PROCESS FOR TREATING KERATIN FIBERS TECHNICAL FIELD

The present invention relates to a process for treating keratin fibers, in particular the permanent deformation of keratin fibers, such as hair, as well as an agent and a kit to be used for the process. BACKGROUND ART

Many hair care products are marketed nowadays to easily style, texturize and add some weight to the hair, especially to thinning hair, amongst which foams and styling gels or hair lacquers may be mentioned as examples. These products enable shaping of the hair but are removed with shampoo and thus are required to be applied on a daily basis.

The most general technique for obtaining a long-lasting deformation of the hair consists, in a first step, of opening the keratin S-S disulfide bonds (cystine) with a composition comprising a suitable reducing agent (reducing step) then, once the thus treated hair has been rinsed, generally with water, reforming said disulfide bonds in a second step, by applying an oxidizing composition onto the hair which has been placed beforehand under tension, using curlers for example

(oxidizing step, also called fixing step) so as to give the hair the desired form in the end.

The new shape that is imposed to the hair by means of a chemical treatment, such as explained above, is relatively long-lasting and is relatively resistant to washing operations with water or shampoo, as compared to the usual simple methods for temporarily reshaping the hair by using foams, styling gels, or lacquers.

Many compositions and processes for the above chemical treatment have been proposed.

Generally, they offer good performances on the day of treatment.

DISCLOSURE OF INVENTION

However, there are various drawbacks as follows in the above chemical treatment process that may not be suitable from the view point of consumer's expectations:

Insufficient long-lastingness against environmental stress (mechanical constraints from brushing, frequent shampoos, light exposure, high humidity and the like);

Insufficient perm efficiency on natural hair;

High levels of hair degradation, especially in repeated applications or in combination with other chemical treatments such as oxidative coloration; and

Long processing time.

Thus, an objective of the present invention is to provide a new treatment process, in particular a permanent deformation process, for keratin fibers such as hair, which provides good curl lastingness. Another objective of the present invention is to provide strong perm efficiency for natural hair by the above new treatment process for keratin fibers. Another objective of the present invention is to prevent a high level of hair damage by a treatment process for keratin fibers.

A further objective of the present invention is to reduce the time required for conventional treatment processes, in particular permanent deformation processes, for keratin fibers, for example, providing a quick permanent shaping process for keratin fibers.

The above objectives of the present invention can be achieved by a process for treating keratin fibers, preferably hair, comprising the steps of:

applying to the keratin fibers a cosmetic composition comprising at least one reducing agent in an amount of from 0.01 to 10% by weight relative to the total weight of the composition and at least one source of ion(s) of formula:

wherein

X is a group selected from the group consisting of O ^" , OH, H ₂ , 0-OH, and O-COO ^" in an amount of from 0.01 to 10% by weight relative to the total weight of the composition;

placing the keratin fibers in an occlusive space; and

heating the keratin fibers.

The process may further comprise the step of rinsing the keratin fibers after the step of applying the cosmetic composition to the keratin fibers and/or after the step of heating the keratin fibers.

The occlusive space may be formed by at least one coating means. The coating means may be rigid or flexible. The coating means may comprise at least one member selected from the group consisting of a film and a sheet.

According to the present invention, mechanical tension may be provided to the keratin fibers by at least one reshaping means selected from the group consisting of a curler, a roller, a plate and an iron. According to the present invention, the keratin fibers may be heated at from 50 °C to 250 °C during the step of heating the keratin fibers. The keratin fibers may be heated by at least one heater providing at least one selected from the group consisting of hot air, hot steam, high frequency induction heating, microwave heating, infra-red ray irradiation, laser, and flash lamp irradiation. The above coating means and/or the reshaping means may comprise the heater.

The reducing agent may be selected from thiol reducing agents and non-thiol reducing agents. It is preferable that the reducing agent is selected from thioglycolic acid, cysteine, cysteamine and sodium sulfite.

The cosmetic composition may preferably comprise the reducing agent(s) in a total amount of from 0.01 to 5% by weight, preferably from 0.1 to 4% by weight, relative to the total weight of the composition.

The source of ions may be selected from the group consisting of carbonate salts and

hydrogencarbonate salts. The cosmetic composition may preferably comprise the source of ion(s) in a total amount of from 0.1 to 8% by weight, preferably from 0.5 to 5% by weight, relative to the total weight of the composition.

The weight ratio of the reducing agent(s)/the source(s) of ion(s) in the cosmetic composition may be from 0.1 to 10, preferably from 0.2 to 7, and more preferably from 0.3 to 4.

The pH of the cosmetic composition may range from 2 to 12, preferably from 5 to 9.5.

Thus, the present invention can provide a new treatment process, in particular a permanent deformation process, for keratin fibers such as hair, which can provide good curl lastingness and/or strong perm efficiency, can prevent a high level of hair damage, and/or can reduce the time required for treating the keratin fibers.

Another aspect of the present invention is a cosmetic composition for treating keratin fibers to be heated in an occlusive space, comprising at least one reducing agent in an amount of from 0.01 to 10% by weight relative to the total weight of the composition and at least one source of ion(s) of formula:

wherein

X is a group selected from the group consisting of O ^" , OH, NH ₂ , 0-OH, and O-COO ^" in an amount of from 0.01 to 10% by weight relative to the total weight of the composition.

The present invention also relates to a kit for treating keratin fibers, comprising:

a device comprising

at least one coating means to form an occlusive space, and

at least one heater to heat the keratin fibers in the occlusive space; and

a cosmetic composition comprising at least one reducing agent in an amount of from 0.01 to 10% by weight relative to the total weight of the composition and at least one source of ion(s) of formula:

wherein X is a group selected from the group consisting of O ^' , OH, NH ₂ , 0-OH, and O-COO ^" in an amount of from 0.01 to 10% by weight relative to the total weight of the composition.

BEST MODE FOR CARRYING OUT THE INVENTION

In order to achieve good performance, conventional perm products for keratin fibers such as hair contain a relatively high concentration of a reducing agent, for example, thioglycolic acid.

Additionally, some technologies use a heating process during the reducing step of keratin fibers in order to increase the chemical action of such reducing agent(s). These technologies use hot-ak/hot-steam/far-infrared to heat the keratin fibers rolled up on, for example, a plastic roller.

Because the heating process is usually performed in an open environment, the keratin fibers are heated to at most less than 50 °C, and cannot be heated furthermore due to the vaporization of water or moisture in the keratin fibers. At the end of the heating step, the reduced keratin fibers are rinsed, oxidized and rinsed again. The advantage of employing this heating process is a small improvement in perm performance and curl lastingness in comparison with a classical cold perm process.

However, in order to achieve better performance, strong reducing agent(s) as well as oxidizing agent(s) in a higher concentration are used. Therefore, keratin fibers undergo a significant or critical degradation that is not preferable for customers when considering repeated applications or further chemical treatments (for example, perm and coloration).

After diligent research, the inventors have discovered that it is possible to achieve better perm performance without generating significant or critical degradation of keratin fibers by using a cosmetic composition comprising at least one reducing agent in a specific amount range and at least one specific source of ion(s) in a specific amount range in association with a specific heating process during the permanent deformation treatment for the keratin fibers. The above specific heating process is performed in a closed or occlusive environment, which limits the evaporation of water or moisture from the keratin fibers and maintains the keratin fibers at a higher temperature in the wet state. Accordingly, the treated keratin fibers show good curl lastingness with good perm efficiency. Indeed, according to the present invention, an oxidative step is no longer required to achieve a stable permanent wave formation, unlike in a classical perm process. Thus, a one-step process can be achieved by the combination of the above new cosmetic composition with the above new heating process. This can considerably reduce the time required for a permanent deformation process for keratin fibers.

Hereinafter, the cosmetic composition according to the present invention will be explained in a more detailed manner. In the following description, the expression "at least one" is equivalent to the expression "one or several". (Cosmetic Composition) The cosmetic composition used for the present invention comprises at least one reducing agent. Two or more reducing agents may be used in combination. Thus, a single type of reducing agent or a combination of different type of reducing agents may be used.

The reducing agent may be selected from thiol reducing agents and non-thiol reducing agents.

The "thiol reducing agent" here means a reducing agent with at least one thiol group. The thiol reducing agent may preferably be chosen from the group consisting of thioglycolic acid and derivatives thereof, in particular esters thereof such as glycerol or glycol monothioglycolate; thiolactic acid and derivatives thereof, in particular esters thereof such as glycerol

monothiolactate; 3-mercaptopropionic acid and derivatives thereof, in particular esters thereof such as glycerol 3-mercaptopropionate and ethyleneglycol 3-mercaptopropionate; cysteamine and derivatives thereof, in particular CM acyl derivatives thereof such as N-acetylcystearnine and N-propionylcysteamine; mono-thioglycerol and derivatives thereof, in particular esters; cysteine and derivatives thereof, in particular esters such as N-acetylcysteine, N-alkanoylcysteine and cysteine alkyl esters; and salts thereof.

As the above salts, mention may be made of, for example, ammonium salts; primary-, secondary- or tertiary-amine salts; alkaline metal salts; and, alkaline earth metal salts. As the primary-, secondary- or tertiary-amine, for example, monoemanolamine, di-isopropanolamine or

Ixiethanolamine, respectively, may be mentioned.

Other suitable examples of the thiol reducing agent that may be used in the cosmetic composition for the present invention include, but are not limited to, sugar N-mercapto alkyl amides such as N-(mercapto-2-ethyl)gluconamide, β-mercaptopropionic acid and derivatives thereof; thiomalic acid; pantheteine; N-(mercaptoalkyl)ro-hydroxyalkyl amides such as those described in European Patent Application No. 0 354 835 andN-mono- or N,N-dialkylmercapto 4-butyramides such as those described in European Patent Application No. 0 368 763; aminomercaptoalkyl amides such as those described in European Patent Application No. 0432000 and

alkylarrnnomercaptoalkylamides such as those described in European Patent Application No. 0 514282; (2/3) hydroxy-2 propyl thioglycolate; and the hydroxy-2 methyl- 1 ethyl

thioglycolate-based mixture (67/33) described in French Patent Application No. 2 679448. The thiol reducing agent(s) is/are used in a total amount of from 0.01 to 10% by weight, preferably from 0.01 to 5.0% by weight, more preferably from 0.1 to 4.0% by weight, and even more preferably from 1.0 to 4.0% by weight, relative to the total weight of the composition.

The "non-thiol reducing agent" here means a reducing agent with no thiol group. The non-thiol reducing agent may preferably be chosen from the group consisting of sulfites, bisulfites, sulfinates, phosphines, sugars, reductones and hydrides. More preferably, the non-thiol reducing agent may be selected from ammonium sulfites and bisulfites as well as metal sulfites and bisulfites, more preferably alkali metal or alkali earth metal sulfites and bisulfites, and more preferably sodium sulfites and bisulfites. As the sulfinates, mention may be made of sulfinic acid salts, and benzenesulfinic acid salts such as sodium salts thereof. The sulfinic acid derivatives as described in FR-A-2814948 can also be used. A preferred sulfinate compound is 2-hydroxy-2-sulfinatoacetic acid, disodium salt. As the phosphines, mention may be made of monophosphine and diphosphines as described in FR-A-2870119. According to one particular embodiment of the present invention, the phosphine(s) can be chosen from the compounds of formula (I) below:

in which:

L is a linker that represents a covalent bond or a divalent hydrocarbon-based radical optionally comprising one or more hetero atoms chosen from an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom;

m is an integer equal to 0 or 1 ;

q is an integer equal to 1 or 2;

p is an integer equal to 0 or 1;

R , R and R , which may be identical or different, represent:

a hydrogen atom;

a halogen atom;

a hydroxyl radical;

a carboxyl radical;

a monovalent hydrocarbon-based radical optionally comprising one or more hetero atoms chosen from a sulfur atom, an oxygen atom, a nitrogen atom, a phosphorus atom and a silicon atom, optionally substituted with one or more radicals chosen from:

a halogen atom,

a hydroxyl radical,

an alkoxy radical,

a haloalkyl radical,

an amino radical,

a carboxyl radical,

an alkoxycarbonyl radical,

an amido radical,

an alkylaminocarbonyl radical,

an acylamino radical,

a mono- or di(alkyl)amino radical,

a mono- or di(hydroxyalkyl)amino radical,

an N-aryl-N-alkylarnino radical,

an aromatic or heteroaromatic ring, which is unsubstituted or substituted with one or more radicals chosen from a halogen atom, a hydroxyl radical, an alkoxy radical and a mono- or di(alkyl)amino radical, a cyano radical,

a radical that increases the solubility of the phosphine in water, such as sulfonate, sulfrnate, phosphonate or carboxylate radicals,

a substituted or unsubstituted, aromatic or non-aromatic heterocyclic radical;

a substituted or unsubstituted aryl radical;

a substituted or unsubstituted arylalkyl radical;

an arylalkyloxy radical;

a substituted or unsubstituted, aromatic or non-aromatic heterocyclic radical;

a silyl radical;

it being understood that:

when q= 1 , m=0 and p= 1 ;

when q=2, m=l and p=0 or 1 , with:

when p=0, the linker L is attached to the phosphorus atom; and

when p=l , the linker L is attached to one of the radicals R , R and R ,

and acid-addition salts thereof.

In all the above definitions, when a radical is substituted, the substituents are chosen from halo, hydroxyl, alkyl, haloalkyl, alkoxy, amino, mono- or dialkylamino, mono- or dmydroxyalkylamino and carboxyl. For example, the radical p-methoxyphenyl is a substituted aryl radical.

Preferably, the radi •cals R 31 , R 32 and R 33 do not simultaneously represent a hydrogen atom.

Advantageously, but optionally, at least one of the radicals R , R and R denotes, as a hydrocarbon-based radical, an optionally substituted alkyl radical.

According to one particular embodiment of the invention, R , R and R are chosen from a hydrogen atom; an alkyl radical; a cycloalkyl radical optionally substituted with one or more alkyl radicals; an alkoxy radical; an alkoxyalkyl radical; a haloalkyl radical; a cyanoalkyl radical; a hydroxyalkyl radical; a carboxyalkyl radical; a halogen atom; a hydroxyl radical; a carboxyl radical; an alkenyl radical; a mono- or dialkylamino radical; an N-aryl-N-alkylaminoalkyl radical; an aryl radical optionally substituted with one or more radicals chosen from an alkyl radical, an alkoxy radical, a mono- or dialkylamino radical, a mono- or dialkylarriinoalkyl radical, a haloalkyl radical, a hydroxyl radical, a carboxyl radical, a halogen atom, and an aryl radical substituted with a mono- or didl ylaminoalkyl radical; an arylalkyl radical; an arylalkyloxy radical; a pyrrolidino radical; a furyl radical; a morpholino radical; a thienyl radical; a pyridyl radical; a trialkylsilyl radical; and an alkyl radical substituted with a pyrrolidino radical, a furyl radical, a morpholino radical or a thienyl radical.

By way of example, R , R and R may be chosen from a hydrogen atom; a methyl radical; an ethyl radical; a propyl radical; an isopropyl radical; an n-butyl radical; an isobutyl radical; a tert-butyl radical; an octyl radical; a cyclohexyl radical; a cyclopentyl radical; a methoxy radical; an ethoxy radical; a methoxypropyl radical; a chloroethyl radical; a cyanoethyl radical; a hydroxymethyl radical; a hydroxypropyl radical; a carboxyethyl radical; a chlorine atom; a hydroxyl radical; a carboxyl radical; atrifluoromethyl radical; a chloromethyl radical; an allyl radical; a vinyl radical; a dimemyl-anino radical; a diemylamino radical; a di(isopropyl)arnino radical; a phenyl radical; an o-tolyl radical; an m-tolyl radical; a p-tolyl radical; a dimethylphenyl radical; a trimethylphenyl radical; an o-methoxyphenyl radical; an m-methoxyphenyl radical; a p-methoxyphenyl radical; a dimethoxyphenyl radical; a trirnethoxyphenyl radical; an

o-(dimemylamino)phenyl radical; an m-(dimethylamino)phenyl radical; a

p-(dimemylamino)phenyl radical; a di(tert-butyl)phenyl radical; a tri(tert-butyl)phenyl radical; a trifluoromethylphenyl radical; a bis(trifluoromethyl)phenyl radical; an o-fluorophenyl radical; an m-fluorophenyl radical; a p-fluorophenyl radical; an o-chlorophenyl radical; an m-chlorophenyl radical; a p-chlorophenyl radical; an o-hydroxyphenyl radical; an m-hydroxyphenyl radical; a p-hydroxyphenyl radical; a 4-(diemylaminomethyl)phenyl radical; a

3,5-dimethyl-4-methoxyphenyl radical; a 2-methylbiphenyl radical; a benzyl radical; a benzyloxy radical; a naphthyl radical; a morpholino radical; a morpholinomethyl radical; a pyrrolidino radical; a furyl radical; a pyridyl radical; a thienyl radical; a trimethylsilyl radical; a

2-(4-diemylaminomethyl-phenyl)phenyl radical; a 5-methyl-2-isopropylcyclohexyl radical; an N-methyl-N-phenylaminomethyl radical; and a carboxyphenyl radical.

The phosphines that are useful in the context of the invention may be optionally salified with strong mineral acids, for instance HC1, HBr, H ₂ S0 ₄ or HBF ₄ or organic acids, for instance acetic acid, lactic acid, tartaric acid, citric acid or succinic acid.

According to one particular embodiment of the invention, the phosphine(s) that is (are) useful in the context of the invention is (are) chosen from monophosphines. For example, when the phosphine(s) is (are) of formula (I), q is then preferably equal to 1.

Examples of monophosphines that may be mentioned include (hydroxymemyl)phosphine; tri(hydroxypropyl)phosphine; bis(hydroxymethyl)(phenyl)phosphine; allyldiphenylphosphine; benzyldiphenylphosphine; bis(3,4,5-trimemoxyphenyl)cUorophospliine;

bis(3,4,5-trimemoxyphenyl)phosphine; benzyloxy(diisopropylarnmo)memylphosphine;

bis(diisopropylarnino)cUorophosphine; bis(2-cyanoethyl)phosphine;

bis(3,5-di-tert-butylphenyl)cWorophosphine; bis(3,5-di-tert-butyl-phenyl)phosphine;

bis(diemylammo)memylphosphine; bis(diemylamino)cMorophosphine;

bis(diemylammo)phenylphosphine; bis(3,5-dimethyl-4-methoxyphenyl)chlorophosphine;

bis(3 ,5-dimemyl-4-memoxyphenyl)phosphine; bis(3 ,5-dimethylphenyl)chlorophosphine;

bis(3,5-dimemylphenyl)diemylammophosphine; bis(3,5-dimethylphenyl)phosphine;

bis(3,5-ditrifluoromemylphenyl)chlorophosphine; bis(3,5-cUtrifluoromemylphenyl)phosphine; bis(4-fluorophenyl)cUorophosphine; bis(2-furyl)cUorophosphine; bis(2-furyl)phosphine;

bis(hydroxymethyl)phenylphosphine; bis(4-methoxyphenyl)phenylphosphine;

bis(3 ,5 -dimemylphenyl)phosphine; bis(3 ,5 -di-tert-butylphenyl)c orophosphme;

bis(3,5-di-tert-butylphenyl)phosphine; bis(3,5-di fluoromemylphenyl)c orophosphine;

bis(3,5-ditrifluoromemylphenyl)phosphine; bis(4-fluorophenyl)cUorophosphine;

bis(4-memoxyphenyl)cMorophosphine; bis(4-memoxyphenyl)phenylphosphine;

bis(4-memylphenyl)cWorophosphine; bis(4-methylphenyl)phosphine;

bis(4-trifluoromethylphenyl)cMorophosphine; bis(4-trifluoromemylphenyl)phosphine;

bis(diemylarrnno)memylphosphine; bis(diemylamino)phenylphosphine;

bis(hydroxymemyl)phenylphosphine; bis(o-tolyl)chlorophosphine; bis(o-tolyl)phosphine;

bis( yrrolidmo)memylphosp ne; butyldichlorophosphine; butyldiphenylphosphine; tert-butyldiphenylphosphine; cyclohexyl(diemylarnmo)chlorophosphine;

cyclohexyl(dimemyl-ammo)cMorophosphine; cyclohexyldicWorophosphine;

cyclohexyldiphenylphosphine; 2-cWoroemyldiphenylphosphine;

2-(dicyclohexylphosphino)bip enyl; 2-dicyclo-hexylphosphmo-2'-(N,N-dimemylam

diemyl-ammodiemylphosphine; dimemylarnmodicUorophosphine;

(4-dimemylammophenyl)diphenylphosphine; N-[(diphenyl-phosphinyl)methyl]-N-memylariiline; o-diphenylphosphinobenzoic acid; 2-memoxy(dicUorophosphino)benzene;

4-memoxyphenyl(diethylammo)cMorophosphLne;

4-memoxyphenyl(dimemylarrnno)cMorophosphine; (2-memoxyphenyl)memylphenylphosphine; 2-methoxyphosphinobenzene; (5-memyl-2-isopropylcyclohexyl)diphenylphosphine;

triphenylphosphine; diallylphenylphosphine; dibenzylphosphine; dibutylphenylphosphine;

dibutylphosphine; dicyclohexylchlorophospiiine; dicyclohexylphenylphosphine;

dicyclohexylphosphine; diemylcMorophospbine; diethylphenylphosphine; diethylphosphine; diisobutylphosphine; diisopropylchlorophosphine; diisopropylphosphine;

dimemyl(phenyl)phosphine; dm ethyl(1rimethylsilyl)phosphine; dimethylchlorophosphine;

diphenyl(o-tolyl)phosphine; diphenyl(p-tolyl)phosphine; diphenyl(trimemylsilyl)phosphine; diphenylcWorophosphine; diphenylphosphine; diphenylpropylphosphine;

diphenylvmylphosphine; di-tert-butylcWorophosphine; di-tert-butylhydroxyphosphine;

di-tert-butylmemylphosphine; di-tert-butylphenylphosphine; di-tert-butylphosphine;

divmylphenylphosphine; emyl-dicMorophosphine; ethyldiphenylphosphine;

isopropyl-dicWorophosphine; methoxydiemoxyphosphine; memyl-dichlorophosphine;

memyldiphenylphosphine; memyl-phenylcWorophosphine; phenylphosphine;

propyldichlorophosphine; tert-butylbis(trimemylsilyl)phosphine; tert-butyldichlorophosphine; tert-butyldiethylphosphine; tert-butyldiphenylphosphine; tert-butylphosphine;

tri(m-tolyl)phosphine; tri(o-tolyl)phosphine; tri(p-tolyl)phosphine; tricyclohexylphosphine;

1ricyclopen1ylphosphine; triemylphosphine; triisoburylphosphine; Iriisopropylphosphine;

trimemylphosphine; tri-n-butylphosphine; tri-n-octylphosphine; tripropylphosphine;

tris( 1 -naphthyl)phosphine; tris(2,4,6-tiimemylphenyl)phosphine;

tris(2,6-dimethoxyphenyl)phosphine; tris(2-carboxyemyl)phosphine; tris(2-cyanoethyl)phosphine; tris(2-ftiryl)phosphine; tris(2-methoxyphenyl)phosphine; tris(2-thienyl)phosphine;

s(3,5-dimethyl-4-memoxy)phosphine; tris(3-chlorophenyl)phosphine;

s(3-fluoro-phenyl)phosphine; tris(3-methoxyphenyl)phosphine;

Ms(3-methoxypropyl)phosphine; tris(4-chlorophenyl)phosphine; tris(4-fluorophenyl)phosphine; 1xis(4-methoxyphenyl)phosphine; tris(4-morpholino)phosphine; tris(hydroxymemyl)phosphine; tris(trimethylsilyl)phosphine; s[3,5-bis(trifluoromemyl)phenyl]phosphine;

tri-tert-butylphosphine; 2-cyanoethyldiphenylphosphine;

2-dicyclohexylphosphino-2'-methylbiphenyl; bis(2,4,6-trirnethylphenyl)phosphine; and

2-(di-tert-butyl-phosphino)biphenyl.

Preferably, the monophosphines are chosen from trihydroxymemylphosphine;

trihydroxypropylphosphine; and bis(hydroxymethyl)phenylphosphine.

According to another particular embodiment of the invention, the phosphine(s) that is (are) useful in the context of the invention is (are) diphosphines. When the phosphine(s) is (are) of formula (I), q is then preferably equal to 2. Preferably, p is equal to 0 and the linker L is a covalent bond or a divalent radical chosen from a binaphthylene radical; a methylene radical; an ethylene radical; a propylene radical; a butylene radical; a pentylene radical; a hexylene radical; a phenylene radical; a meta-dimethylenebenzene radical; an N-methyl-N'-methylhydrazo radical; a vinylene radical; and a diethyleneoxy radical.

As examples of diphosphines that are useful in the context of the invention, mention may be made of 2,2'-bis(dicyclohexylphosphino)- 1 , 1 '-binaphthyl;

2,2'-bis[bis(3,5-dimemylphenylphosphmo)]-l,l'-binaphthyl;

1.4- bis[bis(3 ,5-dimemylphenyl)phosphino]butane;

1.2- bis[bis(3 ,5-dimethylphenyl)phosphino]ethane;

bis[bis(3,5-dimemylphenyl)phosphino]methane;

1.5- bis[bis(3 ,5-dimemylphenyl)phosphino]pentane;

1.3- bis|¾is(3,5-dimethylphenyl)phosphino]propane;

2,2'-bis[bis(3,5-ditrifiuoromemylphenyl)phosphino]- 1 , 1 '-binaphthyl;

1.4- bis[bis(3 ,5-ditrifluoromemylphenyl)phosphmo]butane;

1.2- bis[bis(3,5-ditrifluoromemylphenyl)phosphino]ethane;

bis[bis(3,5-ditrifluoromemylphenyl)phosphino]methane;

1.5- bis-[bis(3,5-ditrifiuoromemylphenyl)phosphino]pentane;

1.3- bis[¾is(3,5-ditrifluoromemylphenyl)phosphino]-propane;

1 ,2-bis(di-tert-butylphosphino)benzene; 1 ,4-bis(di-tert-butylphosphino)butane;

1.2- bis(di-tert-butylphosphino)ethane; 1 ,3-bis(a^-tert-butylphosphinomethyl)benzene;

1.3- bis(di-tert-butylphosphino)propane; 1 ,2-bis(dicWorophosphino)benzene;

1.3- bis(dichlorophosphino)benzene; 1 ,4-bis(dichlorophosphino)benzene;

1.4- bis(dichlorophosphino)butane; 1 ,2-bis(dichlorophosphino)- 1 ,2-dimethylhydrazine;

1.2- bis(dicUorophosphino)ethane; bis(dicUorophosphino)methane;

1.3- bis(dichlorophosphino)propane; 1 ,2-bis(dicyclohexyl-phosphino)benzene;

2,2'-bis(dicyclohexylphosphino)- 1 , 1 '-binaphthyl; 1 ,4-bis(dicyclohexylphosphino)butane;

(2R,3R)bis(dicyclohexylphosphino)butane; (2S,3S)-bis(dicyclohexylphosphino)butane;

1.2- bis(dicyclohexylphosphino)ethane; bis(dicyclohexylphosphino)methane;

1.3- bis(dicyclohexylphosphino)propane;

bis[2-(4-diemylammomemylphenyl)phenylphosphino]ethylether ;

1 ,2-bis(diemylphosphino)ethane; 1 ,2-bis(dimemyl-phosphino)benzene;

1.4- bis(dimemylphosphino)butane; 1 ,2-bis(dnnethylphosphino)ethane;

bis(dimemylphosphino)methane; l,3-bis(dimemylphosphino)propane;

1.2- bis(diphenylphosphino)benzene; 1 ,3 -bis(diphenylphosphino)benzene;

1 ,4-bis(diphenylphosphino)benzene; 2,2'-bis(diphenylphosphino)- 1 , 1 '-binaphthyl;

1 ,4-bis(di-phenylphosphino)butane; 1 ,2-bis(diphenylphosphino)ethane;

cis- 1 ,2-bis(diphenylphosphino)ethylene; trans- 1 ,2-bis(diphenylphosphino)ethylene;

bis(2-diphenylphosphino)ethyl ether; 1 ,6-bis(diphenylphosphino)hexane;

bis(diphenylphosphino)methane; 1 ,5-bis(diphenylphosphino)pentane;

1.3- bis(diphenylphosphino)propane; 1 ,2-bis(ditrifluoromemylphosphino)ethane;

1.2- bis[(2-memoxyphenyl)phenylphosphino]ethane; 1 ,2-bis-(phenylphosphino)ethane;

1.3- bis(phenylphosphino)propane; bis-2-[( henyl)(3-pyridyl)phosphinoethyl]ether;

l,2-bis(phosphino)benzene; l,2-bis(phosphino)ethane; bis(phosphino)methane;

1 ,2-bis(trifluoro-memyl)phosphino)ethane; bis(di-tert-butylphosphino)pentane; and tetraphenylbiphosphine.

According to one particular embodiment of the invention, the phosphine(s) that is (are) useful in the context of the invention is (are) soluble in a cosmetically acceptable medium. Preferably, the phosphine(s) that is (are) useful in the context of the invention is (are) water-soluble.

In the context of the present invention, the term "water-soluble" means any phosphine whose solubility in water is greater than 0.01 wt% at 20°C. Preferably, the phosphine is

trmydroxymemylphosphine.

As the sugars, mention may be made of ribose, glucose, maltose, galactose, lactose, and xylose.

As the reductones, mention may be made of ascorbic acid and erythorbic acid. As the hydrides, mention may be made of boron hydrides such as sodium borohydride, lithium hydride, and phosphorous hydride. Precursors of hydrides and especially of boron hydrides such as diborane, tetraborane, pentaborane, decaborane and dodecaborane can be used.

Preferred non-thiol-based reducing agents are chosen from sulfites, bisulfites and phosphines.

The non-thiol reducing agent(s) is/are used in a total amount of from 0. 1 to 10% by weight, preferably from 0.01 to 5.0% by weight, more preferably from 0.1 to 4.0% by weight, and even more preferably from 1.0 to 4.0% by weight, relative to the total weight of the composition. It is preferable that the reducing agent is selected from thioglycolic acid, cysteine, cysteamine and sodium sulfite.

It may be preferable to use non-thiol reducing agent(s) because the malodor derived from sulfur atom(s) can be reduced or avoided.

The cosmetic composition used for the present invention comprises at least one source of ion(s) of formula:

wherein

X is a group selected from the group consisting of O ^' , OH, NH , 0-OH, and O-COO ^" . Two or more sources may be used in combination. Thus, a single type of source or a combination of different type of sources may be used.

Suitable sources of these ions may be inorganic salts such as sodium, potassium, lithium, calcium, magnesium, barium, and ammonium salts of carbonate, peroxycarbonate, carbamate,

hydrogencarbonate ions and mixtures thereof. As examples of the above inorganic salts, mention may be made of sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, lithium carbonate, lithium hydrogencarbonate, calcium carbonate, magnesium carbonate, barium carbonate, ammonium carbonate, ammonium hydrogencarbonate and mixtures thereof.

Suitable sources of these ions may also be organic salts such as organic base salts of carbonate, peroxycarbonate, carbamate, hydrogencarbonate ions and mixtures thereof. As an example of the above organic salts, mention may be made of amino acid carbonates and guanidine carbonate.

Among carbonate salts, ammonium carbonate, sodium carbonate, potassium carbonate, guanidine carbonate and its derivatives are preferable.

Among hydrogencarbonate (bicarbonate) salts, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and its derivatives such as tetraethylammonium bicarbonate and triethylammonium bicarbonate are preferable. Among carbamate salts, ammonium carbamate is preferable.

Among peroxycarbonate salts, sodium peroxycarbonate and potassium peroxycarbonate are preferable. As the ion sources, carbonate salts and hydrogencarbonate salts are preferable. In particular, sodium carbonate and sodium hydrogencarbonate (called bicarbonate) are more preferable.

The source(s) of the above ion(s) is/are used in a total amount of from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, more preferably from 0.5 to 5% by weight, and even more preferably from 1.0 to 3% by weight, relative to the total weight of the composition, depending on their solubility.

The weight ratio of the reducing agent(s)/the source(s) of ion(s) in the cosmetic composition may be from 0.1 to 10, preferably from 0.2 to 7, and more preferably from 0.3 to 4.

In a preferred embodiment, the cosmetic composition used in the present invention comprises at least one reducing agent in an amount ranging from 0.01 to 5% by weight, and if the reducing agent is a thiol reducing agent, in combination with at least one source of ion(s), in an amount ranging from 0.01 to 10% by weight, relative to the total weight of the composition.

In another preferred embodiment, the cosmetic composition used in the present invention comprises at least one reducing agent in an amount ranging from 0.01 to 10% by weight, and if the reducing agent is a non-thiol reducing agent, in combination with at least one source of ion(s), in an amount ranging from 0.01 to 10% by weight, relative to the total weight of the composition.

The pH of the cosmetic composition may range from 2 to 12, preferably between 5 and 9.5, and more preferably between 7.0 to 9.0. Since the pH of the cosmetic composition is not relatively high, damage to the keratin fibers by the composition can be reduced.

In order to adjust the pH, an acidic or alkali agent(s) other than source(s) of ion(s) of the invention may be used alone or in combination. The amount of the acidic or alkali agent(s) is not limited, but may be from 0.1 to 5% by weight relative to the total weight of the composition. As the acidic agents, mention may be made of any inorganic or organic acids which are commonly used in cosmetic products such as citric acid, lactic acid, phosphoric acid or hydrochloric acid (HQ). HC1 is preferable. As the alkali agents, mention may be made of any inorganic or organic basic agents which are commonly used in cosmetic products such as ammonia; alcanolamines such as mono-, di- and tri-ethanolamine, isopropanolarnine; sodium and potassium hydroxides; urea, guamdine and their derivatives; basic amino acids such as lysine or arginine; and diamines such as those described in the structure below:

R1 R3

N-R-N

R2 R4 wherein R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a Ci-C ₄ alkyl radical, and Ri, R ₂ , R ₃ and Rj independently denote a hydrogen atom, an alkyl radical or a Ci-C ₄ hydroxyalkyl radical, which may be exemplified by 1 ,3-propanediamine and derivatives thereof. Arginine and monoethanolamine are preferred.

The cosmetic composition used in the present invention may also comprise at least one additional ingredient. The amount of the additional ingredient(s) is not limited, but may be from 0.01 to 20% by weight relative to the total weight of the composition. The additional ingredient(s) may be selected from the group consisting of volatile or non volatile, linear or cyclic, amine-type or not, silicones, cationic, anionic, non ionic or amphoteric polymers, peptides and derivatives thereof, protein hydrolyzates, synthetic or natural waxes, and especially fatty alcohols, swelling agents and penetrating agents, as well as other active compounds, such as anionic, cationic, non ionic, amphoteric or zwitterionic surfactants, agents for combating hair loss, anti-dandruff agents, associative-type or not, natural or synthetic thickeners, suspending agents, sequestering agents, opacifying agents, dyes, sunscreen agents, fillers* vitamins or provitamins, mineral, vegetable or synthetic oils, as well as fragrances, preserving agents, stabilizers, and mixtures thereof. The cosmetic composition used in the present invention preferably comprises water and may advantageously contain one or several organic solvents, which particularly include alcohols, such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or polyols or polyol ethers, such as ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof, such as propylene glycol monomethylether, butylene glycol, dipropylene glycol as well as diethylene glycol alkyl ethers, such as diethylene glycol monoethylether or

monobutylether. The water may be present in a concentration of from 10 to 90% by weight relative to the total weight of the composition. The organic solvent(s) may then be present in a concentration of from 0.1 to 20% by weight, and preferably from 1 to 10% by weight elative to the total weight of the composition.

The cosmetic composition used in the present invention may exist in any form such as a lotion, a gel, thickened or not, a foam, or a cream. (Keratin Fiber Treatment Process)

The process for treating keratin fibers according to the present invention can be performed by applying onto the keratin fibers the cosmetic composition as described above;

then placing the keratin fibers in an occlusive space; and

then heating the keratin fibers,

According to the present invention relating to the treatment process for keratin fibers, keratin fibers such as hair are subjected to a specific heating process which is performed in an occlusive space.

The heating process can be performed by any heating means which can be freely controlled to realize the temperature desired for the process.

The heating process may preferably be performed by using a special heating device or devices that can form an occlusive space to restrict the evaporation of evaporable components such as water in the above-described cosmetic composition from keratin fibers and keep a predetermined temperature in the heating device throughout the process.

If the evaporable components such as water in the above-described cosmetic composition evaporate from the keratin fibers, most of the heat energy applied to the keratin fibers will be consumed by the evaporation, and therefore the temperature of the keratin fibers cannot increase up to the predetermined temperature until all evaporable components in the cosmetic composition evaporate.

The above heating device may comprise a heat energy source being either in contact with keratin fibers or apart from keratin fibers, and at least one means to form an occlusive space surrounding the keratin fibers.

The heat energy source is used to heat keratin fibers. The heat energy source may be at least one heater providing at least one selected from the group consisting of hot air, hot steam, high frequency induction heating, microwave heating, infrared ray irradiation, laser, and flash lamp irradiation.

The occlusive space may be formed by at least one coating means. A plurality of coating means may be used. The coating means may be rigid or flexible.

The coating means may comprise at least one member selected from the group consisting of a film and a sheet. The material of the film or the sheet is not limited. For example, the film or the sheet may comprise a thermoplastic or thermosetting resin, a paper, a textile, a bonnet, a metal foil such as aluminum foil, and the like.

For example, the film or sheet may be set on a heating rod, a heating bar or a heating plate which is covered by keratin fibers. According to the present invention, the coating means may comprise the heat energy source. Therefore, for example, the film or sheet which includes a heater may be set on a rod, a bar, or a plate which is covered by keratin fibers.

The occlusive conditions can restrict the evaporation of evaporable components such as water in the above-described cosmetic composition applied to keratin fibers, and therefore the temperature of the keratin fibers can be increased higher than that obtainable by a conventional heating process or device for the keratin fibers in open conditions. Furthermore, the keratin fibers can be heated effectively, and the keratin fibers can be heated evenly.

According to one variation of the present invention, the occlusive space may comprise apertures, the surface area of which is less than 5%, preferably less than 3% and more particularly less than 0.5% of the total surface area of the coating means. According to this variation, the total surface area of the coating means comprises the surface area of, when it is present, an opening means for the coating means.

The apertures may be passages, holes or orifices, which may allow an exchange of air between the occlusive space and the exterior thereof, especially when the reaction such as forming vapor inside the occlusive space is too great. On the other hand, a person skilled in the art could form the apertures such that the diffusion of heat in the occlusive space is not impaired.

The keratin fibers can be heated at from 50 °C to 250 °C, preferably from 60 °C to 200 °C, more preferably from 60 °C to 150 °C, even more preferably from 60 °C to 90 °C, during the step of heating the keratin fibers.

The heating process may be performed for an appropriate time which is required to treat the keratin fibers. The time length for the heating process is not limited, but it may be from 1 minute to 2 hours, preferably from 1 minute to 1 hour, and more preferably from 1 minute to 30 minutes. For example, the time for heating may be from 5 to 20 minutes, preferably from 10 to 15 minutes.

The keratin fibers may be rinsed after the step of applying the cosmetic composition onto the keratin fibers and/or after the step of heating the keratin fibers. (Permanent Deformation Process for Keratin Fibers)

According to one embodiment of the process for treating keratin fibers according to the present invention, keratin fibers are subjected to permanent deformation such as permanent waving or straightening.

According to one embodiment of the permanent deformation process, the keratin fibers may be subjected to mechanical tension which is typically used for permanent deformation. The permanent deformation process for keratin fibers when mechanical tension is applied to keratin fibers may be performed as follows. First, keratin fibers are subjected to mechanical tension for deformation. The mechanical tension can be applied to the keratin fibers by any means to deform the keratin fibers to an intended shape. For example, the mechanical tension may be provided by at least one reshaping means , selected from the group consisting of a curler, a roller, a clip, a plate and an iron. The reshaping means may comprise at least one heater as described above. If the keratin fibers are rolled around a curler, this rolling-up may be performed on the entire length of the keratin fibers or, for example, on half the length of the keratin fibers. Depending on, for example, the desired hairstyle shape and amount of curls, the rolling-up may be performed with more or less thick locks. Next, the above-described cosmetic composition is applied to the keratin fibers. The application of the cosmetic composition may be performed by any means, such as a brush and a comb. The keratin fibers to which the mechanical tension has been applied should be treated with the cosmetic composition. It may be possible that the keratin fibers are left as they are for a certain amount of time, if necessary.

Lastly, the above-described heating process is performed. The heat energy is applied to the keratin fibers under occlusive conditions as described above.

This process for permanent deformation of keratin fibers may be performed without any step of oxidizing the keratin fibers. Therefore, the time required for the process according to the present invention can be shorter than that for a conventional process which needs an oxidizing step.

Furthermore, damage to the keratin fibers by the oxidizing step can be avoided.

The keratin fibers may be rinsed after the step of applying the cosmetic composition onto the keratin fibers and/or after the step of heating the keratin fibers.

One embodiment of the treatment process according to the present invention may be a process for reshaping or permanently deforming keratin fibers, in particular hair, comprising:

a) a step of placing the keratin fibers under mechanical tension by rolling them up on at least one reshaping or mechanically tensioning means so as to form curls;

b) a step of applying the above-described cosmetic composition to the keratin fibers;

c) an optional step of rinsing the keratin fibers,

d) a step of placing at least one coating means on the reshaping or mechanically tensioning means or vice versa to form one or more occlusive spaces; and

e) a step of heating the keratin fibers at a temperature of between 45 ± 2 or 3 °C and 250 ± 2 or 3 °C, preferably for 1 minute to 2 hours. However, the time for the heating should not be limited.

In this process, the temperature can be set, adjusted and regulated by using one or more heating means, and may be measured with a thermo-measurement probe such as Digital Surface Sensor Module, reference MT-144, sold by Sakaguchi E.H VOC Corp (Japan), set on the keratin fibers. Normally, the probe is set on a single keratin fiber. However, it is advantageous that the probe be set on the part of the keratin fibers which directly contacts with the occlusive space, and more preferably, the probe be set on the part of the keratin fibers which directly contacts with the occlusive space and forms the curl end of the keratin fibers, if a curler is used. Preferably, the temperature is measured at atmospheric pressure of 101,325 Pa

According to the present invention, the temperature of the keratin fibers may be constant with a fluctuation of ± 2 or 3 °C over the head, if the keratin fibers are hair, of an individual, and the probe may be set on any type of keratin fibers.

If the keratin fibers are hair, according to the present invention, the constant temperature with a fluctuation of ± 2 or 3 °C can be obtained for any type of hair, and the temperature of the hair can be controlled to be constant ± 2 or 3 °C during the heating of the hair at a certain temperature. Thus, the hair style becomes uniform and homogeneous for the entirety of the hair, and a further excellent hair style can be finally obtained.

Advantageously, the coating means may comprise one or more thermal insulating materials, and more advantageously, the coating means may consist of the material(s).

The term "thermal insulating material" means any material which has an electric conductivity of from 0 to 1 W/m°C (PVC: 0.17 W/m°C). Preferably, the heating means may be adjusted such that the temperature measured on the keratin fibers is 50 °C or more, more preferably 55 °C to less than 150 °C, and further more preferably less than 100 °C. It is preferable that the heating be performed by heating via electrical resistance. Advantageously, the coating means is impermeable with regard to the cosmetic composition used in the step b).

In the above embodiment, at least one of the reshaping or mechanical tensioning means and at least one of the covering means may include a heater.

In the above embodiment, "occlusive space" means that when the coating means is placed on the reshaping or mechanical tensioning means, or vice versa, they together form a closed structure in which heat can diffuse, but heat cannot diffuse out of or is difficult to diffuse out of the closed structure. It is preferable that the coating means and the reshaping or mechanical tensioning means can form the occlusive space when they are set on the head, if the keratin fibers are hair.

The occlusive space may form a condensation cage in which water and a component or components in the cosmetic composition used in the step b) may evaporate from the keratin fibers, adhere to the wall of the coating means, and drop onto the keratin fibers. This cycle may be repeated during the heating of the keratin fibers. Thus, the keratin fibers can be always kept wet, and drying and deterioration of the keratin fibers will be prevented.

The formation of the occlusive space is an important characteristic of the present invention, because the keratin fibers in the occlusive space can be kept wet and the temperature of the keratin fibers can be kept constant. Preferably, the process of the present invention may comprise an additional step of tightening the coating means on the head of an individual, if the keratin fibers are hair, by an elastic cord, an extensible band, or a stretch.

According to the process of the present invention, because of the occlusive space in which the cosmetic composition can be continuously condensed on the keratin fibers, the amount of a cosmetic component or components in the cosmetic composition is advantageously reduced as compared to the processes in the prior art. The amount of each of the cosmetic components may be from 0.3 to 3 wt% of the composition.

In a preferred embodiment, a coating means may be placed on each hair curler as the reshaping or mechanically tensioning means, if the keratin fibers are hair. In other words, each of the hair curlers, if two or more hair curlers are used, may be covered individually by a coating means. It is advantageous to cover each hair curler because leaking to the scalp of the cosmetic composition which has been applied onto keratin fibers in the step b) can be prevented.

In another preferred embodiment, a coating means may cover all hair curlers, if two or more hair curlers are used. In other words, the coating means may cover the entirety of the head if the keratin fibers are hair.

Advantageously, the occlusive space formed in the step d) may be maintained during the step e). In other words, the coating means may be removed only after the step e) or after the stopping of the heating in the step e).

If necessary, the cosmetic composition may be applied to keratin fibers before applying mechanical tension to the keratin fibers. It may be possible that the keratin fibers are left as they are for a certain amount of time, if necessary, before and/or after applying mechanical tension to the keratin fibers, before and/or after applying the above-described cosmetic composition to the keratin fibers, and before and/or after heating the keratin fibers.

After the above step e), if necessary, the keratin fibers may be fixed by oxidation after being taken out from the coating means. (Products)

The present invention also relates to a cosmetic composition for treating keratin fibers, possibly under mechanical tension, to be heated in an occlusive space, comprising at least one reducing agent in an amount of from 0.01 to 10% by weight relative to the total weight of the composition and at least one source of ion(s) of the formula:

wherein

X is a group selected from the group consisting of O ^' , OH, N¾, O-OH, and O-COO ^" in an amount of from 0.01 to 10% by weight relative to the total weight of the composition.

This composition may not need to be used in combination with an oxidizing agent which is used in a conventional permanent deformation of keratin fibers, in particular hydrogen peroxide. Therefore, if keratin fibers should be permanently deformed, the cosmetic composition may be used in one step, whereas two steps (reducing step and oxidizing step) are necessary in the conventional permanent deformation of keratin fibers.

This composition may have the same technical features as those of the composition described above.

The present invention also relates to a kit for treating keratin fibers, comprising:

a device comprising

at least one coating means to form an occlusive space, and

at least one heater to heat the keratin fibers in the occlusive space;

and

a cosmetic composition comprising at least one reducing agent in an amount of from 0.01 to 10% by weight relative to the total weight of the composition and at least one source of ion(s) of the formula:

wherein

X is a group selected from the group consisting of O ^" , OH, N¾, O-OH, and O-COO ^" in an amount of from 0.01 to 10% by weight relative to the total weight of the composition. The coating means and the heater, as well as the cosmetic composition in the kit, may be the same as those described above.

EXAMPLES The present invention will be described in more detail by way of examples, which however should not be construed as limiting the scope of the present invention.

The following compositions were prepared (active ingredients in wt%). Composition 1

Composition 2

Composition 3

Composition 4

Composition 5

COMPARATIVE EXAMPLES 1-2 and EXAMPLES 1-3 Comparative Example 1 Composition 1 was applied for 15 minutes on a 1 g Japanese hair swatch previously wrapped on a 1.7 cm perm-roller. Then the perm-roller was covered by a plastic film and plugged on a Digital Perm Machine (Oohiro, model ODIS-2). After the heating process at 90°C for 15 minutes, the hair was rinsed and dried.

Comparative Example 2

Composition 2 was applied for 15 minutes on a 1 g Japanese hair swatch previously wrapped on a 1.7 cm perm-roller. Then the perm-roller was covered by a plastic film and plugged on a Digital Perm Machine (Oohiro, model ODIS-2). After the heating process at 90°C for 15 minutes, the hair was rinsed and dried.

Example 1 Composition 3 was applied for 15 minutes on a 1 g Japanese hair swatch previously wrapped on a 1.7 cm perm-roller. Then the perm-roller was covered by a plastic film and plugged on a Digital Perm Machine (Oohiro, model ODIS-2). After the heating process at 90°C for 15 minutes, the hair was rinsed and dried. Example 2

Composition 4 was applied for 15 minutes on a 1 g Japanese hair swatch previously wrapped on a 1.7 cm perm-roller. Then the perm-roller was covered by a plastic film and plugged on a Digital Perm Machine (Oohiro, model ODIS-2). After the heating process at 90°C for 15 minutes, the hair was rinsed and dried. It was clearly noticed that the composition had no odor.

Example 3

Composition 5 was applied for 15 minutes on a 1 g Japanese hair swatch previously wrapped on a 1.7 cm perm-roller. Then the perm-roller was covered by a plastic film and plugged on a Digital Perm Machine (Oohiro, model ODIS-2). After the heating process at 90°C for 15 minutes, the hair was rinsed and dried.

A curl retention test was performed on the curled hair described in Comparative Examples 1-2 and Examples 1-3. For that purpose, the hair swatches were kept under straight constrains for 5 hours at 40°C under a 95% relative humidity. The curl long-lastingness was evaluated by comparing artificial shape before and after this curl retention test. The results are shown in Table 1. Table 1

++: very good curl efficiency or very good curl retention

+: good curl efficiency or good curl retention

-: low curl efficiency or low curl retention

Table 1 shows that the present inventions can provide better curl efficiency and curl retention effects.