WO2009063042A1

WO2009063042A1 - Thickened reducing composition

Info

Publication number: WO2009063042A1
Application number: PCT/EP2008/065541
Authority: WO
Inventors: Françoise Pataut; Kiyofumi Matsumoto
Original assignee: L'oreal
Priority date: 2007-11-15
Filing date: 2008-11-14
Publication date: 2009-05-22
Also published as: FR2923713A1; FR2923713B1

Abstract

The present invention relates to a reducing composition for the first step of a hair permanent reshaping operation, comprising, in a cosmetically acceptable medium: - one or more thiol reducing agent(s), - one or more organic disulfide compound(s), and - one or more non cellulosic thickening polymer(s).

Description

TH I CKE N E D R E D U C I N G COM POS ITI ON

The present invention relates to a method for permanently reshaping the keratin fibers, especially for permanently reshaping the hair, comprising a reducing step and an oxidizing step, whereby the reducing step is carried out using a specific thickened reducing composition.

The most usual art to obtain a permanent reshaping of the hair does consist, in a first step, in opening the keratin -S-S- disulfide bonds (cystine) with a composition comprising a suitable reducing agent (reducing step), and then, once the thus treated hair has been rinsed, in reforming in a second step said disulfide bonds, by applying onto the hair which has been beforehand set under tension (with curlers or equivalent) or otherwise shaped or straightened by other means, an oxidizing composition (oxidizing step, also called fixing step), so as to give the hair the expected shape in the end. This method thus makes it possible to indifferently either wave the hair (perming method), or to decurl or straighten the hair (straightening method). The new shape which has been imposed to the hair by means of a chemical treatment, such as hereabove, is temporally substantially long-lasting and does in particular resist to washing operations with water or shampoo, as opposed to the usual simple methods for temporarily reshaping the hair like using hair setting methods.

Reducing compositions suitable for implementing the first step of a perming operation do typically contain sulfites, bisulfites, alkyl-phosphines or preferably thiols as reducing agents. Amongst the latter, those that are traditionally used include cysteine and various derivatives thereof, cysteamine and derivatives thereof, thiolactic acid or thioglycolic acid, as well as salts and esters thereof, especially glycerol thioglycolate.

Oxidizing compositions useful for implementing the fixing step are mostly compositions based on hydrogen peroxide or alkaline metal bromate.

In the methods for permanently reshaping the hair, especially in perming methods, the reducing compositions often come in a liquid form. As a drawback, such compositions, once applied on the hair, do then suffer from running down the forehead, the nape, the face or from getting into the eyes, what bothers the user. In some methods for permanently reshaping the hair, as for example in reshaping methods without curlers, for decurling, in a so called "direct" perming method, that is to say an application of the reducing composition prior to winding up, then a winding-up, thereafter a rinsing time and then an application of the fixing composition, or in a so called "digital perm", that is to say an application of the reducing composition prior to winding up, a rinsing time, then a winding-up, thereafter a heat treatment, and then an application, it is preferred to use sufficiently thickened reducing compositions so as to make their application easier, to enable a better distribution of the product onto the hair, to prevent the reducing composition from running down, and to allow the hair to stay in place as expected. Moreover, such formulation type is highly appreciated by the user because it turns out to be easy and comfortable to use.

However, the formulation of thickened compositions is particularly difficult, especially because of frequently occurring time-related instability problems. There are indeed many phenomena which typically occur such as, in particular, a reduction of the product viscosity and/or a decrease of the reducing agent concentration and/or the formation of an unpleasant smell, or all these drawbacks at the same time. In addition, the preparation method of the thickened compositions may be particularly complicated, as it is the case for emulsions for example. A reducing agent is known from EP 940 136, comprising as a first component a thiol reducing agent-containing composition and as a second component a thickening polymer-containing composition as an oily or an aqueous dispersion, or as a reverse emulsion. The two components are intended to be mixed with each other at the time of use. However, such a reducing agent, while being quite acceptable on the whole, does suffer from phase separation problems.

A reducing composition, straightening cream, is known from the French patent application, filling number 0654853, filled November 10, 2006 and not yet published, comprising a thiol reducing agent, for example thioglycolic acid, an organic disulfide compound, for example diammonium dithiodiglycolate, and a thickener, for example oleyl alcohol.

A reducing agent is known from JP3522572, comprising a reducing composition containing ammonium thioglycolate as a thiol reducing agent, dithiodiglycolate as an organic disulfide compound and carboxymethyl cellulose as a thickening polymer.

Neither of these documents of the prior art does mention that such reducing compositions are stable over time and have a pleasant smell.

Therefore, there is a need for providing a reducing composition which solves the problems of the prior art.

The applicant discovered that a thickened reducing composition comprising a thiol reducing agent, an organic disulfide compound and a non cellulosic thickening polymer has an excellent stability over time, is very easy to produce on the industrial scale, is ready to use as a single unit, and does enable an excellent distribution of the product onto the whole hair, while preserving it from running down.

It is thus an object of the present invention to provide a reducing composition for the first step of a hair permanent reshaping operation, characterized in that it comprises, in a cosmetically acceptable medium:

- one or more thiol reducing agent(s),

- one or more organic disulfide compound(s), and

- one or more non cellulosic thickening polymer(s). As used herein, a "thiol reducing agent" is intended to mean a reducing agent comprising at least one -SH thiol function, said one or more thiol function(s) being optionally in the form of an organic or inorganic salt.

As used herein, a "reverse emulsion" is intended to mean a water-in-oil emulsion. The thiol reducing agent(s) which is or are present in the composition of the invention are preferably selected from thioglycolic acid, thiolactic acid, glycerol monothioglycolate, cysteamine, N-acetyl cysteamine, N-propionyl cysteamine, cysteine, N-acetyl cysteine, thiomalic acid, pantetheine, 2,3-dimercaptosuccinic acid, N- (mercaptoalkyl)-ω-hydroxyalkyl amides, N-mono- or N,N-dialkylmercapto-4- butyramides, aminomercapto-alkylamides, N-(mercaptoalkyl)succinamic acid and N- (mercaptoalkyl) succinimide derivatives, alkylamino mercaptoalkylamides, 2- hydroxypropyl thioglyconate and (2-hydroxy-1 -methyl)ethyl thioglycolate azeotropic mixture, mercaptoalkyl aminoamides and N-mercapto-alkyl alkanediamides, and salts thereof. Suitable examples of thiol reducing agents as salts include especially reducing agents in the form of ammonium salts, such as ammonium thioglycolate, or in the form of amine salts, such as monoethanolamine thioglycolate.

The thiol reducing agent(s) is or are used in sufficient amounts to reduce the keratin fiber disulfide bonds. Generally, the thiol reducing agent(s) represent(s) from 0.1 to 20%, preferably from 5 to 15% by weight of the composition total weight.

The disulfide(s) which is or are present in the composition of the invention may be any type of disulfides that is traditionally used in cosmetic compositions.

In a preferred embodiment of the invention, the disulfide(s) which is or are present in the composition of the invention is or are selected from compounds of formula:

R-S-S-R'

wherein R and R', being the same or different, represent a linear, branched or cyclic, saturated or unsaturated hydrocarbon group, which may be interrupted by one or more heteroatom(s) selected from sulfur, oxygen, nitrogen, silicon or phosphorus, and which may comprise one or more substituent(s) selected from hydroxyl, amine, carbamate, carbonate, hydrazine, ether, carboxylic acid, ester, amide, cyano and ureido groups, and salts thereof. To be particularly mentioned are dithiodiglycolic acid and diammonium dithiodiglycolate.

Generally, the disulfide compound(s) which is or are present in the composition of the invention represent(s) from 0.1 to 10%, preferably from 2 to 5% by weight of the composition total weight. Preferably, the non cellulosic thickening polymer(s) which is or are present in the composition of the invention is or are selected from:

- copolymers of ammonium acrylate and acrylamide, generally in a W/O reverse emulsion, such as BOZEPOL C marketed by the HOECHST company, - copolymers of acrylamide and acrylamido-2-methyl propane sulfonic acid, generally in a reverse emulsion, such as SEPIGEL 305 marketed by the SEPPIC company,

- copolymers of sodium acrylate and acrylamide, generally in a reverse emulsion, such as SEPIGEL 901 marketed by the SEPPIC company, - copolymers of trimethyl ethyl ammonium methacrylate chloride and acrylate, generally in an oil dispersion, such as SALCARE SC 92 marketed by the ALLIED COLLOIDS company,

- homopolymers of ethyl trimethyl ammonium methacrylate chloride, generally in an oil dispersion, such as SALCARE SC 95 marketed by the ALLIED COLLOIDS company.

The thickening polymers are preferably in the form of an aqueous or an oily dispersion, or of a reverse emulsion.

Preferred polymers are copolymers of AMPS and acrylamide such as SEPIGEL 305. The thickening polymer(s) is or are present in the composition of the invention in such amounts that the composition has a sufficient viscosity so as not to run down the scalp and/or so as to maintain the reshaping that has been imposed to the hair.

Preferably, the thickening polymer(s) represent(s) more than 3.5% by weight, preferably from 4 to 20% by weight, more preferably from 4 to 10% by weight of the composition total weight, bounds inclusive.

To improve the cosmetic properties of the hair fibers or to reduce or prevent their damaging, the reducing composition of the invention may also comprise one or more cosmetic active agent(s).

The cosmetic active agent(s) which may be present in the composition of the invention may be selected from alkaline agents, anionic, non ionic, cationic or amphoteric surfactants, anionic, cationic, non ionic or amphoteric treating agents, waxes, polymers that are different from those previously defined thickening polymers, swelling agents and penetrating agents, fatty alcohols, lanoline derivatives, ceramides, agents for combating hair loss, anti-dandruff agents, suspending agents, sequestering agents, opacifying agents, dyes, sunscreen agents, preserving agents and fragrances.

The alkaline agent(s) may especially be selected from monoethanol amine, diethanol amine, thethanol amine, isopropanol amine, propanediamine-1 ,3, alkaline or ammonium carbonate or bicarbonate, organic carbonate such as guanidine carbonate, or alkaline hydroxide, used either alone or in combination. The surfactant(s) used include those traditionally present in perm reducing compositions and may be of the non ionic, anionic, cationic or amphoteric type. To be especially mentioned are alkyl sulfates, alkyl benzenesulfates, alkyl ethersulfates, alkyl sulfonates, quaternary ammonium salts, oxyethylenated fatty alcohols, such as oxyethylenated oleyl alcohol, alkyl betaines, oxyethylenated alkylphenols, fatty acid alkanolamides, oxyethylenated fatty acid esters, as well as non ionic surfactants of the hydroxypropyl ether family.

The treating agent(s) may be selected from volatile or non volatile, linear or cyclic silicones, or combinations thereof, polydimethyl siloxanes, quaternized polyorganosiloxanes, those described in the French patent application 2 535 730, amino-alkyl group-containing polyorganosiloxanes modified with alkoxycarbonylalkyl groups such as those described in the patent US-A-4, 749,732, polyorganosiloxanes such as polydimethysiloxane- polyoxyalkyl copolymers such as dimethicone copolyol, polydimethyl siloxanes with stearoxy-(stearoxydimethicone) end groups, copolymers of polydimethylsiloxane and dialkylammonium acetate, or copolymers of polydimethylsiloxane and polyalkylbetaine described in GB-A-2 197 352, polysiloxanes organomodified by mercapto or mercaptoalkyl groups such as those described in FR-A- 1 530 369 and EP 0 295 780, as well as silanes such as steroxytri methyl silane.

Additional treating agents may also be used such as waxes, polymers different from the previously defined thickening polymers and selected from cosmetically acceptable polymers which may be cationic, anionic, non ionic or amphoteric polymers, swelling agents and penetrating agents to promote the reducing agent efficiency such as dimethyl isosorbitol, urea and derivatives thereof, pyrrolidone, n-alkylpyrrolidone, thiamorpholinone, alkyleneglycol or dialkyleneglycol alkylethers such as for example propyleneglycol monoethylether, dipropyleneglycol monoethylether, C₃-C₆ alkanediols such as for example propanediol-1 ,2, imidazolidinone-2, as well as other compounds such as fatty alcohols, lanoline derivatives, ceramides and especially ceramides as such, glycoceramides and pseudoceramides especially described in FR-A-95/1399, and in DOWNING Journal of Lipid Research, Vol. 35, p.2060, 1994 or in FR-A-2 673 197, EP-A-O 227 994, WO 94/07844, WO 92/05674, whose content is incorporated therein as a reference, active agents such as pantothenic acid or panthenol, agents for combating hair loss, anti-dandruff agents, suspending agents, sequestering agents, opacifying agents, dyes, sunscreen agents, as well as fragrances and preserving agents. The pH value of the reducing composition does generally range from 7 to 1 1 .

The cosmetically acceptable medium for the reducing composition of the invention is preferably an aqueous medium composed of water and may advantageously comprise cosmetically acceptable organic solvents, including more particularly alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or polyols or polyol ethers such as, for example, glycerol, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof such as, for example, propylene glycol monomethylether, butylene glycol, dipropylene glycol as well as diethylene glycol alkylethers, such as for example, diethylene glycol monoethylether or monobutylether. Organic solvents may then be present in amounts ranging from about 0.1 to 20% and, preferably, from about 1 to 10% by weight of the composition total weight.

The reducing composition of the invention is very easy to produce on an industrial scale. The thickening polymer(s) is or are introduced under stirring into the composition comprising the thiol reducing agent(s) and the organic disulfide compound(s). There is no need to supply any additional heat.

It is another object of the present invention to provide a method for permanently reshaping the keratin fibers, especially for permanently reshaping the hair, comprising:

- a step for applying onto the keratin fibers a reducing composition such as previously defined, said keratin fibers being set under mechanical tension before, during or after said application, and then, after an optional rinsing-off,

- a step for fixing the keratin fibers, either by contacting said keratin fibers with the oxygen present in the air, or by applying onto said keratin fibers an oxidizing composition comprising at least one oxidizing agent.

The step for setting the hair under tension may be implemented by using any known suitable mechanical means such as for example hair rollers, curlers, or any other manual means.

In an optional step of the method of the invention, the hair may undergo a thermal treatment, after application of the reducing composition, by heating to a temperature ranging from 30 to 60 °C. This heating step may optionally enable to adjust the final hair curling degree.

In practice, such an operation may be carried out using a hood hair dryer, a hair dryer, an IR-emitting device and other usual heating devices. It is of course also possible to work at room temperature.

The keratin fibers may be rinsed after the application of the reducing composition and before the application of the oxidizing composition.

According to a particular embodiment of the invention, the rinsing step after the reduction is not required, especially when the hair has been shaped by means that are not mechanical means.

Generally speaking, prior to rinsing or to applying the oxidizing composition, the hair onto which the reducing composition was applied is allowed to stand for a few minutes, generally between 3 and 60 minutes, and preferably between 5 and 30 minutes, so that the reducing agent has sufficient time to correctly act on the hair.

During this waiting step, it should be preferably made sure that the hair does not become dry and thus remain wet until the next step has to be carried out. Hair caps or protecting gels may thus be used to that end. As previously explained, the method of the invention may comprise a step of applying an oxidizing composition.

The oxidizing composition generally comprises at least one oxidizing agent selected from hydrogen peroxide, urea peroxide, alkaline metal bromates ; polythionates and persalts such as perborates, percarbonates and persulfates, and enzymes such as peroxydases and two-electron oxydo-reductases. Using hydrogen peroxide or enzymes is particularly preferred.

The oxidizing agent(s) generally represent(s) from 0.1 to 15%, preferably from 0.5 to 10%, by weight of the oxidizing composition total weight. Preferably, when the oxidizing agent is an aqueous solution of hydrogen peroxide, the oxidizing composition used in the method of the invention comprises at least one hydrogen peroxide-stabilizing agent.

Suitable examples thereof especially include alkaline metal or alkaline-earth metal pyrophosphates, such as tetrasodium pyrophosphate, alkaline metal or alkaline- earth metal stannates, phenacetine or acid and oxyquinoline salts, such as oxyquinoline sulfate (8-hydroxyquinoline sulfate). More advantageously, at least one stannate is used, in combination or not with at least one pyrophosphate.

The hydrogen peroxide-stabilizing agent(s) generally represent(s) from 0.0001 % to 5% by weight and preferably from 0.01 to 2% by weight of the oxidizing composition total weight.

To improve the cosmetic properties of the hair fibers or to reduce or prevent their damaging, the oxidizing composition used in the method of the invention may also comprise one or more cosmetic active agent(s), such as those previously mentioned for the reducing composition. Generally, the pH value of the oxidizing composition does range from 1 to 13, preferably from 1 .5 to 8.

The vehicle for the oxidizing composition is preferably an aqueous medium composed of water and may advantageously comprise cosmetically acceptable organic solvents, such as those previously mentioned for the reducing composition of the invention.

When the hair has been set under tension using a mechanical means, said mechanical means or curlers and equivalent, which maintained the hair under tension in the desired shape along the treatment, may be removed from the hair, before or after the fixing step. The waiting time for the oxidizing composition does range from 3 to 30 mn, and particularly from 5 to 15 mn.

After the application of the oxidizing composition, the hair is generally thoroughly rinsed, generally with water.

The present invention will be illustrated by the following example. Example

A reducing composition is prepared according to the invention. The formulation is as follows (expressed by weight of the total weight):

Ammonium thioglycolate 6.4%

Monoethanolamine thioglycolate 5.4%

Diammonium dithioglycolate 2.5%

Monoethanolamine 2% Glycerol 3%

Oxyethylenated oleyl alcohol 1 %

Fragrance 0.4%

SEPIGEL 305 from SEPPIC 4% MA

Water qs 100 g

The preparation method of the reducing composition is as follows. SEPIGEL 305 is introduced under stirring into a lotion comprising the other components. There is no need to supply any additional heat.

The composition is stable and is very easy to apply onto the hair. For permanently reshaping the hair, the reducing composition is applied onto wet hair. The reducing composition is allowed to remain in contact with the hair for 10 minutes. Thereafter, the oxidizing composition is applied onto the hair. The waiting time is 5 minutes, before rinsing with water. A beautiful curly hair is obtained as a result.

Claims

1 . A reducing composition for the first step of a hair permanent reshaping operation, characterized in that it comprises, in a cosmetically acceptable medium:

- one or more thiol reducing agent(s),

- one or more organic disulfide compound(s), and

- one or more non cellulosic thickening polymer(s).

2. A reducing composition according to claim 1 , wherein the thiol reducing agent(s) is or are selected from thioglycolic acid, thiolactic acid, glycerol monothioglycolate, cysteamine, N-acetyl cysteamine, N-propionyl cysteamine, cysteine, N-acetyl cysteine, thiomalic acid, pantetheine, 2,3-dimercaptosuccinic acid, N- (mercaptoalkyl)-ω-hydroxyalkyl amides, N-mono or N,N-dialkylmercapto-4-butyramides, aminomercapto-alkylamides, N-(mercaptoalkyl)succinamic acid and N-(mercaptoalkyl) succinimide derivatives, alkylamino mercaptoalkylamides, 2-hydroxypropyl thioglyconate and (2-hydroxy-1 -methyl)ethyl thioglycolate azeotropic mixture, mercaptoalkyl aminoamides and N-mercapto-alkyl alkanediamides, and salts thereof.

3. A reducing composition according to claim 1 or 2, wherein the thiol reducing agent(s) represent(s) from 0.1 to 20%, preferably from 5 to 15% by weight of the composition total weight.

4. A reducing composition according to any preceding claim, wherein the disulfide(s) is or are selected from compounds of formula:

R-S-S-R'

wherein R and R', being the same or different, represent a linear, branched or cyclic, saturated or unsaturated hydrocarbon group, which may be interrupted by one or more heteroatom(s) selected from sulfur, oxygen, nitrogen, silicon or phosphorus, and which may comprise one or more substituent(s) selected from hydroxyl, amine, carbamate, carbonate, hydrazine, ether, carboxylic acid, ester, amide, cyano and ureido groups, and salts thereof.

5. A reducing composition according to any preceding claim, wherein the disulfide compound(s) represent(s) from 0.1 to 10%, preferably from 2 to 5% by weight of the composition total weight.

6. A reducing composition according to any preceding claim, wherein the thickening polymer(s) is or are selected from copolymers of ammonium acrylate and acrylamide, copolymers of acrylamide and acrylamido-2-methyl propane sulfonic acid, copolymers of sodium acrylate and acrylamide, copolymers of thmethyl ethyl ammonium methacrylate chloride and acrylate and homopolymers of ethyl trimethyl ammonium methacrylate chloride.

7. A reducing composition according to any preceding claim, wherein the thickening polymer(s) come(s) as an aqueous or an oily dispersion or as a reverse emulsion.

8. A reducing composition according to any preceding claim, wherein the thickening polymer(s) represent(s) more than 3.5% by weight of the composition total weight.

9. A reducing composition according to any preceding claim, wherein the thickening polymer(s) represent(s) from 4 to 20%, preferably from 4 to 10% by weight of the composition total weight.

10. A reducing composition according to any preceding claim, which comprises one or more cosmetic active agent(s) selected from alkaline agents, anionic, non ionic, cationic or amphoteric surfactants, anionic, cationic, non ionic or amphoteric treating agents, waxes, polymers that are different from those previously defined thickening polymers, swelling agents and penetrating agents, fatty alcohols, lanoline derivatives, ceramides, agents for combating hair loss, anti-dandruff agents, suspending agents, sequestering agents, opacifying agents, dyes, sunscreen agents, preserving agents and fragrances.

1 1. A reducing composition according to any preceding claim, wherein the pH value does range from 7 to 1 1.

12. A method for permanently reshaping the keratin fibers, especially for permanently reshaping the hair, comprising:

- a step for applying onto the keratin fibers a reducing composition such as defined in any preceding claim, said keratin fibers being set under mechanical tension before, during or after said application, and then, after an optional hnsing-off, - a step for fixing the keratin fibers, either by contacting said keratin fibers with the oxygen present in the air, or by applying onto said keratin fibers an oxidizing composition comprising at least one oxidizing agent.

13. A method according to claim 12, wherein the reducing composition is allowed to act for 3 to 60 minutes, preferably for 5 to 30 minutes.

14. A method according to claim 12 or 13, wherein the keratin fibers are rinsed after the application of the reducing composition and before the application of the oxidizing composition.

15. A method according to any of claims 12 to 14, wherein the oxidizing agent(s) is or are selected from hydrogen peroxide, alkaline bromates, polythionates and persalts, such as perborates, percarbonates and persulfates.

16. A method according to any of claims 12 to 15, wherein the oxidizing agent(s) generally represent(s) from 0.1 to 15%, preferably from 0.5 to 10% by weight of the oxidizing composition total weight.

17. A method according to any of claims 12 to 16, wherein the pH value of the oxidizing composition does range from 1 to 13, preferably from 1.5 to 8.

18. A method according to any of claims 12 to 17, wherein the oxidizing composition is allowed to act for 3 to 30 minutes, preferably for 15 minutes.