding agent, wherein the binding agent is represented by the formula where, A, B, C, and D are reactive moieties capable of reacting with free thiol groups each containing one or more charges, wherein each of reactive moieties A, B, C, and D independently contains a moiety selected from the group consisting of vinyl sulfone, acrylate group, methacrylate group, styrene group, acrylamide group, methacrylamide group, maleate group, fumarate group, and itaconate group; (R)bonds are groups containing two or more charges, where the charges are opposite to the charges of the reactive parts, where R is a monomer, n = 1-10, and where (R)n is a polymer, and the sum of the charges is zero, and where the reactive parts are ionically bound to the bonding group; where each of p, q, r, and s is independently an integer from 0 to 25, and where the sum of p q r s is equal to or greater than 2; with the proviso that the binding agent of formula I is not a trimaleate salt H2N-(CH2)3-N<1>(G)-(CH2)4-NH2 where G is a substituent that is attached to the secondary amine group of spermidine, selected from chained or unchained, linear or branched alkyl groups consisting of 1 to 6 carbon atoms, where one or more carbon atoms are optionally replaced by fluorine, namely methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene; aryl or aryl-alkyl group, such as phenyl, naphthyl, benzyl, tolyl, where one or more carbon atoms is optionally replaced by fluorine, and where said aryl-alkyl groups include substituted or unsubstituted, linear or branched alkyl groups formed with 1 to 6 carbon atoms, where one or more carbon atoms are optionally substituted with fluorine, namely methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene; substituted or unsubstituted cycloalkyl groups of 3 to 8 carbon atoms which are optionally substituted with substituted or unsubstituted, linear or branched alkyl groups of 1 to 6 carbon atoms, where one or more carbon atoms are optionally substituted with fluorine, namely methyl, ethyl, trifluoromethyl, trifluoroethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, ethylene, vinyl, propylene, butylene. 63. A shampoo or conditioner according to claim 62, wherein the reactive moieties and thiol groups react to form carbon-sulfur (C-S) covalent bonds. 64. A shampoo or conditioner according to any one of claims 62-63, wherein A, B, C and D are the same. 65. A shampoo or conditioner according to any one of claims 62-63, wherein at least one of A, B, C and D is different from the other reactive moieties. 66. Shampoo or conditioner according to any of claims 62-65, wherein the linking group is a polyfunctional molecule, wherein the linking group is optionally independently substituted with one or more substituents selected from the group consisting of hydrogen, halogen, cyano, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine, hydroxy, formyl, acyl, carboxylic acid (-COOH), -C(O)R<1>, -C(O)OR<1>, carboxylate (-COO-), primary amide (eg, -CONH2), secondary<amide (eg, -CONHR1), -C(O)NR1R2, -NR1R2, -NR1S(O)>2<R2, -NR1C(O)R2, -S(O)>2<R2 , -SR1, and ->S(O)2NR<1>R<2>sulfinyl group (eg, -SOR<11>), and a sulfonyl group (eg, -SOOR<1>); where R<1> and R<2> can each independently be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl and heteroaryl; where each of R<1> and R<2> is optionally independently substituted with one or more substituents selected from the group consisting of halogen, hydroxyl, cyano, nitro, amino, alkylamino, dialkylamino, alkyl optionally substituted with one or more halogen or alkoxy or aryloxy, aryl optionally substituted with one or more halogen or alkoxy or alkyl or trihaloalkyl, heterocycloalkyl optionally substituted with aryl or heteroaryl or =O or alkyl optionally substituted with hydroxyl, cycloalkyl optionally substituted with hydroxyl, heteroaryl optionally substituted with one or more halogens or alkoxy or alkyl or trihaloalkyl, haloalkyl, hydroxyalkyl, carboxy, alkoxy, aryloxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, and dialkylaminocarbonyl. 67. A shampoo or conditioner according to any one of claims 62-66, wherein the binding agent is or 68. Shampoo or conditioner according to any one of claims 62-67, which further contains one or more cosmetically acceptable excipients, where one or more excipients are selected from the group consisting of water, surfactants, vitamins, natural extracts, preservatives, chelating agents, perfumes, maintenance agents, antioxidants, chelating agents, hair coloring agents, proteins, amino acids, moisturizing agents, fragrances, emollients, penetrating agents, agents for thickeners, viscosity modifiers, hair strengtheners, film formers, emulsifiers, delay agents, propellants, liquid agents, carriers, salts, pH adjusters, neutralizing agents, buffers, hair conditioners, antistatic agents, anti-frizz agents, anti-dandruff agents and combinations thereof. 69. A shampoo or conditioner according to claim 68, wherein the binding agent is present in an amount ranging from 0.01 wt.% to 50 wt.% of the formulation. 70. Chamon or conditioner according to any one of claims 68-69, wherein the binding agent is present in an amount ranging from 2.5 to 3 wt.% of the formulation.