Keratin Treatment Formulations and Methods

Abstract

Formulations, kits, and methods for rebuilding the disulfide bonds in keratin found in hair, skin, or nails. Hair that is damaged due to a hair coloring treatment and/or other reducing treatment, such as during a permanent wave, can be treated with the formulations containing one or more active agents. The formulations may be applied subsequent to a hair coloring treatment or simultaneously with a hair coloring treatment. Use of the active agent formulations during a permanent wave treatment prevents the reversion of the hair to its previous state, for at least one week, preferably at least three months, more preferably at least one year, most preferably greater than one year, after one or more than one application of the formulation. Application of the active agent formulation to skin or nails can help repair damaged disulfide bonds due to natural wear and tear or natural aging.

We claim: 
     
         1 . A method for treating hair comprising:
 (a) applying to the hair a formulation comprising an active agent,   wherein the active agent has the formula:   
       
         
           
           
               
               
           
         
       
       wherein Z is a linker or is absent; 
       m and n are each an integer independently selected from 0-6, and the sum of m+n is equal to or greater than 2; 
       B is a functional group capable of forming a covalent bond with a nucleophile; and 
       A is an ionizable functional group. 
     
     
         2 . The method of  claim 1 , wherein B is independently selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
       wherein R is independently selected from the group consisting of hydrogen, C 1-6  alkyl groups, aryl groups, or an ionizable functional groups; Z′ is oxygen (O), NH or is absent, and G is carbon (C) and g is 1, or G is sulfur (S) and g is 2; and A is independently selected from the group consisting of: —COOH, —SO 3 H, —PO 3 H 2 , —N(R 1 ) 2 , —N(R 1 ) 3 ; wherein R 1  is independently selected from the group consisting of a hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl and heteroaryl groups; wherein each R 1  is independently unsubstituted or substituted with one or more substituents. 
     
     
         3 . The method of  claim 1 , wherein the linker Z is an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocycloalkyl group, or heteroaryl group,
 wherein the alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, or heteroaryl group, is unsubstituted or substituted one or more times by a halogen, cyano, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine, hydroxy, oxo, formyl, acyl, carboxylic acid (—COOH), —C(O)R 1 , —C(O)OR 1 , (—COO − ), primary amide (e.g., —CONH 2 ), secondary amide (e.g., —CONHR 1 ), —C(O)NR 1 R 2 , —NR 1 R 2 , —NR 1 S(O) 2 R 2 , —NR 1 C(O)R 2 , —S(O) 2 R 2 , —SR 1 , —S(O) 2 NR 1 R 2 , —SOR 1 , or —SOOR 1 ;   wherein R 1  and R 2  are each independently selected from the group consisting of a hydrogen, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, heterocycloalkyl, and heteroaryl group, wherein each of R 1  and R 2  is independently unsubstituted or substituted with one or more substituents.   
     
     
         4 . The method of  claim 1 , wherein the linker Z is a C 1-4  alkyl group. 
     
     
         5 . The method of  claim 4 , wherein the alkyl group is substituted with one or more substituents replacing a hydrogen on one or more carbons of the alkyl hydrocarbon backbone or the alkyl group is substituted with one or more heteroatoms within the hydrocarbon carbon backbone, or a combination thereof, and
 wherein the substituents are selected from the group consisting of oxo, hydroxyl, carboxyl, amido, and amino groups.   
     
     
         6 . The method of  claim 1 , further comprising the step of:
 applying a first formulation comprising a reducing agent capable of reducing disulfide bonds in the hair to produce free thiol groups,   wherein the step is performed prior to step (a).   
     
     
         7 . The method of  claim 6 , wherein the reducing agent is selected from the group consisting of thioglycolic acid and its derivative salts and esters, thiolactic acid and its derivative salts and esters, cysteine and its derivatives, cysteamine and its derivatives, inorganic sulfites, sodium metabisulfite, other inorganic bisulfites, dithiothreitol, dithioerythritol, organic phosphines, and Japanese relaxers. 
     
     
         8 . The method of  claim 1 , further comprising prior to or simultaneously with step (a),
 applying to the hair a coloring formulation comprising a hair coloring agent and a reducing agent capable of reducing disulfide bonds in the hair to produce free thiol groups.   
     
     
         9 . The method of  claim 8 , wherein prior to step (a), the coloring formulation is applied to the hair. 
     
     
         10 . The method of  claim 1 , further comprising prior to or simultaneously with step (a), applying to the hair a bleaching formulation comprising a bleaching agent to lighten the hair and produce free thiol groups. 
     
     
         11 . The method of  claim 10 , wherein prior to step (a), the bleaching formulation is applied to the hair. 
     
     
         12 . The method of  claim 1 , wherein the formulation further comprises one or more pharmaceutically acceptable excipients selected from the group consisting of water, surfactants, vitamins, natural extracts, preservatives, chelating agents, perfumes, preservatives, antioxidants, proteins, amino acids, humectants, fragrances, emollients, penetrants, thickeners, viscosity modifiers, hair fixatives, film formers, emulsifiers, opacifying agents, propellants, liquid vehicles, carriers, salts, pH adjusting agents, neutralizing agents, buffers, hair conditioning agents, anti-static agents, anti-frizz agents, anti-dandruff agents, and combinations thereof. 
     
     
         13 . The method of  claim 1 , wherein the active agent is present in an amount ranging from about 0.01 wt % to about 10 wt % of the formulation. 
     
     
         14 . The method of  claim 1 , wherein the active agent is present in an amount ranging from about 0.5 to 3 wt % of the formulation. 
     
     
         15 . The method of  claim 12 , wherein the one or more excipients are present in an amount ranging from about 50 wt % to about 90 wt % of the formulation. 
     
     
         16 . The method of  claim 1 , wherein the formulation is in the form of a gel, cream, lotion, shampoo, or conditioner. 
     
     
         17 . The method of  claim 1 , wherein step (a) is repeated one or more times. 
     
     
         18 . The method of  claim 1 , further comprising:
 (b) rinsing, shampooing, or conditioning the hair, or a combination thereof,   
       wherein step (b) occurs subsequent to step (a). 
     
     
         19 . The method of  claim 18 , wherein step (b) is performed about 10 minutes after step (a). 
     
     
         20 . The method of  claim 8 , wherein the hair coloring agent is selected from the group consisting of highlighting agents, permanent coloring agents, demi-permanent coloring agents, and semi-permanent coloring agents. 
     
     
         21 . The method of  claim 1 , wherein the active agent is selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
       and simple salts thereof. 
     
     
         22 . A kit comprising:
 (a) a first formulation comprising a hair coloring agent and a reducing agent capable of reducing disulfide bonds in hair to produce free thiol groups, and   (b) a second formulation comprising an active agent,   
       wherein the active agent has the formula: 
       
         
           
           
               
               
           
         
       
       wherein Z is a linker or is absent; 
       m and n are each an integer independently selected from 0-6, and wherein the sum of m+n is equal to or greater than 2; 
       B is a functional group capable of forming a covalent bond with a nucleophile; and 
       A is an ionizable functional group. 
     
     
         23 . The kit of  claim 22 , further comprising a shampoo, a conditioner, instructions for use, a developer, gloves, or a combination thereof. 
     
     
         24 . A method for treating hair comprising:
 (a) applying to the hair a formulation comprising an active agent,   wherein the active agent has the formula:   
       
         
           
           
               
               
           
         
       
       wherein Z is a linker or is absent; 
       m and n are each an integer independently selected from 0-6, and the sum of m+n is equal to or greater than 2; 
       B is a functional group capable of forming a covalent bond with a nucleophile; 
       A is an ionizable functional group; and 
       C contains an ionic group and a functional group capable of forming a covalent bond with a nucleophile, and has a charge opposite to that of the ionizable group A, and 
       o is an integer value independently selected from 0-6, such that the sum of charges of C and A is zero. 
     
     
         25 . The method of  claim 24 , wherein B is independently selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
       wherein R is independently selected from the group consisting of hydrogen, C 1-6  alkyl groups, aryl groups, or an ionizable functional groups; Z′ is oxygen (O), NH or is absent, and G is carbon (C) and g is 1, or G is sulfur (S) and g is 2; and A is independently selected from the group consisting of: —COOH, —SO 3 H, —PO 3 H 2  and —N(R 1 ) 2 , —N(R 1 ) 3 ; wherein R 1  is independently selected from the group consisting of a hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl and heteroaryl groups; wherein each R 1  is independently unsubstituted or substituted with one or more substituents. 
     
     
         26 . The method of  claim 24 , wherein the linker Z is an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocycloalkyl group, or heteroaryl group,
 wherein the alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, or heteroaryl group is unsubstituted or substituted one or more times by a halogen, cyano, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine, hydroxy, oxo, formyl, acyl, carboxylic acid (—COOH), —C(O)R 1 , —C(O)OR 1 , (—COO − ), primary amide (e.g., —CONH 2 ), secondary amide (e.g., —CONHR 1 ), —C(O)NR 1 R 2 , —NR 1 S(O) 2 R 2 , —NR 1 C(O)R 2 , —S(O) 2 R 2 , —SR 1 , —S(O) 2 NR 1 R 2 , —SOR 1 , or —SOOR 1 ;   wherein R 1  and R 2  are each independently selected from the group consisting of a hydrogen, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, heterocycloalkyl, and heteroaryl group, wherein each of R 1  and R 2  is independently unsubstituted or substituted with one or more substituents.   
     
     
         27 . The method of  claim 24 , wherein the linker Z is a C 1-4  alkyl group. 
     
     
         28 . The method of  claim 27 , wherein the alkyl group is substituted with one or more substituents replacing a hydrogen on one or more carbons of the alkyl hydrocarbon backbone or the alkyl group is substituted with one or more heteroatoms within the hydrocarbon carbon backbone, or a combination thereof, and
 wherein the substituents are selected from the group consisting of oxo, hydroxyl, carboxyl, amido, and amino groups.   
     
     
         29 . The method of  claim 24 , wherein the active agent is: